Document NEjxqVv7azXm38OkvDnZoR4GV

U.S. DEPARTMENT Of COMMERCE National Tacttaical Infomation Strvica PB-253 110 AN APPRA SAL OF TESTS AND STANDARDS FOR THE EVALUATION OF ELECTRICAL INSULATING FLUIDS National Bureau of Standards PREPARED FOR Energy Research and Development Administration 14 May 1976 HONS 0H7135 K. J r~ KEEP UP TO DATE \ Between the time you ordered this report-- which Is only one of the hundreds of thou- sends in the NTIS fnformetlon coilectlon avail able to you--and the time you are reading this message, several new reports relevant to your interests probably have entered the col lection. . Subscribe to the Weekly Government Abetrecta series that wilt bring you sum maries of new reports as toon as f/iey are received by NT/S from the originators of the research. The WGA's are an NTIS weekly newsletter service covering the most recent research findings In 29 areas of Industrial, technological, and sociological Interest-- Invaluable Information for executives and professionals who must keep up to date. 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At TilOH(S) ' . PKH1 OKUINII ORGANIZATION NAMF AND ADDRFSS NATIONAL IUREAU OR STANDARDS DEPARTMENT OR COMMERCE WASHINGTON O.C. 2021* (2, SfKirnoHnji Ovftdfi<?.*rioa Nam mJ Addrfin City, 5ftp, ZIP) Energy Research and Development Administration 20 Massachusetts Avenue Washington, D.C. 205^5 IS. SUl'Pl.liMENTARY NOTKS . 'PB253110 S. I'ublit niiun May 14 r 1976 4. Pt'larffiaji 0*niH(i,m (mJ. 1. Pcrluffliini Ornn. Rcpyit N.> HBSIR 76-105li TO. PTMji-u/T.,k/*(vS lhn ftp. 2110506 H. CdMrici/GtiAi No. tj. . Trp* of Rrpi Co*crtd A H.imk) Final 14* Sponsoring Agency Codv >4. APSTRACT */(A iOO- ward at Ian lattual mammary matt alfilflcmt Mlammallan. II iatumanI Inclvdat a il0,IUc*nt HbUottapIty or Uiatalara autray, attrition It harm,) Based on a literature study and interview with representatives of the electric utility industry, manufacturers of insulating fluid* and electrical apparatus, government regulatory agencies, organisations preparing standards and codes, trade associations and Independent testing laboratories, the status of existing standards and test procedures for Insulating fluids Is reviewed. Askarel-type transformers and capacitors are described and the characteristics of several currently-used as well as new candidate insulating fluids are given. The possible impact of codes and government regulations on the Introduction of new fluids Into use Is reviewed. Needs for new or revised test procedures and standards are noted and recommendation* made for research and development efforts as well as administrative actions to facilitate the qualifying of new ineulatlng'^lulda as acceptable replacements for tbe askarels currently In use In a certain class of transformers end capacitors..,. MQNS 0^7138 17. KLY VOKDS flit to order. cipftifilt only Af Aral toller pi tfi first kty wont imtm a proper narra; fry iimlcoJoniJ Askarel; capacitors; insulating fluids; liquid insulators; polychlorinated biphenyls] trtn.foracra JUGS SUBECT TO CHANGE II. A\AILA0IUTY Qf UitUeiiod If. SECURITY CLASS (THIS REPURT) ,1' ufi oe PAGES Ko Official Ontfibuiior. Do Not ftaltaac to NTIS Q Orjff From Sup. of Due., U-S. Co#rrna*nt Printing Offitt ' lighinaton. U.t . ?010I. RD Cmi. No. CM ErOnfer N*hom*1 Technic*! Information Service (NTIS) SpfngiifM. Vjfgfn,# JJMl * |t UNCLASSIFIED 20. SECURITY CLASS (THIS PACE) unclassified *' ~' - , IJ *yiCOMM-PC 1.0" " NBSIR 76-1064 AN APPRAISAL OF TESTS AND STANDARDS FOR THE EVALUATION OF ELECTRICAL INSULATING FLUIDS Electricity Division Institute for Basic Standards National Bureau of Standards Washington, D C 20234 May 14. 1976 Final Report Prepared for Energy Research and Development Administration Electric Energy Systems Division Contract No. E(49-1B| - 2062 / vN U.s. DEPARTMENT OF COMMERCE, EIHot L Rloherdeon. Secretary James A. Baker. Ill, Under Secretary Dr. Betsy Ancker-Johnson, Aswittmt Secretary for Sofmeo and Tothnatopy NATIONAL BUREAU OF STANDARDS, Imeel AmHer, Aetirtf Dkootor (0/ MONS 0*>7 13*S AW APPRAISE OF TESTS AND STANDARDS FOR THE EVALUATION OF ELECTRICAL INSULATING FLUIDS David B. Hiller, Principal Investigator, Purdue University, Consultant to Electricity Division, BBS; Vincent I. Bower, F. Ralph Kotter and Oskars Petersons, Electricity Division, NBSt and Merritt M. Birky, Clayton M. Huggett and AndreJ Macek, Fire Science Division, NBS qi7 V1*0 *Q*S it Table of Content# 1. Summary - 1-1 Introduction 1.2 Appraisal and Recommendations 1-3 Acknowledgments 2. Status of Test Techniques and Standards for Rev Insulating Fluids -- A Summary 2.1 "Askarel-class" Transformers 2.2 "Ask&rel-clasa" Capacitors 2.3 Available Insulating Fluids 2.3.1 Fluid Characteristics 2-3*2 Test Techniques and Standards 2.3*3 Flammability 2.3*1* Toxicity 2-3*5 Degradability 2.>4 The Scope and Influence of GovernmentRegulations 2.5 The Scope and Influence of Insuranceend Fire Code Regulations 3. Appraisal and Recoanendations 3.1 Electrical Teats on Fluids 3.2 Flammability Testa for Hew Fluids 3.2.1 Flash and Fire Points 3-2.2 Oxygen Index 3.2-3 Autoignition Teste 3.2.b Spray Flasssabillty Tests 3.2.5 Arcing Tests 3.3 Toxicity Tests on Fluids 3.3.1 Appraisal 3.3.2 Recommendations 3.It Recommendation on Degradability andBiodegradability TestB 3.5 Insulation System Tests and Standards --Transformers 3.5.1 Insulation System Tests 3.5.2 Standards -- Transformers Page 1 1 2 9 9 10 10 10 11 11 12 13 lit 15 17 17 19 20 21 21 21 22 22 22 2k 25 26 26 28 it- HONS 047141 Section 1 Summary 1.1 Introduction Askarels, the principal constituents of which are polychlorinated biphenyls (PCBs), have been used for over forty years as insulating fluids in power capacitor and flame proof transformer applications. However, recently they have come under close scrutiny and criticism because of suspected toxicity and long persistence in the environment. Large scale use of PCBs has now been restricted to electrical equipment applications under stringent controls to prevent accidental spills. As a result of these concerns and the possibility of further restrictions being placed on the use of PCBs, alternative fluids are being considered; however, so far none has gained general acceptance. Among the factors impeding the acceptance of new fluids are the coat considerations d the excellent electrical properties of PCBs. Besides these maj or fac. rs, it was felt that lack of adequate test procedures and test-related performance standards for the evaluation of new fluids did present an impediment to their acceptance. For example, the question was asked; Are the existing flanability performance requirements and ` the associated tests realistic in terms of fire risks! Of equal concern were tests and requirements regarding toxicity and degradability of the material in the environment. Could one arrive at concisely defined yet meaningful requirements for these properties coupled with a comprehensive set of tests and measurements! In the early part of 197i the National Bureau of Standards was approached by the Energy Research and Development Administration concerning standards for testing new nonflansable insulating fluids for transformers and capacitors. The objective was to detail in a report or position paper the test methods and standards and the test-related research and development required to facilitate the evaluation and qualifications of new insulating fluids for distribution transformers and power capacitors. In the study leading to this report the authors attempted to find answers to the type of questions mentioned above and to identify test-related roadblocks to the acceptance of new insulgting fluids. The material for this report was gathered in literature reviews and interviews with representatives of the electric utility industry, manufacturers of insulating fluids and electrical apparatus. Government regulatory agencies, organizations preparing standards and codes, trade associations, and independent testing laboratories. The resources and the time frame of the project were such that not every test for the properties of insulating fluids could be examined in detail--American Society for Testing and Materials (A8TM) standards (see Appendix A.3.2) list about 10 properties--nor do vs believe that such an examination would have been desirable snd cost effective. Instead ve took the position of responding to problem areas as brought to our attention by numerous personal contacts. The status portions, Section 2 and the Appendix, review the existing test procedures and standards for insulating fluids. They also describe the askarel-type transformers and capacitors and stress the interdependence between the insulating fluid and the rest of the device. 1 HONS O*?!**2 To illustrate the properties of inauleting fluids and trends in the fluid development, several existing and proposed insulating fluids are described. Finally, since a nev material introduced in commerce must meet the requirements of numerous codes and Government regulations, an outline of these is provided at the end of Section 2, with details In the Appendix. The appraisal and recommendations are the authors' considered opinions. In Section 3 ve comment on the entire field of testa sad standards without firm suggestions for a division of the recomended future work among the industrial, trade organisation, or public sectors. In 1.2, we emphasize those areas which would benefit from public support. Admittedly, the public and industrial responsibilities cannot be always clearly delineated. During this investigation we ware frequently close to the PCB controversy. However, our scope and objectives did not include the evaluation of merlta and deficiencies of FCBs; we do not pass Judgment in this area. Similarly, although several potential replacement fluids are mentioned in the report, ve offer no firm conclusions regarding the availability and suitability of replacements. The identification of commercial materials and their sources tn this report ia made for illustrative purposes only. In no case does this identification imply recommendation by the national Bureau of Standards, nor does it imply that the materials are the best available. 1.2 Appraisal and Recomendationa In this part of the report ve sum&rize our most important conclusions, our appraisal, and our recomendationa for future action. Not all our findings are abstracted here; for a complete appraisal the reader ia referred to Section 3 of the report. The flavor of some of the complex aspects of the problem, such as toxicity and Government regulations, can only be obtained by reading the pertinent parts of the entire report Including the appendix. The aumarized recomendations here are mostly those which va. feel warrant the consideration of public support; they are emphasized for the convenience of the sponsor of this study. Ve are now convinced that the problem of Impedimenta to the acceptance of new fluids la, with only minor exceptions, not associated with formalized teat procedure! aa prescribed by standards docuaents and the associated measurement technology. The U.S. system of voluntary standards is sufficiently flexible to provide for ad hoc exceptions if such exceptions ars warranted. On the other hand, compulsory codes and regulations based on the characteristics of specific existing products rather than on required performance present serious handicaps to progress. While simple laboratory tests on the insulating fluids themselves can be performed using standard procedures, these alone do not suffice for evaluation of the fluid. Essential tests on models and prototypes in advanced stages of development are not readily standardized. 2 HONS 0<t71<3 The latter, however, are eaeential since ultimately the fluid must be qualified in the enviroroMnt Imposed by the equipment. Adverse inter actions among various components of the equipment, rather than an isolated fluid property, may be the real barrier to the acceptance of a fluid. The problems with such system tests are threefold: (l) the test technology and procedures may not be available; (2) the tests may have to be tailored to individual insulation systems; and (3) the tests are very costly. Finally in certain areas such as toxicity, uniform test protocols may not be desirable because of the complexity of the system and required responses. One must accept a lengthy set of experiments in the process of evaluation. Because of the above concerns, ve did not restrict the Investigation t standardised tests and the related measurements, but considered broader spectrin of experimental procedures and regulatory constraints associated with the introduction of new fluids. At its conclusion we see this atqdy as having confirmed the existence of a need for the developaient of additional tests and standards. While for meeting some of these needs the course of action appears clear, for others it does not. Within ths scope of our investigation the moat significant roadblocks appear to be in the flaanability area. The problem lies with the building codes and fire regulations and the lack of a simple procedure for evaluating the risk in actual firs situations. Currant codes and regulations dsallng with the flammability specifications for insulating fluids rtfsr only to specific chemical families--mineral oils and askarels and thus tend to exclude new developments. Furthsrmors, it appears that in some cases flammability performance evaluations are being made with greater consideration given to the properties of ths liquids currently in use than to established criteria of operating and environmental conditions and the fire risks involved. It is highly probable that replacements, dictated by environmental considerations, will have poorer fire resistance properties than the askarels. The problem is to determine how much relaxation of the flsambility requirements may be possible without Introducing undue risk. It Aecomended that Atieonch be conducted in an attempt to develop (tamabititif peAfoAmance CAlteAia (oa new {tuicLi. This work should consider the analysis of past accidents, the environment in which the equipment operates and the failure modes. This research activity must have a strong input from ths insurance industry, Underwriters Laboratories, and personnel from the National Electrical Code Conmittee. The results, if to be of benefit, must be usable in preparation of code revisions. 3 HONS 0471^4 The laboratory teata for Initial screening of material*--flaab and fire point and autoignition teata--appear generally aatiafactory. However, they are teata of relative flammability and not true indicatora of fire safety involving large acale equipment failurea. In the past, the definitive teata for fire safety have been the arc teata involving actual prototypea. Thia is not a aatiafactory atate for the introduction of new fluids since the entire fluid and equipment development procedure must be carried out before the teat can be conducted. Beaides the development coata, the test Itself is very expensive. It would be highly desirable to arrive at a realistic fire-aafety teat procedure using small models of the insulation systems, not necessarily acaled down actual devices. Since actual failures follow electrical arcs and energy releases, arc tests appear promising. They are little explored, > but whatever little has been done in this area haa attracted vide interest. TfuiA ouA itcond necoimnendation in the eUiea {icumCLbillty testing ii io>t the development o( a test tohieh Mould be a nialUtic indicate* o iine kazeuvd. The test involving an arc in a simulated insulation system appears promising. Since any new test has to be implemented in practice through code revisions, interaction with the previously mentioned groups is essential. Questions have been raised about the lack of a quantifiable definition of flammability; indeed the term is largely used in a qualitative and relative sense. We believe any improved definition of flammability of insulating materials, although still relative, must follow the development of an improved test procedure. Whether or not the Insulating fluid passes the test will qualify it as nonflammable or flammable. Potential toxicity is of great concern in the introduction of new fluids. The underlying characteristic of this area revealed in our study is its extreme complexity. Relatively short tests with well defined measurements such as those employed to determine physical properties do not apply here. Inatead, lengthy and numerous experiments must be performed on animals. Ar*examples of the complexity of the subject, a reference work, cited in this report, mentions 27 different organs in which responses can be specifically identified; 22 different routes of administration; and finally 23 levels of animal preference. There are several definitions of toxicity but relatively few standard experimental procedures for determining the toxicity of a new chemical. The attempt to develop a standard set of protocols for routine assessment of the toxicological hazard of a new insulating fluid or any chemical has several dangers that must be recognized: (l) it may laad to unnecessary tests for certain substances; (2) it may fail to ask questions which are of overriding significance; (3) in view of the multiplicity of possible biological systems, it may be wasteful; (It) in view of the multiplicity of responses, some of which may require a long time before the effect can be observed, such testing cannot guarantee the complete safety of a new chemical. It HONS 047145 Two type* of tuti, Aibu oiuf eivtoiUc A-Cwfiw, oki suggested In tkU xtpoxt jo* nputim taxLy cnetning of mJUaIaJU. u believe the early toxicological screening belongs with the development of the Insulating fluid. The fluid manufacturers are either avare of or are studying toxicity of their materials. As the developnent of the fluid approaches the time when there is reasonable probability of actual use. It would be desirable to conduct i^artial, critical and in-depth appraisals of the manufacturer's toxicity data, We Kttoimtnd that independent apputliali of, the toxicity data be iporUoKtd. We favor then since such appraisals will minimise the chances of discovering adverse effects years after the Insulating fluid has been established in commercial use. The degradability of insulating materials in the environment is also a complies i but even a less explored subject than toxicity. The process by whic i substance degrades to naturally occurring compounds may be biological, chemical, or physical. The subjects of toxicity and degradability arc often Interdependent; for example, rapid degradability Implies that the substance is highly reactive and therefore perhaps toxic. In dealing with the question of degradability, the following aspects are Important: the rate of degradation, toxicity of the degradation products, and acciamilation of the original substance and intermediate degradation products in living organisms. There are no standard degradability tests for the electrical insulating fluids, although individual manufacturers have performed experiments on their products. One industry group which has been successful in developing s standardised test for biodegradability, including a definition of what is mesnt by biodegradable, is the Soap and Detergent Association, Their succses has lead us to believe that an attempt to develop a similar procedure for insulating fluids would be a worthy endeavor. Thai, we Ktaoimend AtitaAok to txploKt the development of itandoJuiLzed degradability evaluation procedure*. In the electrical and other areas ve see no major deficiencies in the laboratory type of'bests on insulating fluids. Thers are several minor problems mentioned in Section 3. These concern the typee of cells used for breakdown tests', possibly inadequate tests for moisture content of new fluids; specifications and significance of corona inception and extinction levels. We feel the situation is different for the tests in the more advanced stages of equipment development during which insulation models and proto types are evaluated. Of concern is the stability of tbe insulation system, and how it Is affected by interactions among various components. Such interactions may degrade the insulating properties of the fluid and reduce the life expectancy of the apparatus. An important cause of failure is corona, but there are other factors contributing to Insulation deterioration. It could be argued that tests at this stage are the sole responsibility of the developer of a particular apparatus. We believe, however, that guidelines to uniform system testing would accelerate tbe introduction of new fluids. Having well developed and verified guidelines would 5 MONS Qb 7146 reduce the cost of insulation system evaluation and would facilitate the comparison of results of competitive systems, and the availability of carefully-performed and well-documented results of a validated test will mitigate user reluctance in accepting a new product. Tests in accordance with such guidelines would be expected to uncover possible deficiencies which could cause expensive, unexpected failures at a future date and possible withdrawal of the product. CotUt^uentiy, Ktcormind Kt&eaAch leading to the development o{ {oAmat guldtLintt (o*. tAam^oAjneA and capacitoA inau.lotion iyiten tUti. The long-term performance of an insulation system is often determined through accelerated aging procedures. To arrive at a valid accelerated test, the basic mechanisms of failures must be understood. A study in the basics of insulation failures, as they affect testa, would be desirable. Finally, we consider the effect of published voluntary performance standards, compulsory building codes, end Government agency regulations. These do slow down the process of introduction of new products, if for no other reason than because of multiplicity of requirements which must be considered. Sometimes these requireswnts are ambiguous and conflicting. The impediment is very severe if the codes and regulations recognise only certain specific products. The process of preparing voluntary -standards could be accelerated by encouraging greater user and third party participation in comlttees. This objective could be partly achieved through allocation of a special fund for these purposes. A close liaison should be maintained between the Energy Research and Development Administration and Federal and State regulatory agencies through flow of information in both directions, participation in meetings, and assis tance in project reviews and steering. We Kecowntnd incxemed inttxdepaAtnentat coordination oj \egutatO\y activity. A task force consisting of members of concerned agencies charged with a minimum duty of keeping each other informed would alleviate problems in this area. If the task force could then become the focal point for coordinating the specific actions of the agencies which Impinge on the electrical power industry, and.thus become a center to which the industry could look for guidance, it would be of even greater value. 1.3 Acknowledgments This report is based on information gathered from a large number of sources, and in particular from meetings with many Individuals and groups who are involved in one way or another with insulating fluids. We wish to express our appreciation to these groups, listed below, who very willingly supplied their time, information, and suggestions in order to best meet the stated objectives of this study: Government Regulatory Agencies Environmental Protection Agency (Water and Hazardous Materials Group, Office of Toxic Substances, Environmental Monitoring Laboratory, Environmental Research Laboratory); Department of Health, Education and 6 HONS Qh?lh7 Welfare (Food and Drug Administration, Rational Institute for Occupational Safety and Health, Public Health Service); Department of Labor (Occupational Safety and Health Administration); Department of Transportation (Federal Railroad Administration, Urban Mass Transit Authority); Department of Natural Resources, State of Michigan; and Department of Natural Resources, State of Wisconsin. Manufacturers Dow Chemical U.S.A.; Dow Corning Corporation; Electric Utilities Company; Exxon Research and Development Company, Corporate Research Laboratories; General Electric Company (Transformer Laboratory Operation, Capacitor Products Dept., Research and Development Center, Environmental Protection Operation); McGraw-Edlson Company (Power Systems Division); Monsanto Industrial Chemicals Company (Specialty and Process Chemicals Division); RTE Corporation; and Westinghouse Electric Corporation (Transformers Divisions, Research and Development Center). Electric Utilities Coamonvealth Edison Company; Consolidated Edison Company; Kansas City Power and Light Company; Potomac Electric Power Company. Standards Organizations, Trade Associations and Testing Laboratories American Society for Testing and Materials; Edison Electric Institute; Electronic Industries Association; Factory Mutual ftigineering and Research; International Association of Electrical Inspectors; Manufacturing Chemists Association; National Electric Manufacturers Association; and Underwriters Laboratories, Inc. The authors thank J. E. Cunningham for typing the manuscript, including numerous drafts, under tight deadline conditions. We also acknowledge with thanks the contributions of M. G. Broadhurst and C. G. Malmberg of the Polymers Division, NB8; F. L. Hermach and R. S. Turgel of the Electricity Division, KBS; W. H. Kirchhoff of the Office of Air and Water Measurement, NBB; and G. Carlson, Department of Toxicology, Purdue University, in critically reviewing sections of the report. HONS T Section 2 Status of Test Techniques and Standards for Rev Insulating Fluids -- A Summary "Askarel" Is a generic tern for a class of fire-resistant, synthetic, chlorinated hydrocarbon fluids used by the electric industry for insulation in capacitors and a certain class of transformers. Their "fire resistancegood heat-transfer and non* sludging characteristics and their high dielectric constants nake these fluids particularly attractive for these applications. The industry has grown accustomed to the particular features of the aakarels over the bO-odd years they have been available and many standards and operating guidelines have been developed in the light of their specific characteristics. It le the purpose of Section 2 to review in a summary form the status of existing standards and test procedures for insulating fluids as they relate to the new fluids being proposed as replacements for the askarels (the Appendix contains detailed background material). In reviewing the available procedures, the reader should keep in mind not only the applicability of given procedures to new fluids, but also the adequacy in the face of today's-much more complex and stringent requirements on electrical materials and apparatus. Reliability, fireresistance, nontoxicity and minimum environmental impact demand far more in the way of materials and apparatus testing than was required when aakarels were Introduced. It is an appropriate time, therefore, that the adequacy of Insulating fluids teet techniques and standards be reviewed. In this section, background on the requirements of askarel-lnsulated transformers and capacitors is surveyed in order to identify the operational requirements which new fluids must fulfill within the apparatus environment. Fluids characteristics themselves are then investigated. Finally, existing constraints due to governmental regulation and fire codes are explored to reveal possible additions and changes which might be required in this area to accommodate new fluids. 2.1 "Askarel-class" Transformers Specifications for transformer askarels (proprietary blends of polychlorinated biphenyls (PCBs) and other ingredients) are given in ASTM Standard D 2203-73. The fluid is enclosed in a metal tank, and the transformer windings are completely immersed in the fluid. Askarels are used as the insulants in transformers where the fire resistant , characteristic Is particularly important, These uses include utility and industrial distribution service, where the transformer serves a heavily concentrated load in an urban, commercial or industrial area and where the transformer must be in close proximity to populated buildings. Electric railroads and many electrostatic precipitators also use fireresistant transformers. 0 HONS 04 7 14 9 The fire resistant quality of the askarels Is due. In part, to the nonflammable gas, mostly hydrogen chloride, vhlch Is produced when the fluid le subjected to arcing or high temperature. This gas Is also corrosive, and scavengers muet be ueed to absorb email amounts of hydrogen chloride produced In normal operation. Transformer rooms or vaults mutt be adequately vented to prevent build up of 1C1 vapor, and any leaking or spilled askarel must be contained because of Its toxic and environmental problems. The transformer fluid could be spilled during manufacture, transport, processing, filling, normal operation, service failure, repair or disposal of the transformer. Guidelines have been Issued for proper handling (ANSI1 C107,l-197h; IEEE2 76-197M. Spilling during service most often results from an internal arc causing the transformer tank to rupture. The arc generally starts as a small discharge, and pressure builds up slowly; a pressure relief device, If present, prevents failure from this type of malfunction. Small discharges, however, may grow rapidly to high current arcs. The resulting pressure wave then builds too fast far a pressure relief device to operate. Although a current-limiting fuse can be used to reduce the magnitude of the pressure wave, the tank must be made exceptionally rugged to withstand this condition. Because of intensive*prevent!ve programs, users report very low (0.01 to 0.02$) yearly tank rupturing failures. In spite of tbe low failure rate, indoor mineral-oil insulated transformers are installed In fire-proof vaults in accordance with National Electrical Code recommendations. Vault requirements apply to all mlneral-oll insulated transformers and to askarel-lnsulated transformers rated over 35,000 volts. The flre-reslstance of a transformer fluid muBt ultimately be determined by testing a complete transformer. The askarels were originally qualified by such tests conducted by Underwriters Laboratory. More recently, RTE Corporation has run a set of demonstration tests comparing mineral oil, askarel, silicone fluid, and an RTE proprietary material "RTemp." In this test, the three newer materials were shown to be less flammable than mineral oil; this test could form the foundation for a more rigorously controlled and Instrumented standard test of transformer Insulating fluids. When considering alternatives to mineral oils or aekarels in transformers, in addition to the obvious electrical and thermal properties the following special characterises will have to be considered before a new fluid can be consldared to qualify: material compatibility, ability to impregnate the solid insulation used, hydrolytic stability, fire safety, toxicity and environmental impact, ' Standards for external protection of transformers with new fluids should also be considered; this Includes fusing, circuit breakers, and vault requirements. A large number of standards exist which guide the selection and handling of mineral oil end askarel In transformers. These are listed in A.1.5: presumably similar standards for new fluids would eventually be required. 1American National Standards Institute institute of Electrical and Electronics Engineere 9 HONS 047150 2.2 "Askarel-class" Capacitor* A large percentage of liquid-filled electrical capacitors use askarels as the dielectric fluids, primarily because of their relatively high dielectric constants and the fact that they are approximately equal to the dielectric constant of readily available paper insulation. Their good electrical insulating and stability qualities also make then attractive for capacitors. Although not a prime requirement for large pover capacitors, the fireresistant feature of askarels is also a significant advantage. The fire resistance appears to be important In certain types of snaller ("industrial") capacitors, such as those uaed in conjunction with fluorescent lights and appliance motors. There Is an Interdependence of the transformer and capacitor askarel manufacture which should not be overlooked in considering the economics of substitutes. Capacitors generally fall by an internal arc destroying the electrical insulation. The arc will also often rupture the capacitor tank. Capacitor reliability is generally quite good, with yearly failure rates being less than one-percent. In addition to the special characteristics noted as important in the case of candidate replacement fluids for the askarels used in transformers, the fluids for use in capacitors must possess high dielectric constants. The ease with which the solid insulation can be fully impregnated with the liquid is even more important in the capacitor application. Existing standards for capacitors are described in A.2.5. These deal with the fluids themselves (specifications, acceptance, handling, disposal) sad with the requirements of the total capacitor. 2.3 Available Insulating Fluids 2.3.1 Fluid Characteristics We have described several available new fluids in A.3.1 of the Appendix. For the sake of completeness, descriptions of mineral oils and askarels are also Included. A listing of these substances including their principal properties follow. The askarels are mixtures of polychlorohiphenyls and chlorobenzenes with additives. These liquids have excellent electrical properties and are highly stable,but evidence of their toxicity has developed* Their excellent stability has given them high reliability on the one hand, but also given them the disadvantage of poor degradability in environment. Silicone liquids (mixtures of dimethyl siloxane polymers) have good electrical properties (although the dielectric constant Is not as high as In the case of the askarels). They are useful over a wide temperature range, but are less fire resistant than the askarels and form solids during electrical discharge. They are high molecular weight liquids which appear to be relatively nontoxic. Mineral oils are mixtures of paraffinic (or naphenic) and aromatic compounds of petroleum origin with aromatic additives to prevant oxidation and 10 MQNS 047151 sludging. The electrical properties are satisfactory and the cost is low. Theae materials are flammable (see table p. 12). 'Their toxicity is low and results largely from the toxicity of additives. However, the additives are satisfactorily degradable. Hydrogenated paraffin oils exhibit characteristics similar to those of mineral oils except for higher flash points and consequently lower flansaability. Mixtures containing diaryl tulfones, particularly formulated for capacitors, possess high'dielectric constants. The liquids are somewhat flammable (see table p. 12 ), Their toxicity and elactrlcal properties are now being thoroughly investigated. They appear to be satisfactorily biodegradable. The phthalate esters are readily available in large quantities since they are now used extensively in the plastics industry. Their high dielectric constants (about 5) and othar electrical properties make them more attractive for capacitor than for transformer applications. They exhibit low toxicity and satisfactory degradability although their flammability characteristics (see table p. 12) represent some disadvantage, Butylated monochlorodlphenyl oxides have good electrical properties (dielectric constant about 5). and are being considered for capacitor use. They are flaanable (see table p. 72 ) The alight toxicity resulting from a minor component has been investigated. The fact that the offending component is biodegradable and that its degree of bioaccumulation is also low permits these to remain as candidate liquids. 2.3,2 Test Techniques snd Standards The standards relating to testing of insulating fluids are summarized in A.3.2. These refer to procedures for specific fluids (askarels, silicone fluids, insulating oils) and to specific test techniques independent of the particular fluid being tested. 2.3.3 Flammability fire and explosion are potential hazards in the operation of transformers and to m leaser degree capacitors and aince one outstanding feature of the aakarels is their low flammability, the flammability or "fire resistance" of potential replacement fluids must be evaluated. Flash and fire points are defined as the temperatures at which an ignition source will cause a transient and a continuing flame in the vapors of the fluid. These are the most, widely used measures of flammability. Closed and open cup methods for measurement of these parameters are described and discussed more thoroughly in A.3.1*.11 11 i HONS 047152 In the Section A.3.U on flanmablllty testing, severe! other tests are also described. The Oxygen Index (0.1.) Test is e frequently used technique in vhich the lovest combustion-supporting percent of oxygen In on oxygen-nitrogen mixture is determined. Soete limitations on the use of the 0.1. test are discussed. A heated atomized mist of the substance is sprayed into on open flame in the Spray Flaasability Test; this is a very severe test and has not been applied to any extent In evaluating the flammability of Insulating fluids. Another flaasability test Is the Auto Ignition (A.I.) Test, in vhich the temperature for spontaneous ignition is determined. This has been used for insulating fluids; the A.l. temperatures are generally quite high, veil above normal operating temperatures. The energy release during combustion of an insulating fluid is a very pertinent parameter elnce physical damage to the apparatus and its surroundings is the thing vhich one hopes to eliminate if combustion occurs. Energy release measurements have not been applied to insulating fluids, but in A.3.k suggestions are made tovard this end. A basic problem related to the flsanabillty issue is the general lack of a rigorous, quantized definition of "flemmability." We have used this term, and also such terms as "fire resistant" without ideally having an operationally useful meaning for them. Standardised, interpretable tests such as described above vill provide the data on vhich quantitatively meeningful definitions can be baeed. Tables in A.3.1 end A.3.V summarize existing flammability data for some of the available insulating fluids. 2.3.1* Toxicity The toxicity of the askarels has recently become a significant Issue, leading to severe restrictions on their present day use, and creating the intensified search for substitute fluids. The toxicity of each candidate replacement must therefore be an important parameter to evaluate before the liquid is put into widespread use in electrical equipment. Some reference is given to the toxicity of the various Insulating fluids in A.3.I. In A.3-5, toxicity determination techniques are explored. Perhaps the most important conclusion is that the toxicity issue is extremely complex. A variety of definitions of toxicity are presented in A.3.5, emphasizing that a fluid cannot merely be labeled "toxic" but that its specific toxic actions must be identified. Questions raised Include: At what dose level does any toxic response occur, and whet is the lethal dose? Is the chronic response to long-term, continuous exposure different from the acute response to a single large dose! A large variety of responses occur. Table C p. 66 indicates tbe variety of organs and systems in which responses can be specifically Identified, 12 MGNS 047153 including such thinga as akin, blood, nervous system and liver. Likewise, the reaponae can depend on the route of administration, e.g., orally or by inhalation; 22 different routes are identified in Table B p. 86 . Finally, the toxicity of a given substadee nay differ from one speciea to another; 23 levela of apecie preference are liated in Table A p J5 . The importance of continually improving chemical analysis techniques must be recognised in any attempt to establish definitions or protocols for toxicity. Gas chromatography and mass spectroscopy have, for Instance, greatly advanced analysis, both qualitatively and quantitatively, in recent years. The Rtgli&iy o$ Toxic. EfftctA of Chemical SukUancti, published by the National Institute of Occupational Safety and Health, is identified in A.3-5 as listing all chemicals which are documented as having shown any toxic effect in any species. The effect, dose, administration route, Bpecles and reference source are also given. A.3.5 also contains further governmental legislative and regulatory enactments which give operational definitions of toxicity. These include: The Federal Hasardous Substance Act, Department of Transportation Regulations, Occupational Safety and Health Administration Regulations, Food d Drug Administration Regulations, and Environmental Protection Agency Regulations. 2.3-5 Degradability Because of the highly stable nature of the polychlorobiphenyl molecule, the askarels which accidently or upon disposal reach the environment persist for long times; they are not biologically degraded in the manner or at the rate of most organic compounds. This persistence has amplified the toxicity problem and haa brought out the need to investigate the degradability as well as the toxicity of replacement fluids. . Degradation to sere simple, harmless, environmentally compatible compounds may occur due to natural physical processes or, as in the case of most organics, by biological processes. New compounds require testing for both types of processes. Silicones, for instance, do not biodegrade, but are shown to decompose to basic silica and water in the presence of solar (ultraviolet) radiation, air and water. Tests for biodegradability of potential pollutants Include the River-Die Away Test, continuous activated sludge tests and batch activated sludge tests. The Subcommittee on Biodegradation Test Methods of the Soap and Detergent Association have promulgated a standard sulfonate blodegradabllity test. The Biochemical Oxygen Demand (BOD) and the Oxygen Electrode tests are identified as useful biodegradation tests in the EPA Manual of Methods for Chemical Analysis. All of the above tests are described and referenced in A.3.6. 13 MONS 0A7154 2.1 The Scope end Influence of Government Regulation* In 2.3 above. Federal legislation and regulations were identified &s one source for definitions of toxicity. Ue return to these sources nov to examine the authority and procedures by which governmental bodies will influence the acceptance of new insulating fluids. More detailed examinations and referencing of these various lavs and regulations will be found in A.1*. The Environmental Protection Agency (EPA) has the following authorities from the Federal Water Pollution Control Act: 1. Prepare a list of toxic pollutants; criteria for selection, standards for allowed levels. 2. Assign oil and hasardous substance liability; regulations for reporting and clean-up of spills. 3. Establish pretreatment standards; standards for pretreatment of pollutants which could enter public treatment works. 1. Establish effluent standards; standards for allowed levels of discharge of each identified pollutant. 3. Issue pollution discharge permits; EPA may issue permits limiting the amount of discharge of specific pollutants from identified sources into navigable waters. Various versions of a Toxic Substance Control Act are also being con sidered in Congress. If this Act is passed it is expected that EPA will be given direct control of the use, as well as the discharge, of toxic substances. The Federal Food, Drug and Cosmetic Act empowers the Food and Drug Administration (FDA) to maintain safe levels of food quality in the United States. (Aider this authority, the FDA can regulate the use of poisonous ingredients in agricultural and food processing industries. In the specific esse of the PCBs, the FDA has issued regulations where PCB-contalnlng materials can and cannot ba usad. Thus, new insulating fluids may fall under FDA Jurisdiction if used when food contamination Is possible. Currently, PCBs are allowed in sealed electrical transformers and capacltora; prasumably theae regulations could be stiffened if and when replacement fluids come into generally accepted, covercial use. The Occupational Safety and Health Act directs the Occupational Safety and Health Administration (OSHA) to assure working persona safe and healthful working conditions. Hew Insulating fluids could fall within the Jurisdiction of this Act both during manufacture (of the fluid or the apparatus) and during use of the fluid-filled apparatus in a working area. The Secretary of Labor (through OSHA) la directed to issue standards for toxic substances and to inspect working places in order to enforce these standards. The Secretary of Health, Education and Welfare (through the National Institute of Occupational Safety and Health, NIOSH) is to carry out research and develop the criteria for establishing standards. 11 MONS 047155 HIOSH regularly updates its "Registry of Toxic Effects of Chemical Substances" (see Ref. 5*5 of A.3). This list, for Instance, specifically cites several "Aroclors" (a manufacturer's tradename for mixtures of PCBs), The list should be consulted for toxicity information on other candidate fluids. OSKA regulations have incorporated the vhole of the National Electrical Code, making this code, and specifically Its provisions on transformers and capacitor fluids, part of Federal lav. OSHA has also nov Issued draft technical standards on chloroblphenyls, Department of Transportation (DOT) regulations would have an Impact on new insulating fluids in two ways: 1. Control of the insulating fluid in transformers of electric railroad cars; the availability of a sufficiently nonflammable fluid must be recognized when considering a restriction on askarels in this application. 2. Control of the transportation of fluids; the transportation of hazardous materials falls within DOT'S authority. Class B poisons are defined in l*9CFR 173.3*3. Finally, ve mention that the Department of Health, Education and Welfare (HEW) has regulatory control of solid waste disposal through provisions of the Solid Waste Disposal Act. HEW is, for instance, to publish guidelines on solid waste recovery, collection, separation and disposal. Federally controlled disposal facilities are obligated to follow these guidelines. 2.5 The Scope and Influence of Insurance and Fire Code Regulations The National Electrical Code (NEC) is a guide to the safe Installation of electrieal equipment. It has been adopted, as is, or with modifications, as a pert of the legal building code by many state and local authorities. It has also been Incorporated Into the Federal Occupational 8afety and Health Regulations. The current edition of the NEC mentions only mineral oils and asharels for use as insulation fluldB In transformers and capacitors. Independent testing laboratories such as Underwriters Laboratories (UL) and Factory Mutual Engineering and Research (FM) will carry out testing of apparatus and issue an approval, indicating that the item meets NEC standards. UL has also published flaasaability ratings of materials. FM will issue an "acceptance" rating, indicating that a particular installation meets safety standards. These ratings are important in aiding the Insurance companies to decide whether a given installation should be insured. 15 0<t7l5b HONS Fire safety has always been a major concern associated vitb electrical apparatus, and it vill be particularly important In equipment using new fluids in place of the "fire-resistant" askarels, For building code and fire insurance protection, therefore, new fluids must be acceptable by fire code standards. Further details regarding insurance and fire code regulations will be found in the Appendix (A.?). HONS 047157 16 Section 3 Appraisal and Recossaendatlons 3.1 Electrical Teats on fluids It appears that existing specifications, standards and test procedures are adequate for dealing vith the mineral oils and askarels currently in use. While it does not seea feasible to propose a single specification which could be applied to old as veil as nsv candidate fluids for all applications, it does sea quite feasible to use at least most of the same electrical test procedures for all. So far as ve have befcn able to determine none of the current standard electrical test procsdures called out for insulating fluids actually act to impede the acceptance of nev fluids except perhaps indirectly. An example of this indirect impact is the situation with respect to dielectric breakdown tests dealt vith in two ASTM Standards: D 877 "Standard Method of Test for Dielectric Breakdown Voltage of Insulating Liquids Using Disk Electrodes" and D lfll6 "Standard Method of Test for Dielectric Breakdown of Insulating Oils of Petrolew Origin Using YDE Electrodes." These standards differ in that D 877 calls for a test cell having a small volume and an electrode geometry which provides a near-uniform field, whereas D l8l6 requires a substantially larger cell with electrodes which establish a uniformly decreasing*field about a maximum field point. The liquid in this larger cell is maintained in gentle forced flov between the electrodes. The D l8l6 procedure provides a test which is more sensitive to the presence of moisture in the liquid being tested and is less influenced by the contaminating by-products of previous breakdowns; however, it requires a significantly larger volvme of the test liquid. Either method can be used for testing the candidate silicone fluids; because of breakdown by-products, however, the specified alternative D 877 procedure which calls for refilling the test cell with new fluid prior to each breakdown test must be followed in order to obtain consistent results. The circulation of the liquid avoids this problem if D 10l6 is used. Thus with either procedure the volume of liquid required for the test is several times that required in a mineral oil or askarel test and the higher cost of the silicone fluid then appears as an indirect deterrent to its use. It should be noted thaC*poor repeat breakdown strength of a fluid alone does not necessarily mean poor repeat breakdown strength of the composite system when the fluid is used as the impregnant of a porous solid. ASTM Standard D 2It13 applies to such composite systems. Another indirect deterrent is the obvious requirement that the test fluid not be contaminated by chemical interaction with the smterials used in construction of the test cells. The commercially available cells which are inert to the mineral oils and askarels (and not all are inert to both) are not inert to all new candidate liquids. Still another indirect deterrent may be the fact that current standard test procedures for moisture content are not as satisfactory for silicone fluids or perhaps for other liquids as for mineral oils and askarels. These can only be considered as temporary impediments to the adoption of new fluids since prospective widespread use of any new fluid would soon lead to the development of test procedures suitably tailored to its peculiarities. MONS 047158 17 A characteristic of askarels which adds to their attractiveness as electrical insulating fluids is the behavior when partial discharges (corona) occur. With mineral oil and some other Insulating fluids, the partial discharge inception voltage is significantly higher than the extinction voltage. Thus a temporary voltage excursion which initiates the partial discharge may lead to a prolonged discharge period with a resultant degradation in the properties of the fluid. With askarels, the inception and extinction voltages differ very little so that temporary voltage excursions which lead to partial discharges are inconsequential. This characteristic of an askarel tends to encourage Its being specified as the insulating liquid. Recosnended test procedures relating to this characteristic exist.1 However, eince acceptable limits may vary from one application to another and from liquid to liquid, no universally accepted basis for judging the relative merits of new versus old candidate liquids in this respect is available. The lack of such a standard may be considered another "indirect" deterent to the adoption of nev fluids. The stability of an insulating fluid describes the permanence of its important physical and electrical characteristics in the operating transformer or capacitor. This is an extremely important characteristic since these fluids are expected to operate reliably and essentially unattended in long-service-life apparatus. Although bench tests on the fluids themselves to screen out obviously unsatisfactory candidates are essential, fluid must finally be qualified in the apparatus environment. Such tests are described in Sections 3.$ and 3.6. Within these tests are also Included suggestions for developing cleenlng and maintenance procedures for fluids in service. Finally, guidelines and standards must be developed for proper disposal of new fluids as they come into use. ANSI C107.1, guidelines for proper handling of askarels, would serve as a useful example. These guidelines would have to await quantitative determination of the toxicity and degradability of each nev fluid, and they would have to be cognisant of changing federal and local waste disposal regulations. institute of Electrical fc Electronics Engineers (IEEE) Standard #l5li-i973 "Recommended Practice for the Detection and Measurement of Partial Discharges (Corona) During Dielectric Tests" National Electrical Manufacturers Association (N1MA) Standard ICP-P2-1973 Official Standards Proposal "Test Procedure for Measure ment of Internal Partial Discharges in Capacitors" American Bociety for Testing and Materials (ASTM) Standard D 1868-73 "Detection and Measurement of Discharge (Corona) Pulses in Evaluation of Insulation Systems" 18 HONS 0<t7159 3.2 Flammability Testa for New Fluids Fire safety tests have been classified In a variety of ways [1.2].1 For our purpose, it is convenient to classify them as: (a) properties of materials tests (b) system tests (c) apparatus prototype tests. . Tests of the first class are small scale laboratory tests designed to measure an Intrinsic property of a material which is related to its fire performance, e.g., flash point or heat of combustion. Such tests are useful in developing a qualitative picture of the hazards associated vith the use of a material and for purposes of specification and quality control. They are relatively inexpensive and would be the first tests to be run on new candidate fluids. They do not necessarily predict the hazard potential of a material under actual use conditions. System tests involve the interaction of the material vith the environment and with other elements of the system in which it is Intended to be used. An example is the RTE Arc Tests (A.1.3). System tests attempt to simulate essential features of the device, and thus are less susceptible to standardization than property tests. They are usually larger in scale, require more careful planning and are relatively more costly than tests of component materials. Thus, they would find use in the latter stages of the development and qualification of new insulating fluids. Prototype tests involve the testing of ths complete device under conditions simulating actual use, for example, the Underwriters Laboratories Tests (A.1.3). Such tests can be very expensive, not only because of the cost of the test units and test operation but because most of the development costs of the device will have been incurred before the first unit is ready for testing. They should be undertaken only after a careful analysis of ths conditions under which the device is intended to function, the possible failure modes, and the type of information that is to be sought in the test. The purpose of flammbility tests and standards for insulating fluids is to reduce the probability of loss from fire incident to the use of these materials. In order to set realistic performance atandards and select appropriate test methods, it is necessary to know the properties of the environments in which these fluids will be used, the failure modes that occur, and the consequences of these failures. Ve have been unable to find any systematic compilation of such hazard information in the course of the present study. Consequently, the establishment of suitable flammability criteria for new candidate insulating flulda will at this time be based on Inadequate knowledge of the nature of the hazards which may be encountered. 1 Re Terences shown in brackets, are found in 3>8. 19 HONS 04 7160 Recommendation: It la reconmended that a systematic survey and analysis he made of the environmental conditions in vhich insulating fluids may be used and incidents involving the use of such fluids vhich result in fires or related loss. Current flammability specifications for insulating fluids apply to specific chemical families of fluids and vary from one type to another. This presents a barrier to the introduction of nev chemical types since they do not fit under existing specifications and there are no clear guidelines for acceptability. It appears that seme present performance specifications hsve been established with greater consideration given to performance levels which the fluid in question can readily meet than to the actual requirements of the application. Setting too high a requirement may result in the elimination of promising candidate fluids whose properties are entirely adequate for the intended application. The excellent flaoDabllity performance of the askarels has led to a very low incidence of fires involving these materials. It is highly probable that replacements for these materials, dictated by environmental considerations, will have poorer fire resistance properties than the askarels. The problem is to determine hov much relaxation of flaimsability requirements may be possible without introducing undue risk. This question cannot be answered by reference to the historical record of the performance of devices using askarels. Recommendation: It is reconmended that flammability performance requirements for nev candidate insulating liquids be baaed on a consideration of the environment in vhich they will be used and on analysis of likely failure modea, rather than on the properties of the fluids they are designed to replace. 3-2.1 flash and Fire Points The measurement of Cl^sh and fire points gives important information on the flamiability hazard characteristics of a liquid. The Cleveland Open Cup method (ASTM D 92) is used for this purpose. A number of other methods are available for the measurement of flaah points. Closed cup methods generally give somewhat lover valuea for the flaah point than the open cup method, but the latter has the advantage of permitting the concurrent determination of the fire point. Since the flash point is a relative rather than abaolute measure of flsmnability hazard, the small differences in results between the two methods are of little significance In the present case. An ASTM ad hoc Consnittee on Flash Point Methodology and Government Response is currently considering new test methods with the major objective of resolving conflicting flash point definitions and test methods used in different government regulations [3). The comlttee appears to favor a closed cup, equilibrium temperature method. 20 HONS 047161 Recosnendatlon: The measurement of fleah end fire point! using the Cleveland Open Cup method (ASTM D 92} ehould be retained, at least for the present. Specifications should be set to provide an adequate margin of safety above the highest anticipated operating temperature for the planned application. If a nev flash point test is adopted for regulatory purposes its use for determining the flash point of insulating fluids should be considered, but the determination of the fire point should be retained. ' 3.2.2 Oxygen Index No standard method for determining the oxygen index of liquids Is available. The oxygen index is related to the fire point [h,5]. Since insulating fluids vill have high fire points, heat loss to the apparatus is an Important factor and the measurements ere extremely apparatus sensitive. No meaningful interpretation of the oxygen index of liquids in terms of fire hasard characteristics is availablt at the present time Reconmendatlon: Since oxygen index measurements, as presently made and interpreted, do not provide ueeful Information on the fire hazard characteristics of Insulating fluids, they should not be incorporated Into electrical Insulating fluid specifications. 3.2,3 Autoignltlon Tests Recommendation: The autoignition teat, ASTM D 2155 and similar tests do not simulate any hazard mode identified with the use of devices Incorporating insulating fluids and thus are not appropriate as fire safety teste. They do provide useful information, in conjunction vlth other material property teata, on the general performance properties of materials, and thus awy be useful in the preliminary characterization of nev candidate insulating fluids. 3-2.1< Spray Flammability Teata Recomnendation: Inasmuch as our limited survey of the uses and misuses of insulating fluids has revsaled no circumstances vhich would be Closely simulated by these droplet combustion teats, there is no reason why they should be included in the specifications for candidate replacement fluids. A further survey of accidents and potential accident circumstances may provide grounds for the further consideration of this type of test in the future. 21 HONS q)7162 3-2.5 Arcing Teats Arcing appear*, at thi* time, to be the Boat common failure mode of device* incorporating inaulating fluid*. Failure nay result froei a gradual growth of lov level discharge* during cornel operation or froo sudden overvoltage conditions. Tests which simulate such failures provide essential Information on the fire safety properties of insulating fluids, Such tests have been conducted on an ad hoc basis [6]. There Is need for a standard procedure to permit evaluation and comparison of the fire safety properties of new fluids under simulated use failure conditions. Separate procedures for transformers and capacitors may be needed. Both gradual and catastrophic failures should be sisiulated. The energy release characteristics of the failure should be measured. Recommendation: A standard test method or methods should be developed to simulate the arcing failure of devices incorporating Insulating fluids under appllcstion conditions. The test method should be based on a careful analysis of the observed or plausible failure modes of such devices. Further recommendations regarding such a test will he found in 3.5 and 3.6. 3.3 Toxicity Tests on Fluids 3.3.1 Appraisal The determination of the toxicological basard or risk of a chemical in the environment, whether Insulating fluid or otherwise, depends on a large number of factors. The exposure to chemical toxicants can be divided Into two rather broad categories: (l) direct exposure of humans during the manufacture end handling of fluids including accidental exposure due to spills, and (2) contamination of the environment that may ultimately lead to exposure of animals and humans. These two categories Include both the acute (accidental spill) and the chronic exposures. Both categories, the work environment and environmental contamination, usually prtduce chronic exposure situations, that is, low level sub-lethal exposures that may continue for periods of months and years. This is particularly true in the industrial environment. Therefore this type of study should be emphasized. Both categories require an assessment of the effects of the fluid on a complex biological system that may respond in a multitude of ways. A partial list of the biologic responses that the toxicologist must observe in studies to determine the toxicity of a chemical is given in Table C, page 88. For example the production of tumors (neoplastigeneiis), benign or malignant (carcinogenesis); the production of changes in the offspring, whether transmissible (mutagenesis) or not (teratogenesls); and the production of death are Just a few of the observations that are used as qualifying toxic effects. HONS 047163 22 The observed or measured toxicity vill depend on a number of parameters such ms node of administration (tee Table B, page 86), length of exposure, the animal epeclee used for testing, the period of observation, etc. Many of these factors have been reviewed for PCBe by Kimbrough (see A.3-7, Ref. 11) and further Illustrate the diversity of responses to a chemical using a variety of anlaial species. This review illustrates the difficulty if not the Impossibility of specifying a comprehensive set of test methods. Exposure of humans (industrial toxicology): While a number of agencies have defined toxicity (see A.3-5), there are relatively few standard teats for determining the toxicity of a new chemical. In the first category above, protection of the work environment la generally achieved through the use of a ''threshold" limit value (TLV) formerly known as maximum allowable concentration (MAC). In tbe United States the threshold limit values are set by the American Conference of Governmental Industrial Hygienists and published annually. The TLV may or may not have been arrived at through animal testing to determine "safe" levels. Tbe levels are constantly undergoing revisions as new information and experience becomes available. Perhaps the most recent example of this is the lowering of the threshold limit value for vinyl chloride monomer due to the finding of liver carcinoma (angiosarcoma) in industrial workers who were exposed to low sub-lethal levels of vinyl chloride over a period of 20 to 30 years. While there is no "one" test method used for determining the toxicity of a chemical to humans, the most frequently used chronic and acute teats are: (1) oral LD50; (2) dermal toxicity (akin absorption); (3) irritation to determine the effect on skin, eyes or mucous membranes; (U) inhalation; (3) chronic or ingestion studies. These determinations are generally made on animals and the relationship between human and animal data continues to raise numerous questions that cannot be resolved here. Details on performance of most of these teats are given in tbe text of the federal Hazardous Substances Labeling Act (Public Lav 66-613, see A.3.5). It should be emphasized that these tests are recomendations and not meant to be all-inclusive. Protection of tbe'environment: Tbe second category referred to earlier as the hazard to tbe environment la certainly more complex and generally represents a chronic exposure. Tbe hazard that a particular chemical poses to the environment not only depends on its inherent toxicity but also the chemical and physical properties of the chemical. For example, the chemical stability, water and lipid solubility, blodegrsdabillty, vapor pressure, etc., will determine the extent to which the chemical will survive and be distributed throughout the environment. These factors will determine to a large degree the ability of the chemical to be Involved in bioconcentr&tlon as it proceeds along tbe food chain. Biodegradation or blotransformation, may itself produce a more toxic product, more easily assimilated into biological systems than tbe original chemical. Biological accumulation requires high lipid solubility versus water solubility, high persistence in the biological system, and a low 23 MONS 047164 tendency for complex formation with organic ligands. The degree to which a chemical affect* the environment may lead to chronic exposure of man by the way of the food chain. Thus the foregoing discussions regarding the contamination of the environment may ultimately lead back to human exposure. These factors must be considered in the evaluation of a new insulating fluid. 3-3.2 ReconmendatIons 1. Avoid rigid protocols: Any attempt to develop a standard set of protocols for routine assessment of the toxicological hazard of an insulating fluid, or any chemical, has several dangers that must be recognized. Such a course of action may lead to the use of tests that are unnecessary. In addition, such standard protocols may fail to ask questions that may be of overriding significance. Oiven the multiplicity of the possible biological systems, an all inclusive standardizing test protocol, which considers all possible reactions, would be wasteful of resources if not impossible. Furthermore, such testing would not guarantee the "complete" safety of a new chemical. 2. Multidisciplinary assessment of toxicity requirements: The extent and nature of tests should reflect (1) the possible level of exposure and route of administration to be expected in usage, (2) the consequences that can be expected, and (3) a margin of safety between expected environmental levels and the dose that produces some adverse effect. In terms of insulating fluids it is important to examine the pattern of usage and disposal, the chemical and physical properties and the biological effects of the compound. An understanding of these factors demands that chronic toxicity evaluations be assessed by a sophisticated multidisciplinary group which involves chemists, toxicologists, microbiologists, and biochemists, etc., working together. Anything short of this approach is likely to lead to a repetition of the present FCB situation. 3- Ames test: It is reoomended that all new fluids be screened for mutagenesis In the Salmonella/mlorosome test otherwise known as the Ames test [?]. The mutagenicity of the combustion products of new fluids should.also be screened using this procedure. Since this test is relatively simple and T high correlation has been obtained between carcinogenicity and mutagenicity with large number of chemicals, it should be run prior to any other toxicological studies to determine the mutagenic potency of a new fluid. With data available on the mutagenic potency of a new fluid, a decision to do more extensive testing or to terminate the effort can be made at a relatively early stage. I. Chronic tests for initial screening: While no set of routine animal investigations will be universally applicable for the definition of the toxicological properties of all insulating fluids, a screening procedure is valuable. Since the problem is mainly one of low level chronic exposure, this type of study should be emphasized but acute exposure should not be neglected. In fact many toxicological studies start with acute work even though the exposure is chronic. Since chronic exposure in the work environment is likely to occur through the respiratory tract, this mode of administration should be emphasized. Due to the fact that environmental problans frequently occur by way of water contamination, avian and fish studies are extremely valuable and should be used. 2l< MQNS 047165 Acute toxicity studies are frequently used to: (l) determine relative toxicity in order to determine what type of further studies should he made (chronic and acute), and (2) delineate the specific toxic effect and mechanism of action. Such studies aid in identifying target organ effects which are valuable in the design of chronic exposure studies which is the primary concern in the evaluation of insulating fluids. In addition to LD50 data, acute toxicity tests provide information on species variability, sex differences, and signs of intoxication which include the relationship of the response of primary interest and the dose response curve. , While a specific protocol is inappropriate, general but detailed guidelines, as suggested by the national Academy of Science in "Principles for Evaluating Chemicals in the Environment" (A.3.7, Ref. U) are appropriate It is highly recommended that appendix B and p of that document be rollowea closely in evaluating the toxicological effects of a new insulating fluid prior to Its introduction into commerce. 5. Combustion product toxicology: The toxicological hazards associated with the combustion products of an insulating fluid are likely to represent an acute exposure situation with a single high concentration of products for a relatively short period of time. The major route of exposure is by inhalation. The assessment of this hazard Is complicated by the large number of products that are likely to result during accidental fire. On the other hand, the situation is simplified by the fact that environmental contamination with toxic combustion products is not likely to create a problem since accidental fires are expected to be relatively Infrequent. At the present time there is no accepted or standardized procedure for this type of hazard assessment. However, a recommended protocol for determining the relative toxicological hazard of combustion products for various synthetic materials is under active development In a number of laboratories in the world. This is one of the major objectives of the Program for Toxicology of Combustion Products at the Rational Bureau of Standards. The protocol under development would appear to be applicable with minor modifications to insulating fluids. 3.1* Brnimndatlon on Degradability and Blodegradabllity Testa Our knowledge of the degradability of the materials of interest as PCB replacements comes mainly from several experiments which were dictated by the immediate needs of individual organizations. There has been no coordinated, industry-wide effort to study the degradability of the electrical insulating fluids currently used or proposed for use in transformers and capacitors. A standard degradability test, developed by the Soap and Detergent Association, has been successfully employed in that industry's self policing program. The same test procedure has also proven significant 25 mons 0^7160 In evaluating the biodegradability of the phthalate eaters by that industry. A need exists for a similar standard test procedure, or set of procedures! for evaluating the degradability--biological, chemical, or physical--of electrical insulating fluids. In viev of the urgency and of the almost universal impact of the decisions to be made it seems appropriate to recomend Involvement of governmental agencies--by initial sponsorship and subsidy--In fostering the development of such standard test procedures. Initial emphasis should be on tests applicable to those liquids which appear on other grounds to be the most promising candidate replacements for the askarels. Much stress has been placed upon the toxicity of ashareIs and other widely used fluids. It is clear, however, that the toxicity of the intermediate substances in the breakdown processes of the proposed askarel replacement fluids as well as the fluids themselves should be scrutinized. The ideal solution may be elusive. Since an increase la degradability means an Increase In reactivity, as new insulating materials for use in power transformers and capacitors are sought, rapeated confrontation with dilemmas such as the following must be expected: 1. Increased degradability may bring with it intensified toxicity. . 2. Increase In degredability may increase fire risk. 3. Increased degradability may cause s lowering of reliability of performance of the insulating liquid. A consideration of all these points will necessitate a comprehensive examination of all properties of a fluid along with an examination of all properties of its breakdown products, an immense task. It is evident that until knowledge accumulates ears will have to be exercised and judgment rendered and compromises accepted for each new class of insulating liquids. 3.5 Recommended Insulation System Tests and Standards -- Transformers 3-5.1 Insulation System Tests Tests of the separate properties of new transformer fluids, as described in 3.1, 3.2, 3-3, and 3.1*, are adequate for screening the potential usefulness of the fluids, but they must ultimately be qualified in the true transformer environment. The influences of winding, tank, and core geometries, and of possible reactions between the fluldB and core, tank and solid insulating materials cannot be evaluated outside the actual transformer configuration or its realistic model. 26 MQNS 047167 Each transformer manufacturer will, of course, test new fluids in his own designs, but it would be additionally helpful to have a standard test configuration developed so that different fluids and different fluid/solid combinations can be put on a comparative basis. This would be useful to fluid and transformer manufacturers, transformer users, and to fire insurance, code and regulatory personnel. Each of these interests should therefore be represented in plsnning and guiding the detailed design, initial testing, and preparation of descriptions and instructions for this standard transformer test. As in example, we recommend for consideration the test guidelines described in the remaining portion of this subsection. We must caution that this is only our initial concept of such a teat baaed on a limited exposure to the problem. Firm guidelines for testing can only be established and validated after considerable experimentation. We recommend research which could lead to such guidelines. The following features should be considered for a transformer test: 1. Tank: fixed size, shape (tank material might he considered to he a variable) 2. Bushings: fixed r 3. Sealing and filling techniques: fixed. A provision should be made for regular sampling of the fluid. 1*. Winding; winding insulation; core site, shape, and materials: fixed 3. Internal supporting structure and electrical connections: fixed 6. The size of the standard model should be large enough for realistic instrumentation, but not so large that cost and laboratory sire are excessive. A unit in the range of a few kVA and a few kV might be the right size. Three types of testing should be carried out for an evaluation of a new transformer fluid: stability, corona, and arcing testing. Instrumentation and measurements which might be considered are described below.1 1. Stability tests: The objective of these tests is to measure the permanence of the fluid, and the degree of deterioration of solid surfaces in contact with the fluid. Temperature cycling should occur. The fluid should be sampled at regular intervals and tested for changes in electrical (dielectric constant, dielectric strength, resistivity, loss factor) and physical (density, viscosity, specific heat, flamabillty) properties. Chemical analysis should he carried on to Identify contaminants. The tank walls, core and wire insulation surfaces should be inspected regularly for detection of surface reaction. Standardized procedures should be employed wherever available. 27 *ONS 0*7166 2. Corona fsts*. A standard corona source should be designed into the standard nodal transformer, possibly associated with one of the windings. Corona inception and extinction levels should be neasured, using standard procedures. Corona should persist at a prescribed level for a specified duration. The fluid should be regularly sampled during this tine to measure changes in electrical and physical properties, and to detect contaminants. Tank walls, core and conductor insulation should be regularly inspected for surface reactions. An attempt should be nade to detect and identify any tendency to convert from corona to a higher current arc. Procedures for removing contaminants should he considered. 3. Arcing tests; A standard method should be developed for igniting an arc within the model transformer. Possibly the standard test could include different arc modes, between adjacent layers of a winding, between windings end from one winding to the tank. The following parameters should be controllable variables*, source voltage and impedance or arc current, arc duration and Initial temperature. The following phenomena might be measured or observedt a. Qrowth of arc current and arc length and position. b. Pressure wavs within the tank and on the tank wall. c. Conditions to cause tsnk rupture. d. Energy release from the fluid. e. External firs; fire threat to neighboring structures. f. External blast wave and damage to neighboring structures. g. Escaping combustton/explosion products. After an acceptable insulation modal has been developed and thoroughly tested, the design and testing procedures should be documented for consideration by standards, codes, insurance groups and regulatory agencies. 3.5.2 Standards -- Transformers Several of the ANSI C 57 series of standards dealing with transformers make reference in the title or elsewhere to the liquid filling, i.e., "mineral-oil lamersed," "mineral-oil filled," etc. These are probably only Intended as restrictions to eliminate dry-type transformers since AHSI C 57.80 (Terminology) states "the term oil Includes synthetic liquids as well as mineral transformer oil." However it would seem appropriate that the whole series be studied and necessary modifications made in future revisions to remove the restrictions where they are not essential. In those cases where the restrictions are necessary, corresponding documents which apply to transformers with other insulating liquids should be prepared. Iastm d 1868-73 "Detection and Measurement of Discharge (Corona) Pulses in Evaluation of Insulation Systems" 28 HONS 7 169 Some standards and formal guidelines which might he needed for transformers with new fluids are: 1. Standard sites and ratings. 2. Guidelines for acceptance testing. ' 3. Installation and operation codes. I*. Guidelines for maintenance of new fluids in transformers. 3. Guidelines for storage and disposal.1 6. Guidelines for fusing. The insulation system tests on transformer models described above should be designed to provide the information needed for these new standards and guidelines. While fusing is strictly outside the scope of this study, more flammable fluids could be used if higher levels of fusing were present; the model system tests could place quantitative requirements for fuse protection of new, more flanmable fluids. 3.6 Recommended Insulation System Tests and Standards -- Capacitors 3.6.1 Insulation System Tests Tests of the separate properties of new capacitor fluids, as described in 3.1, 3.2, 3.3, and 3.It, are adequate for screening the potential usefulness of the fluids, but they must ultimately be qualified in the true capacitor environment. The influence of electrode and solid dielectric geometry and possible reactions With these surfaces are essentially impossible to evaluate outside the actual capacitor configuration. Each manufacturer will, of course, teat new fluids in his own capacitor designs, but Tt would be additionally helpful to have a standard teat configuration so that different fluids and different fluid/solid combinations can be put on a comparative basis. This would be useful to fluids and capacitor manufacturers, to capacitor users, and to fire insurance, code and regulatory personnel. All of these Interests should, therefore, participate in guiding the detailed design and use of such a standard capacitor test. The suggested model tests on capacitor insulation systems are Identical in approach to those recommended for transformers in 3.3.1. Many factors responsible for insulation failures in transformers are present also in capacitors. There are several obvious practical differences In the components of transformers and capacitors. Because there are A contributor has suggested that guidelines and standards will also be needed for the proper substitution of new fluids for askarel in existing transformers. 29 HUNS 047170 <11 (Terences, the entire suggested guideline for capacitor Model tests Is described. As for transformers, we again emphasise that the following guidelines are our initial recommendations for a model teat; they point oui a number of details which should be investigated in any model test. However, they are not firm and verified test procedures. These can only be established after considerable experimentation. The following features should be considered for a standard capacitor model test: J. Container: fixed site, shape, material. 2. Bushings: fixed. 3. Sealing and filling techniques: fixed; provision should be made for regular sampling of the fluid, possibly by dismantling one out of a group of teat units at regular intervals. !<. Electrode foil; insulation film size, thickneaaea and roll configuration: fixed. 5. Foil and film materials: variable, ao that the reaction of the test fluid with different foil and film materials can be measured. 6. Foil/film roll supporting structure and electrical connections: fixed. . Three types of testa should be carried out for a complete evaluation of a given fluid/film/foil combination: for stability, for corona effects, and for arcing effects. Instrumentation and measurements which might be made in each teat are described below. 1. Stability testa: The objective of these teats la to measure the permanence of the fluid, and the degree of deterioration of solid surfaces in contact with the fluid. Temperature cycling ahould occur. The fluid should be sampled at regular intervals and teated for changes in electrical (dielectric constant, dielectric strength, resistivity, lots factor) and physical (density, viscosity, specific heat, flammability) properties. Chemical analysis should be carried on to Identify contaminants. The container vails, foil and film should be Inspected regularly for detection of surface reaction. Standardized procedures should be employed wherever available. 2. Corona tests: A standard corona source should be designed into the standard capacitor configuration. This might be the foil itself, or an auxiliary electrode. Corona Inception and extinction levels should be measured, using standard procedures. Corona1 1ASTM D 1868-73 "Detection and Measurement of Discharge (Corona) Pulses in Evaluation of Insulation Systems" 30 MONS 0*7171 should persist st s prescribed level for a specified duration. The fluid should be regularly sampled during this time to measure changes in electrical and physical properties and to detect contaminants. Foil, film and container -walls should be regularly inspected for surface reactions. An attempt should be made to detect and identify any tendency to convert from a corona to a higher current arc. Procedures for removing contaminants should be considered. 3. Arcing tests: A standard method should be developed for igniting an acc within the container. The source voltage and Impedance or arc current, arc duration and Initial temperature should be controllable variables. The following parameters might be measured or observed; a. Arc voltage. b. Pressure wave (intensity and time parameter) within the container. c. Pressure on the container wall. d. Energy release from the fluid. e. Conditions to cause container rupture. f. External fire; fire threat to adjacent capacitors. g. External blast wave and damage to neighboring capacitors and structures. h. Escaping arc products. After a suitable model has been developed and thoroughly tested, the design and testing procedures should be documented for consideration by standards, codes, insurance and regulatory agencies. 3.6.2 Standards -- Capacitors Several guidelines and standards will eventually have to be developed for capacitors with new fluids; these can be grouped in several categories: 1. Standard sizes and ratings. 2. Guidelines for acceptance testing. 3. Installation and operation codes. it. Guidelines for maintenance of new fluids in capacitors. 5. Guidelines for storage and disposal. 6. Guidelines for fusing. 31 HONS 0471^2 These would serve capacitors with new fluids such as ANSI C55.2, NEMA CPI and EIA RS-392 now serve askarel-filled units. The model system tests described above should be designed to provide the information needed for these new standards and guidelines. We should note that EIA is moving in this direction already with its RS-392-1 standard (also AXS1 C83.679) but that the combination of nonaskarel fluid and nonpaper dielectric has not yet been covered by EIA standards. Some brief explanation of the above fusing recommendation is in order. While fusing is strictly outside the purview of this study, it does possess a close relationship to the flammability issue and therefore deserves some mention. A more highly flanoable fluid can possibly be tolerated in a capacitor if the fusing protection is sufficiently good. The system model tests described above should be designed to quantise this trade off between flammability and fusing. 3.7 Standards, Regulations, Codes In previous sections of this report, frequent references have been made to standards, regulstlons, and codes, but mostly in the context of specific test techniques or specific new fluids. In this present section we will briefly review this same material, not in- terms of the techniques themselves but rather to Investigate mechanisms for formal adoption of the techniques. It is true that existing codes and standards are such that locations can be found for initial service testing of capacitors and transformers with new fluids; bowever, new or revised standards will be required ss new fluids, snd new test procedures for tbess fluids are "proved out" in field testing snd as they approach full-scale comerclal use. Because of the long time required in the prepsratlon of such standards, the existing standardising consittees in IEEE, ASTM, TOMA, and EIA should be encouraged to accelerate current efforts and to initiate new programs where neceemary to permit the development of standards to proceed as nearly as possible in parallel with the field testing phase. Of concern in a discussion of the need for new, or the revision of existing, standards documents is the problem of achieving adequate "uaer" participation in the technical society coonlttees which prepare them. It has been called to our attention, for example, that of tha near 100 members of the ASTM D 27 committee which is responsible for insulating fluids standards, only the order of 10* are from utilities, and participation of Federal Government agencies is at a very much lower level although the Government through OSA, DoD, Dol, etc., is perhaps the largest single purchaser of power transformers. It seems evident that greater participation by the "user" group might significantly expedite the preparation of needed standards. 32 047173 kqns Concern with the cotta of staff participation in standardizing activities probably is the principal deterrent to greater involvement both of this "user" group and of the academic coonunity. This concern no doubt also sets a limit to the level of effort in these activities by the manufacturing community which currently appears to be making the greatest contributions. Recommendatlon: Establish a fund to pay travel costs incident to staff participation in the preparation of the most urgently needed standards, in order to broaden the base of industry and academic participation and greatly reduce the time required in the preparation and adoption of nev and revised atandarda. The National Electrical Code (NEC) plays a key role in commercial acceptance and usage of new fluids, as has already been pointed out in earlier sections. It is used by fire insurance companies in Judging the acceptability of installations for insurance coverage, it forma the basis of many local building codes and ordinance*, and it haa been incorporated into federal regulations. It la important, therefore, that the Electrical Coordinating Committee of NEC be cognizant of, and give counsel on development of new flaionablllty testa such as discussed in Sections 3-2, 3.5, and 3*6. Independent testing laboratories such as Underwriters Laboratory and Factory Mutual Engineering and Research must also be given the opportunity to contribute to formulation of these nev flemaabllity test procedures. . Each of the pertinent Government regulatory agencies has its own particular area of concern regarding nev Insulating fluids, and can contribute from its own special strength in developing nev tests, end in interpreting regulations as they apply to nev fluids. In particular, the following specific comments can be made: 1. OSttA*. Consideration should be given to modifying regulations to allow insulating fluids not yet recognized by the National Electrical Code. OSHA might also encourage development of airborne toxicity tests and flammability testa which are particularly adapted to the work place. 2. FDA and State Departments of Public Health; Early evaluation of the new candidate fluids is needed, regarding not only toxicity but also likely avenues or entry into food production and distribution. 3. DOT: The hazards of new fluids particularly associated with transportation should be explored; also a determination should be made whether any new candidate fluids fall within DOT'S existing hazardous or toxic substance classifications. h. HEW: Test procedures will need to be developed for determining toxicity and degradability of new fluids. 33 MUNS 047174 5. EPA. State Department* of natural Resources and Public Health: Analytic procedure! vill be needed for measuring presence * toxicity and degradability of new fluids in the natural environment-, preaent background levels of the substances should also be determined for future comparison. An evaluation should be made of the Impact of proposed toxic substance legislation on the industry If it turns to the new candidate fluids. Recoittnendatlon: Form an interagency task force with representation from each of the federal (and perhaps from a few of the more active and involved state) agencies, charged with the task of developing a consistent governmental approach to solution of the problems imposed by the safety oncern with electrical insulating fluids. If such a task assignment .s not feasible, even the minimal assigned responsibility for keeping ach other end the electrical power industry at large veil informed as o planned actions would well Justify its formation. The task force could become the focal point for the industry's contacts with the Government in this area of concern. 3U MGNS GV?1?5 3.8 References for Section 3 ' 1. A. F. Robertson, "Test Method Categorisation and Fire Hatard Standards." Standardisation Mew. Vd. 3 (1975), pp. 18-20. 2. H. L. Maihotra, "The Philosophy and Design of Fire Tests." Proceedings of the International Symposium on Fire Safety of Combustible Materials, University of Edinburgh, Oct. 1975, p. Ib9. 3. H. A. Wray, "New Flash Point Tester for the Paint Industry." Journal of Paint Technology, Vol. *5 (1973), pp. bb-5b, b, A. F. Roberts, "Extinction Phenomena in Liquids." Proceedings of the Fifteenth Symposium (International) on Combustion. The Combustion Institute, 197b. pp. 305-313 5. D. J. Rasbash, "Relevance of Fire Point Theory to the Assessment of Fire Behavior of Combustible Materials." Proceedings of the International Symposium on Fire Safety of Combustible Materials, University of Edinburgh, Oct. 1975, p. 169. _' 6. D. A. Duckett, "Catastrophic Explosion Tests in Insulating Fluids." Internal Report. RTE Corp., Waukesha, Wisconsin 53186, Rov. 9, 197b. 7- J. McCann, E. Choi, E. Tsmasaki and B. Ames-, "Detection of Carcinogen as Mutagens in the Salmonella/Microsome Test: Assay of 300 Chemicals Proc. Rati. Acad. Bel., Vol. 72, Dec. 1975, pp. 5235-5239. 35 MQNS 0^7176 APPENDIX StAtUS A.l "Askarel-class" Transformers A.1.1 Description of the "askarel class" of transformers Electrical transformers are used to change voltage, current and Impedance levels In a vide.variety of applications in electrical apparatus. These transformers range from the very smallest types In solid-state electronic circuitry to very large 60-Hz power transformers. This study is concerned vltb the following restricted but Important, set of_ t rans formers: 1. Utility and industrial distribution transformers; these Include a wide variety of applications: uses in utility "network" systems, in secondary unit substations and factory load centers; they may be under ground, within buildings or adjacent to buildings or other occupied areas. This group is therefore identified by industrial and commercial use in areas where the load and population densities are high. Typical ratings are 500-2500 kVA, 4-3** kV. 2. High voltage transformers, for electrostatic precipitators which remove particulate pollutants from furnace exhaust gases. 3. Transformers for multiple-unit type electric railroad cars; these are located under the flat-bed of the car. While many precipitator and most railroad transformers are askarelfilled, only 10-15# of utility and industrial distribution transformers identified above a*e the askarel-type. Host power transformers use a liquid insulant which serves two purposes: electrical insulation and cooling. Compared with air insulation, the liquid allows much closer spacing (smaller size) for a given voltage, and compared with air or^solid insulation (as used in "dry-type" transformers), the circulating liquid coolant leads to a much smaller size for a given power rating. Mineral oil was traditionally used for this purpose and la still used for most applications. Estimates sre that as much as 98J of all liquid-cooled power transformers use mineral oil, on an MVA or galIon-of-coolant basis. However, the particular set of applications described above have critical nonflamnabillty requirements since they sre generally located in heavily populated areas or are used In hlgh-temperature or high firerisk conditions. "Askarel" transformer liquid was developed, using blends of the polychlorinated biphenyls (PCBs), in the early 1930's to replace mineral oil in applications where nonflammability was an important requirement. The PCBs for these transformer askarels are manufactured by Monsanto Industrial Chemicals Company and are sold by Monsanto under the trade name "Aroclor." Two grades are presently used (shoving percent chlorination and 1971* domestic sales in thousands of pounds) Aroclor 12l*2 Aroclor 125^ (U2!0 (54*) 6207 6l05 M0NS 04717? 36 Ten to twenty percent of this production goes Into electrostatic precipitator and railroad transformers1; nest of the remainder is used in the utility and Industrial transformers. Approximately 5000 askarel- filled transformers are manufactured per year In the U.B., st a value of about $1*5 million. . The term "askarel" which describes a broad class of fire-resistant {1], synthetic, chlorinated, hydrocarbon insulating liquids is defined more rigorously In the following standards and guidelines. IEEE Std. 76-197**; IEEE Guide for Acceptance and Maintenance of Transformer Askarel in Equipment ASTM D-2283-73; Chlorinated Aromat^c Hydrocarbons (Askarels) for Transformers (V ku see 0-2233-70) National Electrical Code, 1975; Art. 100 ("Definitions"), **50 (Transformers and Transformer Vaults), *t6o (Capacitors). In addition to the fire-resistant characteristics of the askarels, their high dielectric strength, low electrical loss, adequate viscosity, specific heat, and thermal stability, and their nonsludging qualities have combined to make them Increasingly attractive transformer lnsulants since their introduction in 1932 [2]. Their high cost relative to mineral oil has, however, restricted their use to transformers for the abovedescribed fairly well defined set of applications--the "askarel-class" of transformers.2 It is for this set of uses, then, that alternative transformer fluids are being offered, and test methods and standards for these alternative fluids should therefore be responsive to these specific applications. The askarels provide fire-resistance by generating Inert hydrogen chloride upon decomposition. Their flash and fire points are also very high, making them difficult to ignite. Hydrogen chloride is a highly corrosive material, and so extensive special designing and installation must be observed. Only particular, corrosion-resistant winding and tank coating materials can be used, "scavenger" materials must be present in the fluid to take up any small amounts of hydrogen chloride which are generated In normal operation, and in addition the transformer room or vault must be adequately ventilated to prevent buildup of HC1 vapor. It should also be noted that askarels are very efficient solvents and that consequently all solid insulating materials, including gaskets and paints, must be carefully selected, 1These two special uses are growing as mass transportation and air pollution control programs expand. p Askarel transformers are specifically identified in the National Electrical Code and in many local fire codes and ordinances. 37 MONS G*t ? 1 78 Because of the toxicity end environmental problems of the PCBs, drainage from ashare1 transformer installations must also be adequately collected so that small or large scale spilling of fluid, during filling, testing, operation or catastrophic rupture, vill be contained and not reach the ground water or navigable water systems. These special requirements of existing askarel-transformer designs and installations are being identified in order to have a clearer picture of the processes which will be involved in replacing the PCB fluid with an alternative. Either the new fluid will have to be compatible with all of the characteristics of the existing askarel installation, or new installations will hare to be designed to accommodate the new fluid. These constraints will shape the requirements of testing procedures to evaluate and qualify new fluids and transformers filled with new fluids. A.1.2 Sources and consequences of transformer tank rupture In the construction of "askarel-class" transformers, the windings are completely immersed in the fluid. Inside a tank which is sealed to prevent the fluid from escaping.1 The tank must be heavy walled to with stand the sudden pressure of a high-current electrical fault within the tank. The tank is generally finned for convective heat transfer to the surrounding air, and it often has a pressure relief device to bleed off any email but steady rise of gas pressure within the tank (as from occasional low-level arcing or corona). If mineral oil or a new liquid lnsulant such as a silicone fluid is to be used as a replacement for askarel In transformers, one can be sure that containment of this fluid will be a prime objective, for safety, environmental and economic reasons. In anticipation of require ments for containment tests and standards, it vill be the purpose of this section to review tKfc present state of standards, tests and understanding in the area of transformer fluid containment. Although the fluid is held in substantial drums or in the sealed transformer tank, loss of the fluid can still occasionally occur under several different circumstances: a. during transport of the fluid or of the filled transformer, b. daring processing and handling of the fluid by the manufacturer or user, ^The amount of askarel fluid in such a transformer ranges from 1*0 to 1500 gallons, depending on the size and rating of the transformer. 38 MONS 047179 c. lurinp, in-service operation of the transformer, and d. upon disposal at the end of the unit's life. Instructions for proper transport of the fluid and of the transformer are included within the general procedures of the Department of Transportation [3], (eee also Section A.4). In addition, the following are cited as examples of the types of guidelines and standards which could be developed to prevent leakage during acceptance, maintenance, handling and disposal of-transformers and fluids: a. "Guidelines for handling and disposal of capacitor and transformer grade askarels containing polychlorinated biphenyls," ANSI Cl07.1 - 1974; American National Standards Institute, 1430 Broadway, New York, K.Y. 10018. b. "IEEE guide for acceptance and maintenance of transformer askarel in equipment," IEEE Std. 76 - 1974, Institute of Electrical and Electronics Engineers, 345 E. 47 Street, New York, N.Y. 10017. These standards are discussed more fully in Section A.1.5. The oil spill regulations developed and enforced by the Environmental Protection Agency [4] also can serve as a model for Judging the restrictions on other fluids leaking into the environment. These are discussed in Section A.4. A very rugged design is used for transformer tanks in order to maintain containment under most external or Internal stresses likely to be encountered in service. These tank designs are specified by industry standards published by ANSI [5]. Tank dimensions, static pressure withstand capability and corrosion resistance are specified. These standards should be reviewed for applicability with new fluids. Rupture of a transformer tank while in service is most often due to arcing within the tank. This is a very complicated phenomenon which has been studied for many years. The following paragraphs describe the phenomenon, its effects, and possible controls as presented In recent articles by Barkan et. al. [6], Goodman and Zupon [7], Nettleton [8], and Ristuccia and Benton [9]. a. The arc most often starts as a low-current, high-impedance insulation breakdown between adjacent turns somewhere within the transformer windings. "^Revision of this document is currently under way. 39 HONS 04 7l80 to. A "high proportion" [7J of transformer failures result from the gradual buildup of pressure in the tank due to the gas evolved toy the low current arc. The pressure-relief valve present on most network transformers could avoid this as a cause of rupture in this important application of "askarelclass" transformers. Some users claim, however, that the pressure relief valve is more trouble than asset, and therefore avoid its use. A fuse could also be used to clear these lowlevel faults, although network transformers are generally operated without primary fusing. c. The high-impedance arc will grow with time to a high-current fault as the arc attacks the Insulation on more turns. Because the use of pressure relief valves generally prevents the type of tank rupture described in part b. above, the high current arc may be the most prevalent cause of tank failure in the network transformers. We presume that the final growth of current is rapid, creating a bubble of high pressure gas within the fluid. According to Barkan [6], this bubble, as it expands, drives a ''piston" of oil against the tank wall, momentarily overloading the wall and causing rupture. . d. Techniques for calculating the peak tank wall pressure under arcing faults are presented in both the Nettleton [8] and the Barkan [61 articles, but both also point out the difficulty of this for actual tank geometries. The static pressure relief valve is of no use here because of the rapid rate of pressure rise [9], and gas-flute venting techniques are also generally inapplicable for the same reason [6]. There is apparently a proposed revision to the ANSI transformer standard (C57.12.201971) for a standard transformer arc test to determine the necessary tank arc pressure withstand capability [9]. e. Further complicating the pressure calculation are the effects of energy release by burning of the fluid and of fluid products. This energy will build up the pressure, and the pressure wave will have characteristics due to being flame- as well as arc- driven [8], f. One should not rely purely on tank withstand strength to prevent tank rupture under arcing, but rather this should be coordinated with a properly specified current-limiting fuse [6, 9]- The peculiar impedance characteristics of the arc prevent use of the familiar I2t type of fuse specifications; rather, the fuse manufacturers should recommend the proper fuse, based on the user's known voltage and fault-current levels.* 'one user points out that network transformers are often in subways and must therefore be submersible, and fuses are therefore avoided. MQNS 047181 UO Protection against the high current arc Is of great importance, not only because it may be the most prevalent source of "askarel-class" transformer failures, but also because the arc is a high-temperature source which can Ignite the fluid or the decomposition products due to the arc. Thus, protective tests and standards Dust coordinate the available temperature and energy (as for instance determined by a current limiting fuse) with the ignition temperature and energy of the fluid snri of flammable components created by the arc. The "transformer system testing" discussed In A.1.3 will explore this type of testing In depth. It is worth noting at this point that an arc in an insulation fluid can cause & wide range of decomposition products, depending on the chemical nature of the fluid, the availability of reactant gases such as oxygen, and the intensity (temperature) of the arc. Products can be flammable, explosive, corrosive and toxic. As examples, arcs (or low level discharges such as corona) can decompose mineral oil into hydrogen and hydrocarbon gases (and probably water if air is present), while , asharele are known to break down to hydrogen chloride, and some hydro carbon gases. Nitrogen, carbon monoxide and carbon dioxide are also said to result [10] but again probably only in the presence of air.1 ` Not only can these products be directly harmful, but they can also weaken the dielectric strength of the insulating fluid and thereby set the stage for subsequent high current flashover .and tank rupture. One should, therefore, seek standard procedures by which the fluid can be cleaned up at regular Intervals, or after known arcing, In order to avoid future equipment failure. As guides in preparing such standards, we should note the following procedures which are now regularly employed. a. "Scavenger" substances are mixed with askarels to take up the corrosive hydrogen chloride which is produced by occasional low level electrical discharges within the fluid. b. In spite of the presence of scavenger material, users are instructed to bubble nitrogen through the fluid immediately after known arcing in order to pick up hydrogen chloride before it cair*do corrosion daoage. c. The IEEE Standard 76-1971* suggests that moisture content and dielectric strength of askarel be regularly checked if electrical discharge is known to be occurring. Because of the combination of preventive measures outlined above, manufacturers and users report that present transformers of the network type experience about a 0.01 to 0.02J yearly rate of tank rupturing *A recent report (National Conference on PCBs, Chicago, Nov. 1975) indicates that chlorinated dibenxofurans are formed in PCB heat exchanger fluids. Ul HONS 0471B2 failures. Testa, standards, and guidelines must be prepared for new fluida in order that lov failure rates vill also be obtained for nev transformer fluids. Even though a lov rupture rate is experienced with transformers, it is still industry practice, generally backed by fire or environmental code enforcements, in indoor installations to place fluid-insulated transformers in vaults or special rooms. Mineral oil units must be in fire-proof vaults [ll]. Low-voltage askarel transformers need not be In fire-proof vaults but must be installed so that ventilation is adequate to prevent accumulation of t.oxic vapors [12]. Drainage facilities should be such that spilled fluid ... contair ed A.1.3 Transformer system testing In the early days of askarel usage a short-circuit test and an arcing test were performed by Underwriters' Laboratories, Inc., on actual transformers filled with an askarel (General Electric "Pyranol") Details of these tests are reported in the UUtH Eo. 2581 Report, dated September 29, 1931*. More recently, catastrophic explosion (arc] tests with several insulating fluids were performed by DTE Corporation {13]- 1. Underwriters' Laboratories Tests The transformers were rated 60 Hi, 5 kVA, 2200-110 volts. One of these was short-circuited externally. The other was subjected to an arcing test by being connected to a 12,000 kVA generator so as to apply 7,500 volts between the ungrounded 122-volt lead and ground. In both cases, pressure-tight covers were provided with pressure-relief diaphragms designed to rupture at not less than 10-12 paig (69-83 kPa gauge). The results of the two tests were rather similar: no appreciable change in pressure was noted for approximately 2 minutes after current was supplied to the transformer. Thereafter, the pressure increased rather rapidly until the diaphragms ruptured. Large volumes of gases were liberated during the tests, but the gases did not ignite upon application of a test flame. 2. RTE Arc Tests Four insulating fluids were tested: mineral oil, DC-200 Silicone fluid (Dow Corning), hydrogenated paraffin oil "RTemp" (RTE Corporation), and an askarel (Westinghouse Inerteen 70-30). Approximately four gallons of each fluid were used, preheated to 150 C. The containers were covered before the test, but the rupture pressure (presumably roughly the same in all four cases) was not specified. In each test the liquids were subjected to a massive arc discharge: 1*660 to 1*820 A, the arc being initiated with 1*000 volt open circuit. Each of the four samples shoved a violent flash initially and vide spraying of the liquid as the cover was blown free, but only mineral oil continued U2 MGNS 047183 to bum. It Is important to note that mineral oils used in transformers have flash points in the vicinity of 150 C and fire points about 15 C higher. The highly-chlorinated askarels, on the other hftnd, have no fire point up to the boiling point. They have no true flash points but socalled pseudo flash points may be observed under conditions of the test. Silicone fluids have very high flash points at about 300 C (see the section on flammability tests). RTemp, being a high hydrocarbon frart'o-, presumably a)s<i has a high flash point. Thus the tests were conducted with initial fluid temperature near the flash and fire points of mineral oil, but substantially below the flash polntB of tha other fluids. 3. Reaction from Industry The consensus appears to be that both sets of tests (UL and RTS) show askarels to have very low flammability. The UL rating of 2-3 on the scale of 100 for flammable fluids reflects this consensus. Furthermore, the Factory Mutual representatives appear satisfied that the RTE testa show also the silicone fluids and RTemp to have flammabilities in the sane, generally acceptable, range as askarels. UL representatives have not coranented on the RTS testa. On the other hand, the nature of the initial flash in RTE tests and of the observed pseudo flashes in flash point testing of askarels does not appear to be understood; some concern therefore remains. Intense heating of the decomposition products by the arc may lead to some reaction of these products with air. Contributors have also suggested that in arc explosion tests of askarels the fluid is electrically heated to decomposition temperatures, and that decomposition itself is exothermic. As a result, several representatives from industry and insurance business have commented that a carefully standardised arcing test should be developed. Manufacturers, users, and testing laboratory personnel have indicated a willingness to cooperate in developing such a test. A.l.b Alternatives askarels in "askarel-class" transformers; influence on total transformer tests and standards We must emphasise again that the purpose of this study is not to evaluate alternatives to askarels bu rather to survey the status of tests and standards by which such alternatives may be Judged. The characteristics of the available alternatives must be explored, however, to the extent that unique characteristics will influence the definitions of tests and standards. This section will emphasize the effect of alternatives on the total unit, while the Section A.It will look at the rluids themselves. Many concepts originally brought up in A.1.2 ("Sources and consequences of transformer tank rupture") will be revisited in terms of the goals of this section. The characteristics of available alternative fluids are presented In detsil in Section A.3 and therefore need not be repeated here. It Is important to note, however, that these represent a vide range of density, 1*3 MONS 047184 viscosity, operating temperature, corrosiveness, volatility, hydrolytic stability, flammability, etc. Because of the diversity of these values, ve will see that universal fluid performance specifications will be difficult to write without taking into account the unique characteristics of each particular insulant. This will be equally true in establishing performance standards for the total transformer assembly. The important fluid characteristics which must be accounted for in any future transformer standards and specifications are listed below: n* Material compatibility. The chemical activities of the available insulation fluids differ in kind and degree. Tests must, therefore, be devised to measure adequacy of the materials used for protective coating on inside of the tank vails, for insulation on the wire used for the transformer windings, and for miscellaneous other components such as disconnects and fuses which might be in contact with the fluid. b. Temperature. If the particular insulating fluid requires an unusually high operating temperature, all materials used to construct the transformer must be compatible with this temperature, and in addition the location of the operating transformer must be selected to be acceptable to this higher operating temperature. Existlag standards such as: "General Principles for Temperature Limits in the Rating of Electric Equipment," IEEE Std. 1-1969, are probably adequate for this purpose. Standard sampling techniques may also be desired to Insure the stability of the fluids at high operating temperatures. c. Cooling. The fluid in a transformer is used as both an insulating and cooling medium. An economically competitive transformer must have its cooling system design closely matched to the characteristics of the coolant fluid; new fluids will undoubtedly require some redesign of the transformer. This may necessitate new standards on transformer tanks, cooling surfaces, circulating equipment, etc., and the user may demand more thorough cooling specifications on transformers with new coolant fluids*. d. Hydrolytic stability. Water is generally a problem in transformer fluid, but the degree of difficulty will probably change from one fluid to another. Sealing against moisture entry, and processes for removal of water should, therefore, be specified for each new insulant. e. Containment. The different fluids will have different densities and required volumes for any given transformer power and voltage ratings, and space and supporting structure specifications must be made up for each new fluid. The types of seals will also have to be correlated with each fluid, since different fluids have different leakage characteristics. Since rigorous contain ment of any fluid may be the goal of future regulations, standards and tests for evaluating containment of each tank/fluid combination will be of increasing Importance. 1 It MONS 047135 Standards for eactar*l protection should be coordinated with the particular class of transformers, the fluid and the level of tank containment security. By external protection, we mean secondary protection provisions, beyond the tank itself. This Includes both vaults, for extra containment in case of tank failure and protective circuit elements (such as circuit breakers and fuses) to prevent tank rupturing arcs from occurring. Much as an electrical system has its various power and protective elements coordinated with one another, so also might the Industry consider more quantitative coordination of the levels of transformer containment. One might, for instance, consider that increased speed and redundancy of circuit breaker and fuse protections could allow a leas cumbersome and expensive vault structure. Extensive probability analyses of actual operating experience would be required before such a coordination plan could be acceptable for fire codes and insurance purposes. Although no new standards or tests may be required, we include, for completeness, a mention of two other available alternatives, namely drytype and gas-cooled transformers. These transformers depend on ambient air or special gas insulation. The dry types are available now and are being used extensively in place of askarel transformers. Relative reliability and overload capability have been questioned by some users but are quite acceptable to others, which nay mean that standardized tests on these characteristics should be available to resolve such disagreements. Oas cooled transformers are not yet as readily available for substitution. Tests may be required to establish the harmlessnets or the need for containing products of arcing within the insulation gas. Development of these teats should be guided by the extensive existing work on entirs gas-insulated substations. A. 1,5 Test techniques and standards used by manufacturers and users to evaluate fluid-filled transformers The transformer manufacturer and user have the following standards documents available for guidance in selecting and handling the insulating fluid. 1. ASTM^ D 2283-71* "Standard Specification for Chlorinated AromatJ. Hydrocarbons {Askarels) for Transformers." This document gives detailed specifications of the physical, chemical and electrical properties of six askarels which have been, or are being used in transformers and identifies specific test methods. 2. ASTM D 311*6-75 "Standard Specification for Oxidation - Inhibited Mineral Insulating Oil for Use In Transformers and Circuit Breakers." ^American Society for Testing and Materials, 1916 Race St., Philadelphia, Pa. 19103. >*5 MONS 04 718b This document give detailed specifications of the physical, chemical and electrical properties of the oil together with approved test methods. 3. ASTM D 10l<0-T3 "Standard Specification for Uninhibited Mineral Insulating Oil for Use in Transformers and in Oil Circuit Breakers." This document gives detailed specifications of the physical, chemical and electrical properties of the oil together vith approved test methods. ** ANSI* C 59.131-1971 "Guide for Acceptance and Maintenance of Insulating Oil in Equipment" [Also issued as IEEE? Btd. 61-1969]. The purpose of this guide is to assist in evaluating the serviceability of oil received in equipment; oil as received from the refiner for filling new equipment at the installation site, and as processed into such equipment. It also is intended to assist the operator in maintaining his oil in serviceable condition. The guide reconsends standard oil teats and evaluation procedures, methods of reconditioning and reclaiming, the levels at which these become necessary, and the routines for restoring oxidation resistance where required by t)ie addition of inhibitors. 5- IEEE Btd. 76-197** "Guide for Acceptance and Maintenance of Transformer Askarel in Equipment." This guide assists in evaluating askarels as received in tramsformer3, reactors, and accessory equipment operated at power frequencies and in efforts to maintain askarels in serviceable condition. It recommends standardised tests and evaluation procedures. Methods are outlined for reconditioning and reclaiming askarels whenever necessary. 6. ANSI C 107.1-1971*- "Guidelines for Handling and Disposal of Capacitor- and Transformer-Grade Askarels Containing Polychlorinated Biphenyl*." This document gives Jfcypical physical, chemical and electrical properties of askarels used in insulating fluids in transformer and capacitor construction, standard methods by which these properties are measured, details methods of shipping and handling, spells out necessary safety precautions, reconsends labeling practices and details approved disposal techniques. It also lists organisations having facilities for analysis and for disposal and it describes analytical procedures for the determination of PCBs in air, water and sediment. 1Alterlean National Standards Institute, 1930 Broadway, New York, R.Y. 1001B. n Institute of Electrical and Electronics Engineers, 3*5 E. i*T Street, New York, N.Y. 10017. U6 HONS 0<r 7 18 7 T- IEEE Draft "Specification for New, Unused Transformer-type Askarels." This specification covers bulk shipment in tank cars and drums of new, synthetic, nonflammable electrical insulating liquids of the chlorinated aromatic type known as askarels which are used as insulating and cooling media in liquid-filled transformers. While thiB spec! ficatlon Is intended to cover the composition and characteristics of askarels for purchase only and does not apply to liquids in apparatus, a number of discontinued types are included for purposes of identification and historical significance. 8. IEEE Std. 283-1968 "Ouide for Installation of Oil-lwersed Transformers." This document suggests procedures to be followed,In filling with oil those large transformers which are customarily shipped to the point of installation without the oil. 9. A NEMA1 Standards Document titled "Proposal for American National Standard on Mineral Insulating Oil for Use in Electrical Apparatus" is in the final stages of preparation. It is Intended "to provide a functional industry standard that will assure a continuing supply of a single mineral insulating oil that adequately meets the needs of equipment manufacturers and oil refiners." It sets functional limits for the essential physical, electrical, and chemical properties and specifies the ASTM test methods to be used. Presumably it will ultimately replace items 2 and 3 above. 10. FSS-G6A2 Federal Specification W-l-530a "Insulating Oil, Electrical (For Transformers, Switches and Circuit Breakers)." This standard specifies the physical properties required, establishes quality assurance provisions, and gives instructions for testing. It identifies several ASTM documents as forming a part of the specification. 11. FSS-G6A Federal Specification W-l-1219 "Insulating Fluid, Electrical (Noncombustible)." This standard applies to "liquid of the chlorinated aromatic hydrocarbon type (askarels)" with coverage similar to that of W-l-530a. National Electrical Manufacturers Association, 155 E. hit Street, New York, Nev York 1001T. ^Federal Supply Service, General Services Administration, Washington, D.C. 20^05 h7 HONS 047183 The following standards relate to the specifications and performance of the transformer itself: 1. ANSI C 5T.12.00-1973 (also IEEE #fc62) "General Requirements for Distribution, Power, and Regulating Transformers." This standard specifies (1} service conditions! (2) preferred ratings; (3) insulation classes and dielectric tests; (U) tolerances on losses, impedance, ratio, regulation and temperature rise; (5) tests; (6) such construction details as bushing class, marking of terminals, nameplate data, etc.; and (T) short circuit characteristics. 2. ANSI C 57.12.90 (also IEEE #262) "Test Code for Distribution, Power, and Regulating Transformers." This stands;a prescribes methods for performing the tests specified in C 57.12.00-1973 (above) and in the separate transformer standards of the C 57-12 series. The test methods covered are: (1) resistance measurements; (2) electrical Insulation; (3) losses and impedance; (It) ratio and regulation; (5) temperature rise; (6) insulation power factor; (7) polarity and phase relation; and (8) short circuit calculations. C 57-98, an Appendix to C 57-12.90, covers Impulse tests. 3. C 5T.12.90a-19T*t (also IEEE #262A) (Draft Standard) "Distribution and Power Transformer Short-Circuit Test Code." This code defines a procedure by which the mechanical capability of a transformer to withstand short-circuit stresses may be detsonstrated. Other standards and guides in the ANSI C 57 series (there are about 30) include such documents as: C 57.12.20-197^ "Requirements for Ovsrhead-Type Distribution Transformers 67,000 Volts and Below" C 57.12.21-1969 "Requirements for Pad-mounted Compartmental-Type Single-Phase Distribution Transformers" C 57-12.*t0-1967 "Secondary Network Transformers, Subway and Vault Type (Liquid Immersed)" C 57.100-1971* "Thermal Evaluation of Oil-Immersed Distribution Trans formera" C 57.93 (also NEMA TR-5-1956) "Guide for the Installation and Maintenance of Oil-Immersed Transformers" C 57-92 "Guide for Loading Oil-Ismersed Distribution and Power Trans formers" **. NEMA TR1-197** "Transformers, Regulators and Reactors" This document identifies the ANSI transformer standards which have 1*6 HONS 0A7189 been approved nr. NEKA standards and includes sort detailed specifications regarding such characteristics as audible sound levels, external clearances between live parts, accessories, and sons test procedures. 5. NEMA TRll-1967 "Snail Power Transformers with 65c Average Winding Rise and Distribution Characteristics." This covers electrical characteristics and mechanical features of this class of transformers. The above are representative of about ten KB4A standards dealing with various classes of transformers. 6. UL (Underwriters Laboratories) 506 "Specialty Transformers" This standard covers requirements for air-cooled transformers and reactors for general use but does not cover oil-filled units. T. AAR (Association of American Railroads) SM262 "Specifications for Impulse Transformer for Coded Systems Control." 8. AAR SMI65 "Specifications for Transformer, Oil-Immersed, SelfCooled." 9. PM (Factory Mutual) 5-27 "Fire Prevention Transformers." 10. FM 5-275 "Arc-Furnace Transformers." 11. FM lb-6 "Inspection and Maintenance of Transformers." (Note: Items 7-11 above are not in hand and thus no further description is available)- Section A.3.2 should be consulted for designation of the standards and techniques used for specifying and measuring the various fluid material properties identified In the above transformer standards. A.1.6 References, Section A.l Much of the material in this ssction was obtained through pereonal conversations with the manufacturers and users cited in the introduction. In addition to these personal communications, the following sources were found to be helpful: i. In Re: Proposed Toxic Pollutant Effluent Standards, (EPA) FR1 Dec. 27, 1973; testimony on behalf of: 1 Federal Register <*9 MONS 047190 a. General Electric Co., Mr. George B. Farnsworth, March l*t, 197** b. Westlnghouse Electric Corp., Dr. Janes H. Wright, March 15, 197**- ii. "The Role of Polychlorinated Biphenyls in Electrical Equlpnent," General Electric Co., Schenectady, N.Y., Feb. 1*, 1972, {internal publication). . ill. "Study of the Potential Impacts of the Proposed Toxic Substances Control Act, as Illustrated by Senate Bill S. 776," for Manufacturing Chemists Association, Washington, D.C., by Foster D. Snell, Inc., June 26, 1975- lv. National Conference on Polychlorinated Biphenyls, sponsored by Environmental Protection Agency, Chicago, Illinois, Nov. 19-21, 1975. The foil wing specific references have been cited in the text: 1. "Transformer Askarel Inspection and Maintenance Oulde," Monsanto Company Bulletin No. IC/FF-38R, revised March 1975* 2. R. N. Sillers, Electrical Insulating Materials. IEB Monograph lit, 1973; Section 10.2.1. 3. II9CFR1 100-199, revised October 1, 1971*. It, "Oil Pollution Prevention," Environmental Protection Agency, 38 FR 3**l6*t. December 11, 1973. 5. C 57-12.1iO; American National Standards Institute. 6. P. Barkan, et. el., "Overpressure Phenomena in Distribution Transformers witff Low Impedance Faults: Experiment and Theory," F T5 U6b-8, IEEE PE8 Sumer Meeting, San Francisco, Calif., July 19T5. 7. E. A. Goodman, L- Zupon, discussion to Barkan paper (F 75 **6U--8). 8. M. A. Nettleton, "Explosions Due to Faults in Electrical Equipment," Electrical Review. July 25, 19T5, PP- 116-119* 9. D. J. Ristuecia, R. E. Benton, "Ten Most-Asked Questions on Violent Transformer Failure," Transmisalon and Dlatrlbutlon, January 1975, pp. 30-31. 1,C* od^e of Federal Regulations 50 MQNS 047191 JO. A, I. Knovlton, editor-in-chief, Standard Handbook for Electrical Bnalneers. Hlntb Edition. McGraw-Hill Book Co., Mew York, 1957, 1-561, l*-570. 11. National Electrical Code, 1975; Bee. **50-2U, "011-Insulated Transformer* Installed Indoors," MFPA, Boston, (also see Ref. 10, Sections 15-102, >*-572, lU-300). 12. National Electrical Code, 1975; Sec. U50-23, "Askarel-Insulated Transformers Installed Indoors," NFPA, Boston. 13. D. A. Duckett, "Catastrophic Explosion Tests In Insulating Fluids," RTE Corporation, Vaukesha, Wisconsin 53186, November 9, 197**. 51 MOMS 047192 A, 2 "ABkarel-claBs" Capacitors A.2.1 Description of the "askarel class" of capacitors Ab In the case of transformers, there is also a wide range in types and Blzes of capacitors which are used In electrical apparatus. These are used In electronic circuits, for electric energy storage, and for power factor correction purposes. Their ratings can range from a few picofarads to many microfarads, with voltages from a few volts to over one-hundred kilovolts. Although some high-frequency capacitors use air insulation, most capacitors are made up of multiple, thin layers of metal and solid insulation. To eliminate any weakening hy the presence of air, these layer assemblies are then totally immersed in a liquid dielectric1; often paper is used aB one part of the solid Insulator, and this paper is impregnated hy the liquid. In addition to being a good electrical insulator, the liquid should have a high relative permittivity (high dielectric constant, c/c0). The PCBs possess both of these features, and so grades of capacitor askarels have been used in capacitors since the introduction of the askarels in the 1930's. Whereas only a small percentage of transformers contain askarels, nearly one-hundred percent of power and industrial liquidfilled capacitors use this type of liquid lnsulant. Because of the widespread use of PCBs in capacitors, Monsanto in 1971 introduced a more environmentally compatible formulation, Aroclor 1016, especially for capacitors. In 197**, Monsanto sold 21,955 thousand pounds of this fluid; the capacitor market for PCBs Is considerably greater than the transformer PCB demand. The market value for PCB-lnsulated capacitors Is In excess of $100 million per year. Askarel capacitors are often divided into two categories, "power" and ''Industrial.*' The power capacitors are high voltage units which generally contain several gallons of fluid. They are used for power factor correction to increase the efficiency of the electric power system. Additional uses in the "power" category lncluds dc filters, energy storage, and induction heating capacitors. "Industrial" capacitors are generally smaller units which serve a large number of purposes Including motor start snd run, and fluorescent light starting. They are also used in arc welders and power supply filters. The industrial class of capacitors is estimated to use one-half to two-thirds of the demand for capacitor aBkarels. ^Except for a few capacitor types, e.g., mica capacitors, which use only solid Insulation. 52 MONS 047193 Capacitors u' both categories are ^-snerniiy constructed by winding alternate sheets cf metal foil and paper and/or film dielectric in round or flattened rolls. These rolls are connected together inside a closed metal housing which is filled with an askarel. The paper dielectric material has a high permittivity, but it is dried before assembly into the capacitor, and it contains a large volume percentage of open air space. The askarel impregnates the paper, filling the air-Bpace voids. Askarels are superior to mineral oil for this dielectric application because the high permittivity U ^ 6e ) reasonably matches the paper, and therefore causes less non uniformity in electrical stress. The net high permittivity and the high dielectric strength of the askarels also allow for a smaller capacitor for a given power or energy rating. This combination of high permittivity and high dielectric strength alone would suffice to make askarels favorable impregnants for capacitors. Our survey of manufacturers and users indicates that they generally have also come to depend on the stability and nonflammability performance of askarel capacitor fluids. Since power capacitors are often out-of-doors or in vaults, however, it appears that more flammable fluids may in the future be more readily accepted. This may not be true with the industrial capacitors which are often installed in potentially flamiable environments, for example, fluorescent light fixtures and appliance motors in buildings. This flammability issue is further discussed In A.2.3. In considering test techniques for alternate capacitor fluids, then, we can at this time identify the following factor? as significant: dielectric constant (relative permittivity, e/eo), dielectric strength, impregnability, flammability, and stability. Toxicity, environmental degradability and compatibility with other capacitor materials are added to the list in subsequent sectloas. There Is an Important economic interdependence between the capacitor and transformer fluids markets which should not be overlooked in deciding on alternatives to PCBs. The capacitor and transformer askarels have different percentage contents of various PCBs, but they are both formulated from the same basic stock. They, therefore, aid each other In achieving the cost advantages of large scale production. Any shift of either market away from aakarah would influence the price of the askarels for the other use. This facter should be considered in evaluating the relative cost advantages of substitutes for PCBs. A.2.2 Probability and consequences of rupture The rate at which the small industrial capacitors experience a tank-rupturing failure is very low; and when one of these small capacitors fails, there is little loss of fluid.1 The total amount of fluid in all 3mall industrial capacitors is, however, large, as was mentioned previously. ^In a capacitor containing paper insulation, 80$ of the fluid is absorbed and 30 will not spill out even if the can doeB rupture. 53 MOWS 0^719** In the case of the larger, pover-type capacitor, the failure rate has been historically low. Generally, a capacitor will fall by an Internal arc short-circuiting the unit. Each power capacitor should be individually protected by a current-limiting fuse1 which will blow when the capacitor falls, leaving the capacitor-fuse unit open-circuited. If the industrial capacitors contain more than 3 gallons of "flammable" liquid, the National Electrical Code also directs that these be enclosed in a vault if indoors or within a fenced enclosure if outdoors (NEC-1975, Art. U60-2). Often, power capacitors are used in parallel-series connected groups, or banks, and upon failure of one capacitor in the bank, all parallel capacitors will try to discharge through the failed unit. A current-limiting fuse on each unit limits this "in rush" current in order to protect he other capacitors in the bank.2 NEMA standards^ exist for identifying the proper fuse to use to protect any given capacitor. These are somewhat out of date, however, so a manufacturer will generally provide the necessary information for his capacitors. There is need, therefore, for a newly created set of industry-wide standards for protection of new capacitor designs with new types of lmpregnant dielectric fluids. A.2.3 Full capacitor arc testing We have established in Section A.l that nonflammability is an important characteristic of "sskarel-class" transformers and that the insulating fluid has been in the past and should continue to be qualified by full transformer arc testing. We have also recognized the importance of nonflammability of capacitors, but it must be reported that there le little documented experience or interest in arc or flame testing of capacitors. The apparent Justifications for this lack of testing are the low rate of capacitor failure and the small amount of fluid in any one capacitor. Fuse protection as described in A.2.2 also reduces concern for rupture and fire. ^The National Electrical Code calls for "overcurrent protection" on any capacitor operating at potentials greater than 600 V (NEC-1975; Art. 1*60-25). 2 Power capacitors on distribution feeders are often group fused* a CP 1-1971, "Shunt Capacitors," National Electrical Manufacturers Association, New York. See also ANSI C551-1966 (IEEE No. 18), "Shunt Power Capacitors." 5li MQNS 047195 In evaluating the need for full unit flammability testing of capacitor*, one should also keep In nlnd the following factors: a. Hew candidate capacitor dielectric fluldB generfclly are more flammable than askarels. b. The paper and film, vbich make up a large percentage of the bulk material within a capacitor, are generally flanable. c. Power factor correction capacitor* are generally used not elngly but rather In large multiple-unit banks. A study should therefor* be made of the probability of fire spreading from one faulted unit to other capacitors in the bank. d. UBe of many capacitors In large, closely spaced banks also has another riBk. Unless each capacitor is properly fused, all parallel branches of a bank can discharge through a Blngle unit which develops an internal, short-circuit fault. Fusing requirements of capacltorB with new fluids should thersfore not be overlooked. Manufacturers of fluldB and capacitors have privately run occasional 4rc testB on capacitors to study flammability effects after a tankrupturing fault. Ko definitely recosnended format for such tssting has been brought to our attention, however, and the indication is that considerable design and testing would be required before a quantitatively Interpretable and repeatable test could be devised. Several parties Involved In the manufacture and use of capacitors did, however, feel rather etrongly that euch a test should be developed, particularly in light of the increased flssmability of the new fluids. A.2.h Effect of alternative fluids on design and testing of the full capacitor unit The dielectric fjyid must be compatible with all other materials with which the fluid makes contact insids the capacitor casing. As In the transformer situation, the inside coating of the metal capacitor tank must bs nonreectlv* with the fluid. Since the fluid permeates directly to the metal foil electrodes, either the metal and fluid must be compatible or the metal must be treated with a protective coating. In capacitors, the most serious material coordination problem Is between the fluid and the Insulating sheets which separate the foil electrodes. If this is a paper, then the fluid must be able to completely Impregnate the paper, leaving no voids In which corona discharges can be Initiated. Although certain fluid characteristics such as molecular weight and viscosity will help to screen out obviously Improper fluids, adequacy of Impregnation it beet evaluated finally by testing the lmprsgnent fluid in a true film-electrode capacitor geometry. 55 HONS 047196 One should be on the watch not only for lnnediate corona from inadequate impregnation, but alto for weakening of the dielectric strength of the fluid, which can result from the fluid dissolving Impurities out of the solid Insulation material. Incompatibility of a new fluid with the existing film and paper may be solved by selecting new paper and film rather than by rejecting the new fluid. Thus, tests must be devised so that combinations of fluid and solid films can be evaluated on a controllable and comparative basis, and criteria for interpreting these teats must be devised in order that new fluids are not rejected merely because of inadequacies In the paper or film. The best practical combinations of fluid and solid must be compared. In the previous paragraph, we aought the beat combination of lmpregnant and paper from a matarlala compatibility atandpoint. It ia Important, however, to alao coordinate dielectric characteristics. Severely mismatched dielectric constants will cause very uneven electric stress which can lead to corona and flashover in the more highly stressed member. Thus, askarel Is a good fluid to use with paper since both have relatively high dielectric constants. The plastic films which are new In use In capacitors, such as polypropylene, have lover dielectric constants, and are therefore more compatible with lover dielectric constant fluids. Using lover dielectric constant materials means that the capacitance per unit area of electrode is less for a given electrode separation. Larger voltage or slse are therefore needed for the same energy storage Regardless of vhat material is selected, its dielectric constant should be accurately known under actual operating conditions, and its dielectric constant should be measured with the material In the true operating electric field. This may suggest that an extension be made in the ASTM standard teat for dielectric constant (D ?**). The slse of the capacitor is Influenced not only by the dielectric constant, but also by the dielectric strength. Decreased capacitance and energy storage beeguse of decreased dielectric constant can potentially be regained by higher dielectric strength materials which allow higher fields and voltages. The design of the capacitor is, therefore, influenced by the dielectric strength (breakdown Strength) of the fluid. The breakdown strength of the fluid itself may be measured by stsndard test proesdures, ss described in Section A.3.2. Final capacitor designs, and test cspscltor geometries can be svaluated by methods outlined In Section A.2.5. The maximal operating'voltage of a capacitor Is generally aet by Its corona Inception and extinction levels, rather than by the flashover voltage. The low current, but continuous corona discharge causes damage to solid and liquid dielectric material and therefore leads to short life and failure of capacitors even though the operating voltage may be well below the breakdown level. Detection and measurement of corona and particularly of its inception and extinction points are therefore 56 MQNS 04719? extremely Important In order to specify the maximum eafe voltage for long life. Theae corona levela are not characterlatlc of Juat the lnaulatlng fluid* itaelf* however* but rather of the fluid In the actual electrode configuration, Including the electrode material, the microscopic surface conditions, and purity of the electrode/fluid Interface. An absolute measure of corona Inception for a pure. Isolated fluid Is therefore of little value, and one must Instead determine the Inception level for the whole electrode/insulator configuration, assembled according to routines which would be followed In manufacture. Corona measurement techniques are specified* for example, in ASTM D 1868-73. ' In addition to corona, losses In capacitors result from resistive and dielectric properties of the fluid. Theae can generally be evaluated for the pure. Isolated iiquld as described in Section A.3.2. The measurement should duplicate operating conditions (frequency, temperature, electric field) as closely as possible. Oenerally* higher dielectric constant materials exhibit higher loss, because of the large and rapid molecular polarisation changes required by high permittivity materials In ac fields. A final important characteristic of the capacitor dielectric fluid is Its stability. It must show little change in dielectric, chemical or physical characteristics under actual electrical and thermal operating conditions over the many years sxpected life time of the capacitors, frequent consents from fluids manufacturers, capacitor manufacturers and users brought out (1) the importance of this characteristic, (2) tha difficulty in defining and measuring stability, and (3) the importance of the measurement being in as realistic an environment as possible^ l.e., in a teat capacitor configuration. In conclusion, this section has shown that the particular dielectric fluid chosen for a capacitor has a major effect on the total capacitor design. Consequently, and of more major importance to this study, we can further conclude that all aspects of new capacitor dielectric fluids finally need to be evaluated in an environment which simulates realistic operating conditions. A.2.5 Test techniques and standards employed by manufacturers and users to evaluate fluid-filled capacitors The capacitor manufacturers and users havs the following standards dociaents available for guidance in selecting and handling tha insulating fluid. '' 1. A1TSI C 59:11 (alto ASTM D 2233-71*) "Standard Spbclficatlon for Chlorinated Aromatic Hydrocarbons (Askarels) for Capacitors." This document gives detailed spaciflcationa of the physical, chemical and slectrlcal properties of four askarels which have been used as capacitor laprsgnants and details test methods. 57 HONS 047198 2. ANSI C 59-123-1970 (also ASTM D 2297-60) "Standard Specification for Continuity of Quality of Electrical Insulating Mineral Oil for Capacitor a and Cable Accessories." , This document provldea detailed apeclflcationa of the physical, chemical and electrical properties of the oil. 3. ANSI C 59.122-1970 (also ASTM D 2296) "Standard Specification for Continuity of Quality of Electrical Insulating Polybutene Oil for Capacitors." This document provides detailed specifications of the physical, chemical and electrical properties of the oil and details test methods. It. ANSI C 107.1-197** "Guidelines for Handling and Disposal of Capacitor- and Transformer-Grade Askarels Containing Polychlorinated Biphenyls." This docment gives the typical physical, chemical and electrical properties of aakarels used as capacitor lmpregnants, details methods of shipping and handling, spella out necessary safety precautions, recommends labeling practices and details approved disposal techniques. It slso lists organisations having facilities for analysis and for disposal and details an analytical procedure for the determination of airborne PCBs. The following standards Relate to tbs specification and perforaance of the capacitor itself: 1. ANSI C 55.1-lJge (IEEE No. 10) "Shunt Power Capacitora" Definition of terms, ratings, tolerance, operation, production and design testing, fuming. Such characteristic! aa stability, corona start, radio influence voltage, overvoltage, capacitance, leakage, loss and dielectric withstand are identified, but the specific detailed teat techniques are not described, nor are appropriats ASTM procedures cited. Thla standard la for shunt power capacitora without reference to the dielectric fluid; with nonaskarel fluids, certain specified values and limit* might possibly have to change, and specific test procedures may not be the same aa have been traditionally uaed for askarel capacitors. 58 47199 hqns 2. ANSI C 55-2-1973 "Series Capacitors for Transmission and Distribution-line Compensation" This standard includes requirements for safety, rating, and gap settings; functional requirements for protective equipment, alarm devices, servicing, type, and routine tests and a guide for operation. 3. NEMA CPI-1971 "Shunt Capacitors" This standard is similar in coverage to AESI C 55-1- fa. ITA^ HS-392 "Fixed Paper Dielectric Capacitors for Alternating Current Applications" This standard covers the requirements for oil-paper dielectric capacitors hermetically sealed in metal cases for general purpose application on ac voltages. It specifies (1) standard designations, (2) standard test conditions, (3) marking, (fa) quality assurance test programs, (5) tests, and (6) applications suggestions. Although the term "oil" is used, this standard la.meant to apply to askarel-fllled capacitors. I 5. EIA RS-392-1 (AH8I C83.67a-197fa) "Fixtd Paper Dielectric Capacitora with Ron-PCB Impregnant for Alternating Current Application" This standard applies to capacitors with paper dielectric impregnated with non-PCB fluid, llote that there la no existing BIA standard covering non-PCB capacitor fluids with plastic film dielectric. 6. EIA RS-faOl "Paper, Paper/Film, Film Dielectric Capacitors for Power Semiconductor Applications" The coverage of this standard la similar to RS-392 above. O 7. ~UL 810 "Cdpaeitora" (power factor correction capacitors up to 15 kVsr or 600 V) This standard doea not cover capacltora Intended for use as parts of appliancts, motors, transformers or slsctrlc-discharge-lsmp ballasts. It does not specify that the liquid used be nonflammable, but does require that tha oapaeltor be marked to "Indicate whether the liquid is combustible or nonflasable. If the liquid la combustible, the amount of the liquid in gallons shall be indicated." ^Electronic Industries Association, 2001 Eye Street, Washington, D.C. 20006. ^Underwriters Laboratories, 333 Pfingsten Road, Korthbrook, Illinois 60062. 59 047200 A,2.6 Reference*! Section A.2 Much of the material In thla section was obtained through personal conversations vith the Manufacturers and users cited In the introduction. In addition to these personal comunlcations, the following publications and reports were found to be helpful: 1. R. H. Munch, "Mew Capacitor Iapregnanta," Conference paper presented at IEEE Power Engineering Society Meeting, Mew York, New York, Jan. 30, 1975. 2. B. H. Goldy, H. 0. Solberg, "A Mew Liquid Dielectric for Capacitors," Insulatlon/Clrcults. Jan. 1975* 3. John Lapp, "Concepts in Systems Testing of Dielectrics in Capacitors," IEEE Trans, on Power Apparatus and Systems, Vol. PAS 91*, Jan/Feb. 1975, pp. 66-71. ^ li. J. H. Wright, "Coaaents of Westingbouse Electric Corporation." Testimony at hearings regarding "Proposed Toxic Pollutant Effluent Standards" (EPA) (FR Dec. 27, 1973) given March 15, 197*. 5. L. L. Jackson, "Industrial Organic Chemicals as Altsrnativ* Dielectric Fluids," Conference paper presented at IEEE Power Engineering Society Meeting, lew York, lew York, Jan. 197*. 6. Stateaant of Eleetronica Industrie* Association, to EPA, concerning Proposed Toxic Pollutant Effluent Standards, in a letter to the Honorable Russell Train, Administrator, June 25. 1975. 60 0*t72Ql kons A.3 Dielectric and Insulating Fluid# A. 3.1 Available Fluid# In thi# aectlon ve shall treat the major material# available at the present time or potentially available to the electrio power Industry as transformer and capacitor fluids. The power industry in general has viewed with reluctance any change from the use of askarela in certain transformer and capacitor applications because the askarels possessed outstanding electrical characteristics. Furthermore, the askarels have low flammability, and, while not inexpensive, their cost has been at a level the Industry could manage. It Bust be emphasized that there is no other fluid now available which hat quite so broad a range of application and usefulness In the electric power Industry. . The major fluids proposed as substitutes for the askarels In power transformer and capacitor applications are for transformers: (a) silicone liquids, (b) mineral oils, (c) highly saturated paraffin oils. For capacitors, the fluids are (d) diaryl aulfonaa and mixtures, (e) long chain estera of phthallc acid and (f) alkylated monoohlorodlphenyl oxides. The Japanese are reported to be working on a dlarylalkane substitute, and the French on "Chloralkylene," an Isopropyl chlorinated biphenyl.1 There are other fluids which have high dielectric strength and excellent electrical properties such as the fluorocarbons and the perfluoroalkyl furans. These are marketed for use in small devices. Their cost (*25 per liter, end up) probably prohibits their use at the present time in lapge installations such as those that interest ua here. ' A table listing the properties of interest of the fluids described here la appended at the end of this section (page 72). Before proceeding to the consideration of the nonaskarel fluids s few remarks on tbs askarels themselves may not bs amiss. ^Reported at the Rational Conference on Polychlorinated Biphenyls, btvlronmental Protection Agency, Chicago, Illinois, November 19*21, 1975- 6l MONS 0^7202 The Askarels (Polychlorobiphenyls) The askarels are proprietary mixtures of chlorinated biphenyls and chlorinated bentenet, the empirical formulas of which are Cl,c,, Hl,O_ -n Cl n (where i way run from 1 to 10) and Cg Hg_n Cln (where n_ say run from 1 to 6) respectively. These compounds may be represented by the general structural foranl a: m Cl chiorobiphenyl a chlorobentene The proprietary mixtures mentioned above usually are designated as having an effective percentage of chlorine and this percentage usually appears somewhere in their trade numerical designation. The singly chlorinated biphenyls are light oils snd the completely chlorinated (n * 10) biphenyls usually assume the character of a resin or wax. Although first synthesised nearly a century ago [l]1, it was not until the third and fourth decades of this century that they were produced in considerable quantities [2]. It was during these decades that the superior electrical properties of these materials become apparent. Within a few years, large scale manufacture of the askarels was undertaken [3]. Besides the excellent electrical properties and the low flanmabllity of the askarels, it was observed that with the somewhat higher dielectric constant over, say, transformer oils, the capacitor dimensions could be reduced [U]. The askarel fluids have been used in a vide variety of applications outside the electric power industry, mostly as heat transfer fluids, additives to petroleum oils, in textile coatings and in surface coatings snd paints [5)- Applications to sealing compounds, printing inks and papers, and casting waxes are all well attested [5]< The variety and successfulness of application of the askarel mixtures has led to widespread use and unfortunately to their widespread occurrence in the environment. Most of the areas where the polychlorobiphenyls occur in the environment are, of course, associated with eminently intense industrial sctivlty. However, the high chemical stability of the askarels insures their persistence wherever they are transported. References for Section A.3, shown in brackets, will be found in A.3.T. ' 62 HONS qj*7203 The result is thst they are found at some polluting level In e greet many places around the world. The polychlorob1phenyls have been documented as existing in tlorth and South America in both marine and freshwater environments [6-10]. A detailed discussion of these findings may be found in Kimbrough's comprehensive review paper [11]. . There would seem to be little point in expatiating Upon the toxicity of the polychlorobiphenyls In this brief resume since this report concerns the adequacy of tests of prospective replacements for these very fluids. Suffice it ,to say that the polychlorobiphenyls accumulate in, persist in, and are destructive to animal tissues. There it In fact a large body of literature supporting the toxicity of FCBs [see for example 11-15]. More recent reevaluation of poisoning incidents seem to indicate, however, that another substance, polychlorinated dibensofuran (PCDF, formed by oxidation of PCBs during thermal aging] was also present and may have significantly contributed to the toxic action [l6]. - ' < Silicone Liquids ! Probably the foremost contenders among the.silicone liquids as a substitute for the asharsls art mixtures of the dimethyl tiloxane polymers. These mixtures can be made up in a variety of viscosities. One of the most important properties of the dlmethylslllcone liquids is their low temperature coefficient of viscosity [IT]- They are also mechanically resistant to high shear rates [l8, 19]. These compounds are generally inert and art resistant to oxidative and thermal degradation [20, 21]. . The dimethylsilicome liquids may be compounded to have viscosities running from 1 to well beyond 30,000 ceotlstokes. The dielectric constants for all such mixtures remain In the neighborhood of 2.T over many orders of magnitude In frequency [22] and over a broad range of voltages [25]- The flagmablllty of the various mixtures exhibiting this viscosity range may be gauged by the range of the open cup flash points from about 3T C fof*n 1-centistoks fluid to about 320 C for a 200-centistoke fluid [22, 23]. The solid-liquid transitions for the methylsiloxane liquids thst interest us hare, occur for the most part in the neighborhood of -80 to -1*0 C [22]. The dielectric strength of these fluids is in the neighborhood of U0 kV/0.25 cm [22]. The dissipation factor is about 0.0003 at 100 Hs. All in all, these fluids are nearly ideal as power transformer fluids. They do not sludge or oxidise easily and with proper design one obtains good heat transfer. They offer good resistance to acid and alkaline contaadnants in a transformer. Offsetting these virtues somewhat is the fact that when these fluids are subjected to arcs their dielectric strength may be reduced by the formation of solid 6i0g filamentary bridging. In addition there seems to be a possibility of silicon carbide, SiC, being formed in an arc in these 63 MON* liquids. Silicone .nrblde is conductive and refractory, and provide* another impediment to the self-healing of the dielectric liquid [2U], However, It is claimed that self-healing does occur if the liquid Is impregnated into Kraft paper. These drawbacks are much more detrimental to applications in capacitors than in transformers and explain why the liquids are proposed mostly for transformer use. Since the breakdown products of the silicones resemble the products from which they are synthqsised, a few words should perhaps he added here about the chemistry of silicone liquids. Vhat is given below is not meant to represent current proprietary methods of silicone liquid production but to give elementary background material for discussions elsewhere in the report. Early expectations that silicon would possess a structural chemistry analogous to carbon organic chemistry were never fulfilled. Saturated silicon chains analogous to the paraffins can indeed be formed but the silicon-silicon bond is relatively weak. At the beginning of the century Alfred Stock prepared the first few members of the silicon hydride series by dropping [see 26] acid on magnesium silicide: MggSi H Cl S1HU + 8i2 Hg + Si3 Hg + . . . + MgClg . He found that the hydrides were unstable and he was not abla to prepare any compound in pure state higher than 81^11.. [see 26]. The modern silicon compounds which are of interest here^ao not rely on the St-Si bond which is subject to oxidation but upon the stable 81-0-81 bond. From this bond true polymers may b* constructed as was evidenced by the thorough investigstion of compounds of this class by Kipping in the first hair < f the century [see for instance, 27]. We might pursue one possible path to synthesis of a dimethyl silicone. If ve treat sand (SiOg) at about 1000 C with chlorine gas snd a reducing agent (carbon) an important product will be silicon tetrachloride, a corrosive liquid at room temperature (SiClj,). Use of a methyl Orignard reagent (CHjMgCl) will allow attachment of methyl groups to the silicon atom: * 2 CH^HgCl - UH3)2 SiClg + 2 MgClg . This last step is performed commercially by causing silicon to react with methyl chloride at 250-300C with a metal catalyst 81 + 2{CH3C1) (CH3)g - 8i - Clg 6b MGNS 047205 Ths dimethyl silicon dlchloride is most useful because ve simply allow it to react with water: ch3 CH 3 Cl Si Cl + 2HgO + HO - 8i - OH + 2 HC1 ii CH, CH 3 This product is called dimethyl dlsllsnol and will undergo a dehydratlve condensation, thus: CH f3 CH, i3 CH 3 HO C - OH + HO Si OH + HO - Bi Ii i CH CH CH 3 0 ?3 Si I OH + V CH, giving us a primitive dimethyl silicone. A glance at the equation will suggest to the reader that longer chains and cyclic compounds can be built up from our simple silicone, and such is the case. Or course the last reaction may he reversed by altering the conditions, i.e., nay yield sHanois from silicones, a point of interest in the study of the manner in which these compounds may degrade in the environment. These compounds are considered combustible but they have no true coifcustion points. Combustion can be sustained if the heat supplied to the compound is sufficient to cause depolymerisation or decomposition. Thus, only the short chain polymers really burn [25, 28]. The low toxiclt^of the silicone liquids is claimed as an advantage of their use in the applications which concsrn us here. Indead there la little In the literature to refute the contention that the material has extramely low toxicity, and numerous toxicity studies have been conducted at the behest of the manufacturers of the silicones. Mineral Oils Most of the oils used as transformer fluids are complex mixtures of paraffinic and aromatic compounds (as inhibitors) of miners! origin. Many these paraffinic compounds art both saturated and cyclic. Such cyclic compounds sre designated as "naphthenic" by tha petroleum industry. 65 MQNS 047206 The oils sre nearly always ths result of a process where the refining method is tailored to the final use of the product. The aromatic content of the oil must he controlled In order to prevent sludging or oxidation of the paraffin components; but some aromatics are added as oxidation inhibitors. A typical additive which is compounded with the oil as an antioxidant is ditertiary butyl paracresol (JWBP or DBPC) which frequently is added to the extent of a few tenths of a percent [2UJ, Such antioxidants are largely confined to distribution transformer applications. The use of such cosipounds it largely avoided in power transformers where the fluid is hermetically sealed into the transformer under a blanket of nitrogen gas. The addition of aromatic compounds is also designed to inhibit gassing in an oil under the operating conditions of a transformer. The low cost and self-healing properties of mineral oils coupled with their satisfactory electrical properties have contributed to their widespread use. These oils have a dielectric constant of about 2. The dissipation factor is about 0.001 at 60 Hz. The dielectric strength of mineral oils is generally greater than 30 kV/0.25 cm, and 1012 ohm-cm is a typical value for the resistivity of e fresh oil. The toxicity of oils composed entirely of saturated paraffins is very low. Highly saturated oils find perennial use in cosmetic products. Gome of the highly refined oils are pharmacopoeal. The pretence or addition of aromatic inhibitors increases the toxicity of the oils. The degradation of a pure oil in a normal atmoephere probably follows the course of oxidation of alkanes to, ultimately, carbon dioxide and water. Such a process would require high-energy radiation (ultraviolet) for initiation of the reaction. The mechanism of this process is not yet clearly understood because of the paucity of knowledge of slow reactions [31]. All paraffins are to some slight extent soluble in water and can therefore in time react with compounds present in natural waters. Furthermore, volatile fractions of an oil may sscape into the atmosphere where if they are excited by energetic radiation they may form free radicals which readily react with atmospheric components. Whatever the details of the case, it is believed that the degradation products whether produced by physical or biological means are not highly damaging to the environment. The flammability of the mineral oils is considered high since they are hydrocarbons with no quenching atoms (such as halides). If the oil is to be suitable for transformer use It must be both insulating and non-viscous at operating temperatures since it will be used as a convective heat transfer fluid. However in general, the less viscous an oil, the closer it is to its flash point so that a compromise between hazard of fire and efficiency as a heat exchanger is required. These considerations have led power companies to the use of oil in transformers almost exclusively in exterior installations. If a transformer operates with the insulating liquid at a temperature far below its flash point the hazard from fire would seem to be minimal. 66 MQNS 047207 Thsr* la some advocacy (aac for example Duckett PTE Corp., [30)) of using high-purity high-flash-point paraffin olla In inside inatallatlona, much aa askarels are uaed at preaent. The teat used to suggest the auitahllity of olla la diacuaaed in the next aectlon. Hydrogenated Paraffin Olla One auggeated fluid for transformer uae la a product which the FfTE Corporation of Waukesha, Wisconsin la propoalng as a substitute for askarels In transformers In locations proximate to or Inslds buildings. The firm maintains that the high flash point and consequent low flammability of this oil so much reduces hazard from fire in interior installations that the fluid should qualify for service in such installations. This fluid is not produced by the KTB Corporation itself. The supplier is a large oil company [29) end the fluid was designed, or expected to be used, in transformers which operate at temperatures high enough to reduce its viscosity to an acceptable level. The product is marketed as "RTemp." The composition does not appear to bs anything unusual In the way of petroleum oils. It is a high-vlscoslty (flOO cs at 2? C), high-flash-point (296 C) oil with a dielectric strength of about 37 kV/0.25 cm, (ASTM D077), and high resistivity, 10iJ ohm-cm. The oil is a petroleum product twice subjected to a hydrogenation process, thereby acquiring its saturated paraffinic properties. RTemp is therefore a highly stable mineral oil which is claimed to be of food grade (30). It Is presumed that the environmental characteristics of this highly saturated oil would be similar to the pharmacopoeal mineral oils [30). The general physical and electrical properties of this oil resemble the ordinary transformer oils. The flammability properties of RTemp transformer oil are better than moat transformer oils as would be indicated by its high flash point. The expected lower flammability la confirmed in a general way by the surge-cell tests conducted at RTE Corporation by Duckett (30). The surge of electric energy into the oil caused vaporization of the oil and dispersal of the oil outside the test apparatus. Vo fire resulted, however, because the temperature of the liquid oil was wsll below the combustion point. This behavior was in marked contrail to an ordinary transformer oil subjected to the same test which ignited Immediately and did not extinguish, possibly because the transformer oil was initially closer to its flash point than the RTemp and considerably less tnsrgy was required to bring the transformer oil to combustion temperaturs. Oils of the highly saturated type are used in cable and underground applications. In spite of the high viscosity of such oils they are acceptable at the coiaon operating temperatures of transformers In temperate, or even moderately cold, weather. But in the severest cold these oils require the protection of enclosure or burial to maintain their fluidity. Although the PTE surge tests show, and the combustion data predict, that these highly saturated oils are probably safer than ordinary transformer oils, the National Electrical Code Committee will probably need independent testing before explicit acceptance of this fluid. 67 HONS 047208 Mixtures Containing Diaryl Bulfonea These compound* are proposed by one of the major chemical companies of the country as substitutes for the askarels in capacitor use. Tbs basic chemical structure is: where the R is an alkyl group with probably 1-8 carbon atoms, n runs from 1 to 3 and Af Is a pbenyl, naphthyl or lndan group. All these compounds are halogen free [35]* The actual product Is presumably a proprietary mixture of such compounds and other Ingredients such as non-chlorlnated biphenyls. Cited es en example in German and U.8. Patent disclosures [32] is s mixture of tolyl xylyl sulfooe, isopropylbiphenyl end minor ingredients. It is presumed that in use further ingredients will be added to these compounds as antioxidants. The mixtures as proposed have a dielectric constent of about 6. No dielectric strength figures are available at present, but life-tests of capacitors are continually being run by the manufacturer of the fluid [33]> The fluid is tested in ballast-capacitor use fct 1000 volts at 90 C working temperature. The flash point of the mixtures now advocated by the manufacturer it about 150 C, combustion is sustained at about 165 C and the fluid will suto-lgnite In the region of l90 C. The termlnal-to-case resistance is listed as *3 x 10? ohm, the dissipation factor as shout 0.003 [3I). No pourpoint figure is available but the capacitors function well at -50 C [33]. Boas toxicity studies have been conducted by the manufacturer. These studies indicste that irritation can be Induced by intense or prolonged contact of the mixture with eye or skin of rodents. The manufacturer recommends that normal Industrial hygisnlc^recautlons be taken (attainable, in the main, with soap and water) in order to assure safe handling. These materials when fed to rodents broke down into excretable metabolites according to studies conducted by, or on order of, the menufacturer. Polychlorobipbenyls fed under similar conditions persist in tbs snimal body after the eulfone mixtures in the tissue have become undetectable. A toxicity statement is available from the medical department of the manufacturer [35]. 68 MQNS 047209 The Phthalate Esters The phthalate* can be offered Immediately ae products for uae Id the capacitor Industry because they are already supplied by the petroleum Industry as plasticizers for polyvinyl chloride plastics In tonnage quantities. Zn 197?. about 1 billion pounds of some 20 different phthalate estere vere manufactured [36]. The generally excellent electrical characteristics of the esters of phthalic acid make the* natural candidates as substitutes for the askarels in selected capacitor use should the substitution become necessary. They muit be United to low voltage applications, however, because of the problem of corona extinction In the phthalate esters. The phthalic anhydride is typically manufactured fron naphthalene which Is oxidized in the presence of vanadlus oxide to phthalic anhydride _ or alternatively from o-xylene by a similar oxidation process to the same end product The phthalate esCtrs supplied as insulating liquids are mostly diisononyl phthalate (DIRT) and dioctyl phthalate (OOP) [371 - One major manufacturer prefers DIHP Over DOP because of the expected resistance to hydrolysis bestowed by starlc hindrance. The chemical and petroleum companies use various methods for producing the alcohols from which OOP and DIOP are formed l all of which start from petroleum refinery products. They may be typified by the one reaction for 2 ethyl-hexanol which begine with propylene to fora e aldehyde which in turn, by aldol condensation, yields a Cg aldehyde. The Cg aldehyde is hydrogenated to 2 ethyl-hexanol. 69 HONS 047210 C* aldehyde -- 2 ethylhexenol. The 2-ethylhexanol then esterlfles the pbtballc ecld s 0 + (2 R-OH) / C-O-R C-O-R producing the well-known plasticiser 2-diethylhexyl phthalate. 1 The octanols and lsononanola used In the manufacture of Ineulatlng fluida will uue the aaae or siailar reaction! -n their preparation. The aromatic dlhaalc phthalate eater! typified by diiaononyl and dloctyl phthalate hare pacific realatancen In the neighborhood of 101? ohm-cm. In application! aa capacitor fluida they offer a dielectric constant of about $. The voltage breakdown point occurs at around 30 kV/0.25 cm. The boiling point at reduced pressure (5 aa Hg) is about 230 C, and yet the pourpolnt Is in the neighborhood of -50 C. The flash point aa determined by the Cleveland Open Cup Method for these fluids la In the neighborhood of 220 C; fire point Is deterslned by shoving that coabustlon Is sustained at 250 C or thereabout [3fl]. The dlhaalc phthalate esters are available on the market, apparently In any quantity daalred and are Marketed toy at least two | major chealcal companies. At least one equipment manufacturer has modified the design of his capacitors to accoosBodate the pbthalatea as capacitor fluida [371 * Engineers from another capacitor manufacturer report that their commercial uae of the phthalate eatera haa been in low voltage electronic units for the export market. The report by Rutkovskl and Forster [38] presents a auMary of toxicity studies Indicating low toxicity and there la work supportive of the harmleasness of the pbthalatea (39 **0]. For detailed studies of the toxicity of the pbthalatea see [41]. 70 MQNS 047211 / Butylated Monochlorodlnhenyl Oxides On* of the largest chemical companies In the country has for some years been engaged in a Joint effort vith an electrical pover equipment manufacturer in the electrical and environmental evaluation of butylated monochlorodiphenyl oxides. This effort has resulted In the offering of a product to the electrical Industry which may be used In high voltage povar capacitors {b2]. The butylated monochlorodlpbenyl oxides are offered as direct replace ments for PCBs, I.*., no change in capacitor dimensions is required. The electric properties are similar to other dielectric fluids offered. The dielectric constant Is about 5 and the dielectric strength about 35 kV/0.25 cm. The resistivity is about lOf1 ohm-cm; the vapor pressure is low. At room temperature it Is about 10"4 torr. The viscosity is about 10 centistokes at room temperature. The pourpolnt is about -b5 C. The flash and fire points are considerably (about 100 C) above the operating temperature, and the flash point is above that of sosw of the lcrver-chlorinated aakarele. The values Of flash and fir* point are listed as 1Tb C and 199 C respectively by the manufacturer. Prolonged reliability teete have been performed, and the manufacturer has indicated a willingness to produce the material at the million poundper-anmm level [b2], Safety and performance teete vere, as of December 2, 1975, atlll being assessed. The manufacturer states that the major constltusnt of the fluid Is known to be nontoxic to fish. The minor constituent is slightly toxic to fish but Is also the more biodegradable. Solubility Is low as Is bloaccumulatlon. An environmental impact statement may be obtained from the manufacturer [*3]. T1 MQNS 0*7212 12 HONS 047213 1 I A.3.2 Standard* Relating to the Testing of Available Fluid* Three compilation* of ASTM teat procedure* relating to the performance of electrical lnaulatlng liquid* have been Issued: 1. AHSI C 59.2 <al*o ASTM D 117) "Standard Method* of T*tlng Electrical lnaulatlng Oil*" 2. AHSI C 59-62 (also ASTM D 901) "Standard Method* of Testing Askarels" ' 3. AHSI C 59-116 (also ASTM D 2225) "Standard Method* of Testing Silicon* Fluid* for Electrical Insulation." ASTM test procedure* called out In these documents are listed on the next page. The above standards deal vlth the fluids currently In coaon us*. Initial testing of a nev candidate liquid vould logically be done using the procedures already proven appropriate for existing liquids; however, it Is to be expected that some procedures would not be satisfactory and that nev procedures perhaps unique to a particular fluid vould have to be developed. As Illustrations of this situation note (l) that a different test procedure Is required for the detection of Inorganic chlorides In askarels than In oils and (2) that the test procedure for determining the water content of askarels and oils is not acceptable for silicones. In fact, the tabulation indicates that agreement within ASTM on standard test procedures for several Important characteristics of silicones has not yet been reached. i 73 MONS CH7214 A6KARELS Twoi) ELECT. INS, OILS (D117) SILICONE fluids (D2225) Acidity, Approximate D971* Acidity, Approximate, and Polar Contamination Coefficient of Thermal Expan D1903 sion Color D2129 Chlorides, Inorganic * D1821 Chlorine Compounds, D1820, D2U1 Hydrolyzable Dielectric Constant D92>* Dielectric Strength Using D877 Metal Disk Electrodes Dielectric Strength Using VDE Electrodes 2,6 Dltertlary-Butyl Para- Cresol Content Examination, Visual Flash Point Fire Point Gas Content D92 Gae Content (Nonacldlc) Inorganic Chlorides and Sulfates Interfaclsl Tension Neutralization Value D97>t, D661 (Neutralization Number) Oxidation Stability Peroxide Number Pourpolnt D97 Power Factor D92k Refractive Index (and Specific Dl807 Optical Dispersion) Resistivity D1169 Sampling D923 Saponification Number Scavenger Content D1701 Sediment and Soluble Sludge"*" Sludge Specific Gravity DlSlO Sulfur, Corrosive Thermal Stability D1936 VIecoelty D88, Visual Examination D1702 Volume of Oil Dl8o8 Water Content . D1533 D153* D1902 D1903 D1500 D878 ' 0677 D1816 DIU73 D1521* D92 D831 D1827 D878 0971 D66k, D971* BSkliO* 01563 097 D92* D1807 D1169 0923 D91* D1698 D1313, 0131it D1298 D1275 DBS, Ditit5, D2l6l D1315, 01533 D2129 D92*t D92 D97*t 097 D921* D1B07 D1169 D1298 DltitS, D2l6l *D9l3, D1931*, and D2112 also deal with oxidation stability. D31U6 Is called out in "Standard Specification for Oxidation -- Inhibited Mineral Oil for Use In Transformers and Circuit Breakers M 71* HONS 047215 The folloving related ASTM Standard* have recently appeared: D 3300 "Standard Method of Test for Dielectric Breakdown Voltage of Insulating Oils of Petroleum Origin Under Impulse Condition*" D 3303 "Standard Method for Rapid Gas Chromatographic Estimation of Higher Boiling Hoaologue* of Chlorinated Biphenyl* for Capacitor Aekarele" . D 3301* "Standard Method for Analysis of Environmental Jfeterlals for Polychlorinated Biphenyls" (This document is a modified version of Appendix B of AH8I C 10T .1-197**). A.3.3 Test Techniques By Which Electrical Properties Are Evaluated a. Dielectric constant and power factor. Techniques for measurement of the dielectric constant of insulating fluids are veil documented and pose no problems If applied with care. ASTM Standard D 92*t "Standard Method of Test for Power Factor and Dislsctrlc Constant of Electrical Insulating Liquids" outllnse test procedure* and specifies suitable test cells and ASTM Standard D 130 "Standard Method# of Test for A-C Loss Characteristics and Dielectric Constant (Psrmittlvlty) of Solid Electric Insulating Materials" outlines the theory and describes typical measuring circuits. b. Dielectric Strength. While not suitable for determinations of intrinsic dielectric strength, two designs of test calls have gained acceptance for ac measurements of the dielectric breakdown characteristics of Insulating fluids. ASTM Standard D 8T7 "Standard Method of Test for Dielectric Breakdown Voltage of Insulating Liquids Using Disc Electrodes" specifies s cell using 25.** mm fist disc electrodes (with square edges) spaced 2.5 mm and outlines acceptable test procedures. ASTM Standard D l8l6 "Standard Method of Tsst for Dielectric Breakdown Voltage of Insulating Oils of Petroleum Origin Using VDE Electrodes" specifies a call with a propeller for circulating the liquid and having brass elsctrodss, the opposing surfscss of which are spherical In shape and separated 2.0L mm (with an optional spacing of 1.02 mm If the voltage limitation of the teat transformer requires it). A third call and tsat procsdur* la specified In ASTM Standard D 3300 "Standard Method of Test for Dielectric Breakdown Voltage of Insulating Oils of Petroleum Origin Under Impulse Conditions." Alternate electrode configuration* are specified as follows; (l) sphere-to-sphere, using 12.7 mm brass or steal spheres and (2) point-to-sphere, using a 12.7 mn braes or steel sphere and s steal point, with s 0.06 mm radius of curvature. While concern has been expressed by some users regarding the desirability of placing greater emphasis on cleaning the test cell, on care In sample preparation, and on the fact that ths electrode material 75 HONS 0** 12.16 nay slightly Influence the results, these standards are generally considered satisfactory for the purpose. c. Resistivity. ASTM Standard D 1169 "Standard Method of Test for Specific Resistance (Resistivity) of Electrical Insulating Liquids" specifies the test cells and procedures for measurement of resistivity using direct voltage. The theory and measuring squlpment to be used Is specified in ASTM Standard D 257 "Test for DC Resistance or .Conductance of Insulating Materials." These standards appear adequate for the purpose. . d. Partial Discharges (Corona). ASTM Standard D 1868 "Detection and Measurement of Discharge (Corona) Pulses In Evaluation of Insulation Systems"; IEEE Standard 1*5^ "Recommended Practice for the Detection and Measurement of Partial Discharges (Corona) During Dielectric Teste"; and NEMA CP-P2-1973 "Test Procedure for Measurement of Internal Partial Discharges in Capacitors" are similar documents. They deal with a phenomenon vhlch relates to the total system rather than to the fluid alone; however, the corona characteristics of different fluids are often compared Independent of their operating environment in particular apparatus. A.3.U Teat Techniques By Which Pluld Placability Is Evaluated Most would agree that the concepts of combustion and flammability of a material are qualitatively clear and easily understood. The quantitative definition of flemnablllty of the material, that is, whether it vill ignite and then continue to burn under specified temperature, pressure and ambient atmosphere conditions is not, however, as easily achieved. What is required is a flammability test in which all relevant parameters are rigorously controlled end in which the results are unequivocally loterpretable, and this has been difficult to develop to everyone's satisfaction. The various testa which are recognised and in coson use are described below, along with conents on their applicability and shortcomings: a. Plash and Fire Points ...... ......... The only test specified by the stendards-settlng agencies (ASTM, ANSI, RFPA1, IEEE) for insulating fluida, mineral oils and aafcarela, is the Cleveland Open Cup test for flash and fire points (ASTM D 92). The epee ifieat Ions are: Mineral oil: flash point of 146 C (in some areas 130 C); Askarel: no fire point up to boiling point. Beside the D 9? test, ASTM recognizee several other variants for determining the flash point, which* however, are not prescribed for insulating fluids: the Tag Open Cup tester (D 1310), the Tag Cloeed National Fire Protection Association, 60 Batterymarch St., Boston, Itess. 02110 ` 76 . MONS Tester (D 56), end the Pentky-Kartens Closed Teeter (D 93). In ell experiment*! arrangement* the fleeh point 1* determined tgr slowly increasing the temperature of the cup containing the liquid sample. An Ignition source, placed above the surface of the liquid. Is actuated at specified Interval*. The flash point, by definition. Is the lowest temperature of the cup at which the vapors above the liquid surface flash. The flashes are transient, because only the vapor phase burns, not the liquid. In addition to the determination of the, flash point, the D 92 test specifies the procedure of Increasing the .temperature beyond the flash point up to the temperature at which transient application of the lgnltloh source causes continued burning of the liquid. The lowest temperature at which this happens Is the fire point. Determination* of flash and firs points give valuable Indications of flammability hazards, and should continue to be used, Mowevsr, It must be recognized that developments In recent years have progressed significantly beyond the stage at which the standards for insulating fluids were set, and also beyond the etete-of-the-ert prescribed by officially adopted ASTM standards. The following Items should be considered before flash and fire point standards are recoamaded for replacement fluidst (1) There has been a general trend toward closed-cup methods (e.g., D 93). In particular. Underwriter*' Laboratories her* favorsd closed-cup tests for somt time now. These generally give lower flash points than the open-cup variants. Tor example, the flash point* of the Dow Corning 50C8 (silicone) fluid are 30U C and 277 C as determined by D 92 end D 93 test* respectively. (2) The Affix Flash Point Comltts* Is moving tovsrd recosnending International adoption of an "equilibrium" method. Equilibrium methods specify Flash-Mo Flash determination at a seriee of constant (rather than continually Increasing) temperatures. Since in equilibrium methods the entire system, sample and container. Is at the same temperature, complications associated with heat transfer between the sample end the container are eliminated. Therefore sample size Is arbitrary and much smaller samples can be used. In addition, these methods do not depend on viscosity because convective currents within the sample are also eliminated. (3) Scientific analyses of fire-point determination are poorly developed. Therefore, the significance of the test Is not clearly understood. This point will be further discussed In connection with the Oxygen Index test.* b. The Oxygen Index Test .) In th* Oxygen Index (01) test the test sample Is placed Inside a tube containing a mixture of oxygen and nitrogen gases. The gas mixture, normally at room temperature, flova gsntly upward. The sample Is ignited and the percentage of oxygen In the gas mixture Is decreased. 01, by definition, Is the percentage of oxygen In the oxygen/nitrogen mixture at which extinction occurs. *A rsviswer points out that in any event fire point Is of less importance If the more conservative flash point Is used In specifications. 77 KQNS The epecified ASTM 01 technique applies to solid samples only (D 2863) Various laboratories have made their own modifloatIona of the teat to apply It also to liquids, and have reported the resulting data, but there la no uniformity of procedure. Sharply divided opiniona exiat aa to the value of the 01 teat toward a definition of flammability. For example, a limited polling of the industrial opiniona in this survey above that some manufacturers use the teat for practical purposes, while others consider it "worthless." The reasons for this division are not difficult to see. On one hand. It is recognised that the burning of a small laboratory sample (a few grama) in room-temperature environments in no way simulates the behavior of large amounts of combustible materials in a veil-developed fire. On the other hand, there are reaaona why the 01 teat should not be discounted in the context of this survey. Fundamentally, the teat la the prototype of extinction of a diffusion flame, and it bears roughly the same relationship to practical fire-point determinations that the fundamental flammablllty-llmit data do to practical flash-point determinations. Aa was discussed earlier, both fleet) end fire points are specified standards for definitions of flammability of insulating fluids. The problem la, however, that fundamentally meaningful fire point, or 01, tests are more difficult to deeign than the meaningful flash point tests. To obtain consistent extinction data one would have to develop an 01 test for liquids and a fire point tester in suob a way that an 01 value of 21 (i.e., air) ia obtained at the experimental fire point. Recent work at the KBS Center for Fire Research shows that such development would require very careful design of the test geometry. Therefore, an 01 test for insulating fluids should be recoatnded only after aome additional atudy, allowing apeclflcatlona of the testing arrangement. c. Spray Flammability Tssts The ASTM Mist Spray Flammability of Hydraulic Fluids test (0 3119-72T) could be applied also to electric insulating fluids, but ve have no evidence that anyone has done that. The test is s very eevere one, entailing the apraying of a preheated atomised aiet into an open flame. Underwriters' Laboratories consider it too severe and use one of their own variants in its stead (UL File MH 011)66, p. Tl-6). The UL teat consist* of applying drops of the liquid to the surface of a heated steel plate, and observing the "behavior." Factory Mutual Research Corporation has its own spray flamsability test, skin to D 3119. It ia also a very severe one. Most hydraulic fluids do not pass it. Factory Mutual is currently using the results of their spray flammability test to establish acceptable operating temperatures for askarel substitutss. d. Autoignition Temperature (AIT) Several techniques exiet for the beating of liquids in air until they ignite. ASTM D 2155 is a specified procedure for liquid petroleum product*. Underwriters' Laboratories use a similar teat Of their own. 78 M0NS 047219 At one should expect, autoignition temperature* of electric lnsulstlng fluids are quite high. Some reported values sre: 332 *C for a mineral oil and 393 C for Dov Coming 50CB fluid, both by the D 2155 test} 662-670 C for askarsls by the UL test. As in the esse of the sprsy flammability tests, operational conditions, normal or abnormal, are unlikely to give rise to these temperatures in the case of insulating fluids. The AIT test, therefore, does not appear particularly pertinent. (At this pointy It should be mentioned that Underwriters * Laboratories does not evaluate liquid* only on the basis of tests vhich simulate some aspects of actual operations, but also on the basis of the total information about stability and riajimablllty of the liquid. If this philosophy is adopted, then of course the AIT test and any other reproducible test vhich can be tied to some property of the liquid, becomes pertinent. In ftet, UL did use the AIT test among others, to arrive at a numerical flamability rating of aekarels). e. Energy-Release Tests Hazard* tests designed to evaluate the amount of explosive energy released in an accident apparently' have not been used ih connection vlth insulating fluids, but there are good reason* vhy they should be. Buch teats almost invariably give a measure of energy release by the effect on the aurroundlnge: damage to a target, displacement of a target, or generation of a blast wave in air. Since the hazard of an arc-initiated fire in a transformer or capacitor tank may be due to the blast wave damage at veil aa the subsequent fire, a measure of the explosive energy release capability of an insulating fluid vould appear to be useful. Such a test vould be particularly important if it could be ahovn to be a useful screening mechanism before going to the more expensive, full-unit teats discussed in Sections A.2.3 and A.3-3 (sea also Section* 3*5 and 3-6). Direct measurement of the blast vave intensity may be the moat valid energy release teat, aa described more fully in Section 3- The table on peg* 60 summarises presently accepted flammability data on several insulating fluids. fluid flammability measurement, by vhatever teet procedure is adopted, should be carried out under conditions as closely approaching operation a> reasonably possible. In particular, pressure and temperature conditions are knovn and should be duplicated. Thus, power transformers of the "askarel class" have a temperature increase of about 65 C under full load, so that bulk fluid temperatures will probably Dot exceed 100 C even on hot daye. Local temperatures near the transformer winding may be ten to tventy degrees higher. Moat utilities operate their askarel transformers with a pressure relief device as prescribed by the National Electrical Code (Section 1*50-23); the relief pressure le usually only a few pel (20-1*0 kPa). Power capacitor tanka rupture at low pressure* but small industrial type capacitors generally are sealed to li0-50 psi (280-31*0 kPa). The riuid temperatures within capacitors vould not be much above the ambient, which lteelf might vary widely depending on location. 79 047220 mqns ll. *HM m * ioto 111W torM *r Bin topm1 Par Oanlif im ns-n t totoNlia hpar mrnrnr+l Ml M(. oil, pvartliti (mi --1) (nifOntr Oil [ON 0*1) * Mil) > MM MM) (mOlflaO) nut MiLiSl 1 (1)0) 1M 1M rtn **iM ttl flu 1ft OW0U21 m Mi 1)1 ii mif tot] . lafart1 knair MUn Iqirt1 tm CtnlM ifii bb-m Oon* Of1 Ob qtrt1 Pm Ctovmtaf tm patl* flufiiwi Fipir fcraaa rf Una* lOirill* Imlo 1011 kl 1M ItriiUintlitanl} 1ml* in* (I*tn*tl*lfkmol) *> CO (tolrUootMl) tm e MOO lino M v-i-tm Mmrimthrl (u) MMrl (U OH.) Mmurl (1*> 4m.) MMrl fMOOl MlvmtMl Urn 4m.) SSI -- XT* <*1M0* *) ITT in Ml--H M trt m 10* Mo 1M to m **) Vi QiNtflil Pntieti [OH iln Hi tb Mliflil lifimtla m tl* MMDUltrt tor enli| fOCfi r>M la air 91 *Vi 0-J.-*1O1j Minti il llr IX *C {Dim 1U ftaah pDK --m n< X* *C. M *TT Inalir lUli IMnti la air lU *C tX to* Qaftlaii IflTt ; mmnn toftr ||ini tolittf* toniif rat* (i/N4i W XNHflr) MM* *fnr (ttUfl) *atlT iOOto 1. M. EM* mi V* J* Ca*at nl naaaUltr hHniM r tutorIftatt." |f| TTMIMUMI *** TT UfCJ). t. B. r. Barra Ml B. A. TlacMl, HIUmh Plvito * 1>4) wt*w Oil*, MtoriHt tofii CfMlM* Iftt VUtor tottlH IB Itow hflarartav to*(*trt s* T*rB* B*v Tart* Jwiaary U IfTk. y Mwurr* uaa^Mrr, u--iff* rntHflf llH* J"7 IfTt, t. P. T. Ban* an* T, oitotli atltNM>nti filial fruttomn,,.* Qraf*rmf hp*r IfTl Ml* hfliwpt^ aim Cmoiw*. torn, tonntoirtti, ifrll HJi UT J. ' J 80 j` HONS 047221 For a new fluid, with different loaa and heat tranefer characteristics, theae typical values may have to be revised. A.3.5 Bone Teat Techniques For The Evaluation Of The Toxicity Of Dielectric Fluids - In the put, toxicologists have not only made the laboratory assess ments of toxicity, but in many instances they havt modi the final judgment as to tht social count to bt taktn on tht basis of a particular itX of findings. I nittad, tht technical experts thoutd be chargtd with securing an objective independent determination oj the extent, nature, end frequency oi adverse effects. They should be aiked to explain the relative gravity o< that effects jot the target iyittm, be it humane or wildlife. Similarly, other qualified technical experti should be requested to mfce on objective anenment of the benefits o{ use and of alternative materials or procents. However, the final judgment as to a trade-off between an adverse health effect and a desired benefit is a iocicl decision and should be mode with the participation o{ those who are affected. This is not to say that technical experts using their technical expertise will not participate, but it does state that they should not be the sole judges of determining the balance between the benefit and the risk. "Terms such as 1 toxicological insignificance,' 'safe/ 'zero tolerance,' 'no effect level,' and 'negligible risk' have been in rather common use. Ml of these contain in one way or another value judgments or technical implications which have no place in an objective assessment of risk. There is no substance which, under certain circumstances, could not be dangerous and unsafe. There is no battery of tests, however elaborate, which can prove beyond challenge the complete safety oi a chemical. For the toxicologist to apply the terms 'toxicologically insignificant' or 'negligible risk' to a set of observations makes a premature judgment in the wrong arena by the wrong person as to insignificance or acceptability. Attempt has been mode to eliminate such terms from this report. Another cotmon term of wide usage is the 'no-effect level.' This is statistically meaningless and therefore of limited value since it merely means that no effect was observed in studies using a group of animals of particular size. Such an observation is completely compatible with the presence of an adverse effect, which in further studies with larger sample sizes or with different types of observation might lead to a positive outcome. We prefer the usage of the term 'no observed effect, * which should always carry with it a qualifying statement as to size of the group in which no adverse ejject was obstAved." We have opened this section with quotations from the report of the national Academy of Sciences, "Principles for the Evaluation of Chemicals in the Environment"' [hi*], as a forewarning of the complexities and difficulties we may anticipate in looking at the field of toxicology. 81 MQNS 047222 Our knowledge of the toxicity of insulating fluide remits, in the main, from two sources. The first source is clinical observation. In this instance the observer, generally a physician, is confronted with a victim of a toxic condition with which he may have had no prior experience, and even if he is successful in treating the condition, the one event may well remain an isolated one to him. A more informative kind or clinical event (and more costly in human terms) oceurs when there is a mass poisoning euch as the now famous Yusho outbreak of 1963 in Fukuoka, Japan. Here there were a sufficient number of cases for a local medical achool to mount a full scale epidemiological etudy. The study group was successful in determining the origin of the poisoning, polychlorobiphe^yl heat transfer liouid which had leaked into a food preparation vat [ll]. It is evident that the clinician or epide^ologist must seiie his opportunity and extract as much information as possible from the case at hand before the opportunity ie lost. The second source of our knowledge of toxicity coaee from enimal experimentation. In contrast to clinical studies, animal experimentation provides the kind of systematic data which may be acquired by independent observers and confirmed st will. This kind of experiment constitutes the main source of information that a developer of a dielectric fluid submits to government regulatory agencies. It will be mainly this type or experiment which will be deal with in what follows. It is possible to develop a definition of toxicity through the use or populations of animals as is done in the Federal Hazardous Substances Act (PL 86-613 and amendments, 15 U.S.C., CH. 30] vbere the definitions under Section 2 paragraphs (g) through (k) read: " (gI The tenm 'toxic.' ikalt apply to any iubitanct I0then than a nadioactive iubitanct) which has the capacity to product peuonal injury ok tUnea to man thKough ingestion, inhalation, ok abionption thnough any body iunface. (h) IF' The temit 'highly toxic' meant any substance which falls within any of the fallowing caXtgonietla) produces death within fourteen dayt in kali ok moKt than half of a group of ten ok none labonatony white nati each weighing between two hundned and three hundned gnamt, cut a Mingle doit 0^ fifty mUlignami ok leu pen kilognam of body weight, when onally adminZitened ok (bl products death within faunteen dayi in half ok mone than half of a gnoup 0f ten on mate labonatony white nati each weighing between two hundned and thnte hundned gnami, when inhaled continuously fan a ptniod of one houn on Itii at an atmoiphenic concentnation of two hundned panti pen million by volume on leu of gat on vapon of two mUligncmi pen titen by volume on leu of mitt and dust. provided such concentnation it likely to be encounteted by man when the iubitance it used in any neasonably fonuttablt nomen; on |c) produces death within founteen dayi in half on mone than half of a gnoup of ten on mone nabbtts tested in a doiage of two hundned miltignjum on leti pen kilognam of body weight. When administered by continuoui contact with the bane ikin fan twenty-four hount on leu. (21 If the Secretary findi that available data on human expedience with any more recent evaluation [16] suggests that a contaminant of the PCB rather than the PCB itself may have caused the poisoning. 82 MGNS 0ylZZ* Jubilance indicate resuits difftrint from those obtained on animals in the above-named dotage* ok concentrations, the human data shall take precedence. (-cl The term 'corrosive' mta.ru any substance which in contact with Living tissue will cause destruction of tissue by chemical action; but thalt not refer to action on inanimate surfaces. . iy) The team 'irritant* meant any subalance not corrosive within the meaning of tubpanagraph \i\ which on immediate, prolonged, or repeated contact with normal living tibiae wilt induct a local inftamatory reaction. (fe) The term 'strong sensitizer* means a substance which will cause on normal living tissue through an allergic or photodynamic process a hypersensitivity which becomes evident on reappUcation of the same substance and which is designated as such by the Secretary. Before designating any iuba-tance as a strong sensitizes., the Secretary, upon consideration of the frequency of occuwence and severity of the reaction, shall find that the substance has a significant potential for causing hypersensitivity." , Ftqb the operational definitions provided above one can by Beane of a few Bodificatiom, define other operational dafinitlone such aa are found in the Registry of Toxic Effects of Chemical Substances [t>5] of the National Institute for Occupational Safety and Health: "TPLo-Toxce Post Low - the lowest dose of a substance, as published or made available to publish, introduced by any route other than inhalation over any given period of time and reported to produce any toxic effect in non or to produce carcinogenic, teratogenic, mutagenic, or ntoplastigenic effects in humans or animal. TCLo-Toxic Concentration Low - any concentration oi a Jubilance in air to which non or animals have been exposed for any given period of time and that has been reported to produce any toxic effect in man, or to product a carcinogenic, teratogenic,, mutagenic, on ntoplastigenic toxic effect in animals or humans. 1 LPLo~ Lethal Post Low - the lowest dost of a substance other than LPSO introduced by any -toole other than inhalation over any given period of time and reported to have caused death in bom or the lowest single dost introduced in one or none divided portions and reported to have caused death in animals. Entries for lethal doses administered to animals for the qualifying toxic dost, TXPS, tuete made in accordance weth the dose limits of Table I.' *$ee Re<. 45, p. xviii 83 MONS 047ZZh LP50-Lethal Vote fifty * a calculated tbit oj a chtmical dubslance wbcch i* expected to cause the death oj 50% oj an entire population of an experimental animal tptciti, at determined from the exposure to the substance, by any route other than inhalation, of a significant number from that population." Other lethal dose percentages, such as LD1, LD10, LD30, LD99, aa well as others, may be published in the scientific literature for the specific purposes of the author. Such data vould be published in the list if these figures, in the absence of an LD50, were the lowest published in the article. A substance stay qualify by an LDLo published value even though a higher' LD50 value, which nay also exceed the Halts of Table I* was reported in the sane publication. "LCLo-Ltthal Concentration Low the lowest concentration of a substance, other than an LC50, in air which has been reported to have caused death in man or to have caused death in animali uhtn thiy have been exposed for t4 hours or less. Entries for lethal conctnOiatiom for animat* for the qualifying toxic dose, TXPS, were node in accordance with the dose limits of Table 1.1 LC50-Lethal Concentration Fifty - a calculated concentration of a substance in air, exposure to which for 21 hours or less would cause the death of 501 of an entire population of an experimental animal species, as determined from the exposure to the substance of a significant number from that population. These entires qualified in accordance with the dose limits set forth in Table I.' See LP50 above for other parameters which may similarly apply to entries for the list." It has also come to our attention that a scale developed by Hodge la frequently used by toxicologists [561 The complexity of the whole environmental system requires the examination of the effect of pollutant* on acre than ona type of animal. It Is generally considered dsslrable to Include experiments on birds, amphibians, and fish as well ss mammals. In order to obtain an idea of the total Impact of a aubatance upon the envlronaant. The more responsible the concern for the environment, the more detailed will be the experiments, for we are trying to extract from a few telling experiment* information applicable to virtually the whole of nature. To acquaint himself with Just the first notions of the complexity of the subject before us here, the reader might refer to a list of experimental animal* used In toxicity experiments. Such a list la given herewith as Table A. It la taken from the Registry of Toxic Effects of Chemical Substances {1*5 Table III pxx]. The llat run* the gamut from amphibians to man and will doubtless be expanded still further as toxicological studies proceed through the years. In addition to the range of animals to be considered,there is also a variety of methods of administration as given In Table B, taken from [1*5 Table II p. xlx). This list may also be expanded as experimentation continues, "intraocular" for example which does not appear on the list ''See Ref. 1*5, p- xviii mons 8L TABLI A SpOCtM bird -- any domestic w laboratory bird repotted but not otherwise identified bird --wild bird epectm cal cattle chicken child dog domestic animate goal, cheep, bona duck (domestic) frog gerbtl guinea pig bamMer human mamaMl -- ipecies unspecified in reference monkey mouM P*g pigeon quail (laboratory) rabbit rat tquirreJ toad turkey women OrdUr of Pnfenaca for Deta Acqutahkw 23 23 7 11 17 1 4 12 IP 20 13 P 10 1 1 13 1 6 3 1 16 IB 3 2 14 20 21 i . . Deeignatioa bid bd cat ctl ckn chd dog dom ddc frf gib IPg bam tuna W mam man mky mua Pig Pgn qal rbi rat ql tod trk wmn 05 HONS 04722b TABLE B ROUTES OF ADMINISTRATION TO, OR EXPOSURE OF. ANIMAL SPECIES TO TOXIC SUBSTANCES Route intraarterial Intraaural Intracerebral imracervical latradermal Iniraduodenal Inhalation Implant Intramuscular intraplacemal Intrapleural lntraperitonemi inirarenai intratracheal Intravaginai lntravenotn Ocular Oral Parenteral Rectal Skin Subcutaneous Unrtported Abbreviation iat . iai ice icv idr idu ihl imp imi ipc ip* ipr im Hr Ivg ' ivn ocu orl paT rec skn tcu unk Definition administration into the artery administration into the ear administration into the cerebran adminiatration bito the cervix adminiitratioo within the derail by hypodermic needle administration into the duodenum inhalation In chamber, by cannulation, or through mask placed surgically within the body -- location described reference administration of doae into the muscle by hypodermic needle administration into the placenta administration of doae into the pleural cavity by hypodermic needle administration Into the peritoneal cavity administration into the kidney administration into the trachea administration Into the vagina administration of dose directly into the vein by hypodermic needle administration directly onto the surface of the eye or into the conjunctiva) sac per oe, imragtitric, feeding Introduction with drinking water administration into the body through the akin. Reference dud is not specific concerning the route used. COuld be ipr, scu, ivn, ipi, 1ms, ire, or ice administration of dose by way of rectum to the rectum or colon in form of enema, suppository application to the intact akin, dermal, cutaneous administret ion under the skin dose, but not route, it specified in the reference 86 HONS 047227 in this year's edition, but probably will soon as there already are auch studies for aillconea (1*6]. Another Hat of the effects observed {extracted from the same document) given here as Table C (1*5 Table VI p. xxlv] shove the almost endless variety of observations to be met vlth in the field of toxieology. In addition to the foregoing variables and constraints there are to be considered, age, sex, and periods of exposure and observation. The lmporatance of considering these last tvo parameters may be Judged from the National Academy Report ptb). "Acute toxicity con `be defined at exposuht to a tttt agent for 14 houns ok less. This definition vaLU pnovidt foe the 24-houn expolute peniod often used in denmal procedures and the 1 to I-hour pentads often used in the inhalation pnocedunes. The teAM 'acute toxicity' hat often been used to define the imediatt {usually 24 /touts ok tttt) effects of an agent on the animat; it it more appKopKiate to use longer peniods of observation after the tingte expolute in oKden to detect ant/ delayed effects anising oven an extended pentad of time. The 24-houn peniod of oosenvation may detect pninurily phanmacodynamic activity, although othen biological mechanisms might be to aliened at to cause death on othen effects tUthin a tongen penned of obsenvation. A pnotonged observation pentad mould also penmit detection of effects that might be notated to anatomical, biochemical, on hematological changes that mould not cause immediate death. Acute toxicity studies one needed in safety evaluation foe tuo distinctly difftntnt Keatons t one is at a tentening procedure to aid in identifying compounds of such low toxicity that, when considered in nelation to a pnoposed use of tom exposure, extensive investigations to make a judgment of safety are not justified. The other is as a type of acute toxicity procedure designed to delineate the specific toxic effect, and mechanism thereof, which might be associated with a missive exposure or`a nonmat use associated with a high level of exposure to a compound. This latten type of study it designed to assist in the development of an appropriate clinical management program for individuals involved in a misuse oh accident and to assist in appnaisat of the safety of a panticulan use involving significant human exposure, even though that exposure might be chronic in nature. Such studies can aid in identifying target organ effects which may be valuable in the proper design of chronic studies. In the screening type of acute toxicity procedure, the amount of maCental to which an animal is exposed is so massive that it generally bears no practical relationship to the expected human exposure. It is reasonable to establish maximum exposure levels (e.g., 5000 mg/kg onally, 5000 mg/kg denmatty, etc.) for each acute procedure, which can be used to predict that the agent is essentially acutely nontoxic if no advense effects are detected. 87 HONS 04722b TABLE c NOTATIONS DESCRIPTIVE OF THE TOXICOLOGY Abbreviation! ALR BCM BLD BPR CAR CNS COR CUM CVS DDP EYE GIT GLN IRR MM1 MSK MUT NEO PNS PUL RBC SKN SYS TER TFX UNS WBC Definition* (not United to effect* Listed) Allergenic-systemic reaction such ai might be eaperienced by individuals sensitised to peniciliin. , Blood dotting mechaniim -- any effect which increases or decreases dotting time. Blood effects --'effect on all blood elements, electrolyte*. pH, protein, oxygen carrying or releasing capacity. Blood pressure effects -- any effect which changes any aspect of Mood pressure away from normal -- increased or decreased. Carcinogenic -- producing cancer -- cellular tumor, the nature of which is fatal or is associated with the formation of secondary tumors (metastasis). Central nervous system -- indudes effects such as headaches, tmnor, drowsiness, convulsions, hypnosis, anesthesia. Corrosive effects -- buret, desquamation. Cumulative effect -- when substance is retained by the body in greater quantities than is excreted, or the toxic effect is Increased severity by repeated bodtiy insult. Cardiovascular effects -- such- as when heart activity it increased or decreased through aii effect on ventricle or auricle; fibrillation; or when the arterial or venous system is dilated or constricted. Drug dependence -- any indication of addiction or dependence. Eye effects -- irritation, diploplit, cataracts, eye ground, Mindnaee by affecting the eye or the optic nerve. Gastrointestinal tract effects------ diarrhea, constipation, ulceration. Glandular effects -- any effect on the endocrine glandular system. Irritant effect -- any irritant affect on the skin, eye, or mucous membrane. Mucous membrane effects -- irritation, hyperplasia, ciliary activity changed. Muscuio-skeletaJ effects -- such as osteoporosis, muscular degeneration. Mutation or mutagenic -- transmissible changes produced in the offspring. Neopiastiteffect -- the production of tumors. Peripheral nervous system effects. Pulmonary system effects -- effects on respiration and respiratory pathology. Rad Mood ceil effects -- includes the several anemias. Skin affects -- such at erythema, rash, sensitization of skin, petechial hemorrhage Systemic effects -- effects on the metabolic and excretory function of the liver or kidneys. Teratogenic effects -- nontnuismissibie changes produced In the offspring. Toxic effects -- used to introduce the prioripel organ system affected as repotted or the pathology. Unspecified effects -- the to&c effects were unspecified in source. White blood cell effects -- effects on sny of the cellular units other than erythro cytes, including any change in number or form. Editorial note: Death is, of course, another definable response 88 HONS 047229 A decision p*.oct66 bated on both pcuumztvu o{ expeAimtntnlly deAived toitic e{{tct* and lAtimcuttd expo*u\e level* thould be developed through iubchAoncc ttudit* in an tea'll to identify thote compound* and ait* which mexit ckAonic itudie*. In other wcAdi, <U tht knowledge aj txpoiuAt level change* and toxicity information become* available, fuAthtA letting mag not only be dt* treble bat nice**any. However, that there mag be circumttance* othtA than thou which warrant chronic itudie* i* recognized. Structural characterittic* may indicate die need o{ a candrogenic bioattay. No *hoAt-term oa tubckronic te*t* oai known that can give attunance oj| the pretence oi poaibte caAcinogtnic activity. When a new chemical i* pritented {oa evaluation of toxicologic hazard, the chemical and physical chaAocttAittic* o{ the mterial mutt be coniidered *o that appropriate itep* can be taken to etiuAt adequate expoiuhe the animal to the chemical in the variout pAcctduAt*. The chemical liability o{ the agent, vapoA prttturt, tolubiiity, particle tize, etc., can be o< impoAtonet. Before any judgment Aeganding health hazaAd can be made, it i* neett*any to know the intended use and the anticipated Acute, frequency, and level of expo*uAe to man. The type o{ expciurt being cort*2dered i* generally that likely to At*ult {Aom the normal uiage of chemical* AathtA than {Aom an abnormal iituation tuch a* would retult {Aom a *pilt" - [itii, p. 99). A further complication Is the requirement that adequate analytical chemical tachnlquea should exist (for every conceivable compound and metabolite) to detenlne the administered quantity of a toxic substance, to Identify the type and quantity of any contaminants In the substance, and alao to determine the amount and presence In the biological system. Analytical techniques, such as gas chromatography combined with mass spectrometry, vhlch con measure trace materials In vater dovn to levels of 1-10 parts per trillion are available tb7)- Finally, the overall complexity of the subject can be lnfarrad from the criteria for Inclusion of a substance in the Registry of Toxic Effects of Chemical Substances (*5. p. xvl]i "Qualifying Toxic Vote tTXDS), kit toxic do.*u appearing in the Regittry were derived {Aom AepoAt* 0/ the ' toxic e{{ect* produced by individual *ub*tance*. A toxic e{{ect l* de{intd a* any bodily injury -- revertiblt oa iAAtvertible; any tumor - benign oa malignant; any mutagenic OA tcAatogenio effect; oa death which ha* been AepoAted to have retulted {Aom expo*une to a chemical iubttance via tht Atipiratory tract, *kin, eye, mouth, oa any other Aoute. Foa human* the toxic effect i* any toxic e{{ect that wa* AepoAted in the *ouhce Ae{eAtnce. There it no quali{ying limitation to the duAation o{ txpctuAt nox to the quantity o{ concentration of the tubttance, noA i* thiAe a qualifying Limitation o{ the ciACumttanct* that retulted in the txpoiuAe. Kegardltt* o{ the abturdily o< the ciraumitance* that weAe involved in a toxic expoture, it i* attumtd that the tame circumttance* could AtcuA. 89 HONS 04723 For oiujimli the. toxic dote matt bt limited in order that the Hegi*try mitt have practical tuejuInti* a* a guide to hazardou*nt*i to hwnm*. The qualifying *ymptomatotogy toe animat* cannot be elucidated mith any practicality} therefore, `more objective iign* o{ toxic eiiect* nut be relied upon. The production o( tumor* (neopla*tigene*i*l, benign or malignant Icardnogent*i*); the production oi change* in the otf*pring, whether trammiiiible lmutagene*i*] or not Iteratogene*i*h and the production oj death are the criteria that are u*td a* the quatitying toxic effect* tor animal data. For a *ub*tance to be included, there i* no limitation* a* to the time ot txpoiurt, nor the quantity or concentration o( the do*t ot the *ub*tance reported to have earned mutagenic, teratogenic, neoptaitigenic, or carcinogenic e{{ect* -in animal*. Thi* i* btaau*t the do*e-ettect rttatiomkip ha* not been correlated tor animal* and mm. It i* pre*umed that there i* *ome potential tor the occurrence in man ol ettect* *imilar to tho*e noted in animal*, it nan i* expo*ed to there *ub*tanct*." We have nov cone to the point vhere ve have seen the possibility or defining an experimental protocol In terme of populations of animals and ve have teen a few of the effects which are looked for in the tables. It might be veil for the Interested reader to consult a review such as that of Kimbrough [11 ]. vhere an overview of the toxicity of a large number of polychlorinated polycyclic compounds la given. We eee from Kimbrough [11]. and from the Interdepartmental Task Force on PCBs [It8] the following general results for the particular case of the PCBs. 1. Response depends on route of application: inhalation, akin and oral techniques have been usual In PCB studies. <?. Response depends on tpeclee; a large number of animals have been ueed, end data alto exist on human response. 3. A vide variety of specific reactions occur Including liver: size, action, enzyme production; skin: chloracne, edema; reproduction; embryonic effects, gastroIntentinal leelons, chemical parphyrogenlc effects, neurotoxicity, Immune response, death, with sufficiently large doee. It. Response time; because of the stability of the PCBs, they tend to accumulate in specific body tissues and their effects are therefore generally slow to appear and are long lasting. 5. Analytic techniques; sources indicate the problem of identifying contaminants which probably accompanied the PCBs in controlled exposure tests. Because of the accumulation phenomenon, toxic level concentrations may be very low. In addition, regulatory personnel have suggested PCB standards at low as 1 ppt (l part In lO12). Analyses at thle level are routinely available In special situations [**?]. A citation here of three paragraphs of Kimbrough' review should indicate something of the methods, the range, and the vaatneee of the 90 MQNS 0*7231 difficulty of this type of study. Proa page **55 of Kimbrough [11] ve aee: "In a phea*artf reproduction study with Anoclon 12$*,*^*^ a significantly greater di{{tntnce in the number o{ egg* that went pipped out not hatched mu* (Sound in the group o{ hen* that rectivtd SO mg oi PCS* weekly. Egg production and hatchabiiitg HO* tower in this gnoip, tne sunvivat o{ chicken* that did hatch at *ix weeks o{ age was reduced, and the one* that did *urvive were signiiicantty tighter than the conirot*. di In another rat reproduction etudy the lowest do*t o{ Aroctor 125* that ajjected reproduction mu 20 ppm |J5 mg/kg/day) which mani(cried iiieti in a decrea*ed number oi titter* and te** pup* per titter. Neither 1 ppm nor 5 ppm oi Aroctor 1254 had an e{{ect on reproduction in the Sherman *train rat; however, an expoAure o( the dam* to the Aroctor* at 5 ppm or higher incneastd the liven-to-body weight ratio* in weanting rat* 0(( both sexes. At I ppm the incntase in liven weight wa* observed ontg xn Fta and Ftb weanting mate rat*. The dittany levels oi 100, 20. and S ppm o( Aroctor 1260 did not a((eci reproduction; however, tne liven-to-body weight eatio oi 2}-day-old pup* wa* increased at all expoAure tevet*. ,, . Hinh are highly susceptible to the toxic eiiecls oi PCS*. A daily dittany intake oi 10 ppm re*utted in death in about 6 month*. ExpoAure to 5 ppm Aroctor 125* in the daily diet stvenely a((ecied reproduction, '^5 Unjortunatetg, it i* o(ien very di((ic.uii to compare the variou* dittany tevet* that abject diiitntnt Apecie*, *ince the {ood consumption may vany decisively (ro one animal species to anothen and the daily {ood intake in g/kg body weight is o(ien not included in the scienti{ic report. Some mice Attain*, {or i/uiance witt be expo*ed to as much o{ a given *ub*tance that is present in the diet at the concentration o{ 300 ppm as not* on a diet containing 600 ppm or more. With some species it is oi courAe diiiicult or almost impossible to meaAure the iood consumption, but a greater e{{ort in establishing these vtny basic {acts would be helpiul {or the interpretation o{ toxic e{{ect* in di((ereni species." A number of additional U.S. Government Regulations exist giving further operational definition! of toxicity. Among them are: 1. Department of Transportation - Proa CPH Title 1*9 "Transportation" Part 173.31*3. Class B poison ("less dangerous") see. 173*31*3 liquid or solid substance "fcnouM to be so toxic to man as to a{{ord a hazand to health t 91 MQNS Oh723i during transport, o\ which, in the absence oi data on Hunan toxicity... ialt within any one oj the iollowing categories1: 1) Oral toxicity: product death within 4t houni in hali on mm oi a gxoup o{ 10 on none White labonatoKy not* weighing 200 to 300 grams at a single dost o< 50 milligrams on less pen. kilogram oj body weight when administered orally. 2) Toxicity on inhalation: those which pnoduce death within 4t hours in hati ok none than hall oi a group o{ 10 ok none whitt laboKatOKy rats weighing 200 to 500 grams, when inhaltd continuously jon a period o{ one feoun on lets at a conctntAation oi 2 milligrams on less pen liter oi vapor, nett, on dust, pKovidtd Such conctntnation is likely to be tncounttKtd by man when the chemical product is used in any reasonable ioreseeable manntK. 3) Toxicity by skin absoKption: those which pnoduce death within 41 haunt in hali on mone thin hali o< a gnoup o\ 10 on none Kabbits tested it a dosage o{ 200 milligrams on less pen kilogram body weight. When administerea by continuous contact with the bane ifwn jon 24 hount ok less. The ioKegoing categories shall not apply ii the physical characteristics oi the probable hazards to humans as Shown by expedience indicate that -the *ub4tancet will not cause Serious sickness on death. neither the display oi danger on wanneng labels pertaining to use non the toxicity tests set iortk above shall prejudice on prohibit the exemption oi any substances irom the provisions oj Parts 170-(19 oj this chapter. 129 FR 1175!, Pec. 29, 1941, as amended by Awtt. 173-3, 33 FR M922, Oct. 4, 196t; 33 FR (9123, Pec. 27, 1901)." 2, Occupational Safety and Health Administration: Air contamination standards (cm 29 1910-93) citea: "Threshold Limit Values of Airborne Contaminants for 1968," Amer. Conf. on Oovn. Industrial Hygienists. 3. Food and Drug Administration (FDA): FDA rellea on EPA to establish tolerances. FDA also will act on any legitimately verifiable Indication of toxicity of a substance; rather than having its own specific regulatory definitions of toxicity or lists of toxic substances. Tolerance levels for specific substances may, however, be established, as waa done for PCBa on July 6, 1973 (38 FR 10095; also see 21 CPU 122.10) milk manufactured dairyproducts poultry egg* animal feed animal feed components fish Infant foods 2.5 ppm 2.5 5 0.5 0.2 2 5 0.2 1The reader will note the similarity between these definitions and those used in the Federal Hazardous Substance Act (l5 U.S.C., Ch 30) discussed earlier. 92 MQNS 047233 I 1*. Environmental Protection Agency (ZPA)i A Federal Water Pollution Control Act, Amendments of 1972 (Public Law 92-500 96 Stmt. 8l6); the tern "toxic pollutant*" 1* defined In section 592(13): 502(13) "The tenJit 'toxic, pollutant' meant that pollutant*-, ok combinations oi pollutant*, including distase-causing agent*, which after discharge and upon exposure, ingestion, inhalation ** atimilatLon into any organism, either directly fro*: the environment ok indirectly by ingtttion through food chain*, wilt, on the ba*i* of information available to the Adnunistrator, cautl death, disease, bthavoKial abnomulitie*, canct*, genetic mutation*, phy*iological malfunction* {including malfunction* in KtpKoducXion) ok physical deformation*, in *ucA orgarusm* ok their offspring," Section 3Q!*(g) direct* the Administrator of 1PA to publish test procedure guidelines: "504(g) The Administrator thall within one hundred and eighty day* from the date of enactment of tki* title, pKomtgate guideline* e*tabli*hing te*t pKoceduAc* fo* the analy*i* of pollutant* that thall include the factoK* which mutt be provided in any ceKtification puKtuant to tection 401 of this. Act ok permit application pu/uuant to tection 40t of thi* Act." . Test proesdures for 30b(g) were published la 38TR 28753 Oct. l6, 1973; for "chlorinated organic conpound* (except pesticides)gas chromatography ia the approved teet procedure. Section 307 directs the Administration to establish a liat of toxic pollutants: ' "507(e) (a) (I) The AdminittKatoK shall, within ninety day* after the date of enactment of thi* title, puwiih (and from time to time thereafter revise) a li*t which include* any toxic pollutant ok combination of tuch pollutant* foK which an effluent standard {which may include a prohibition of the discharge of *uch pollutant* ok combination of tuch pollutants) will be established undtK thi* tection. The fSministrator in publishing such a list shall take into account the toxicity of -Che pollutant, its persistence, decidability, the usual ok potential pretence of the affected organisms in amr watt**, the importance of the affected oKganitms and the nature and extent of the effect of the toxic pollutant on iuch oKganitmt. (f) Vitkin one hundred and eighty day* aften the date of publication of any Cist, ok Kevition thereof, containing toxic pollutant* ok combination of pollutant* unden paragraph (I) of thi* subsection, the AdminittKatoK, in accordance with tection 553 of title 5 of the United State* Code, thall publish a proposed effluent standard {ok a prohibition) for auch pollutant ok combination of pollutant* which thall take into account the toxicity of the pollutant, it* persistence, dtgAadability, the usual ok potential pretence of the 93 MONS 047234 affected organismi in any waters, the importance of the affected organisms and the nature and extent of the effect of Xht toxic pollutant on inch organisms, and ht shall publish a notict fox a public, heating on such proposed standard to be held within thinly days. As toon as possible after Aucft heating, but not later than Six month* after publication o( Xht proposed effluent standard (oa prohibition), unit** Xht Administrator find*, on the attend, that a modification of *uch proposed standard Ion prohibition) i* justified based upon a pntpondtnanct of evidence adduced at Such hearings, Such standard I or prohibition) shall be promulgated. (3) Ij after a public hearing the Administrator find* that a modification oj such proposed standard (oa prohibition) is justified, a revised effluent standard (oa prohibition) for such pollutant or combination of pollutants shall be promulgated immediately. Such standard (oa prohibition) shall be reviewed and, if appropriate, revised at least every three years. (4) Any effluent standard promulgated under this section shall be at that level which the Administrator determines provides an ample margin of safety,. (5) When proposing or promulgating any effluent standard (oa prohibition) under this section, the Administrator shall designate the category or categories of sources to which the effluent standard (oa prohibition) shall apply. Any disposal of dredged material may be included in Audi a category of source*' after consultation with the Secretary of the Army. (6) Any effluent standard (or prohibition) established pursuant to this section shall take effect on Aucb date oa dates as specified in the order promulgating such standard, but in no case more than one year from the date of such promulgation. (7) Prior to publishing any regulations pursuant to this section the Administrator Shall, to the maximum extent practicable within the time provided, consult with appropriate advisory committees. States, independent experts, and federal departments and agencies," The "List" vaa published according to proposed criteria in 38FR lSObl*, July 6, 1973 "Proposed Criteria.,.," "Pollutants were chosen joA inclusion on the initial list in light of the following criteria; 1, Data from laboratory or field studies indicate that the pollutant could, if discharged into water, constitute a serious environmental threat. The types o( data examined in making this judgment are set forth in Part I below. 2. The pollutant is discharged, or has the potential to be discharged, from point sources and constitutes a very serious environmental threat. 9b HONS 047235 3. Vata are available to utabliih effluent itandaxd* meeting the At4uiA.em.rUi of the Act. 4. Standard retting under Section 307 (a) i* appropriate, and la ntctuaxy became the pxoxpective timing and efftctivenex* of abatement action* undex other provision* of the Act ate not comenAuxate with the natuxe and iexicurne** o{ the problem* identified by the above cxitexia," 1. Explanation of Cxitexia "The fir*t cxitexion concern* the antuaf ox potential damage that a uatex dixchaxge of theit material* nay create by virtue of contain toxicological propertie*. detailed toxicological data axe examined to detexmine whethex one ox moxe of there type* of effect* axe knowni bioaccumulation, carcinogenic, mutagenic and texatogenic effect*, and high acute toxicity. Specifically, the following type* of data axe reviewedi 1. Available data concexning uhethex a *ub*tance ox it* chemical ox biological txan* formation pxoduct i* bioaccumlated thxougk an aquatic mtchanixm to the extent that they xtAult ini (a) Kepxoductivt impairment in any important ipecitx, ox (b) Concentration* in food *ouxce* in exce*4 of applicable federally extablixhed tolerance level*. 2. Vata concerning caxcinogtnic, mutagenic, and texatogenic effect*. UatexiaJU likely to be caxcinogtnic, mutagenic, ox texatogenic to man axe further evaluated a* to their chemical, biological, and phyAical xtability in water. 3. Vata concerning high order of toxicity a* meaxuxed by xhort-term lethality Hit*. In tfu* connection a clarification of a iubitanct a* 'highly toxic' to man according to claxxification* e*tabli*hed by the department of Tranxportation and the Environmental Protection Agency (J<"Tr 7934, ftbruaxy It, 1971, 40 CFR U2.I) and the Environmental Protection Agency and the Food and Vrug AdminUtration texting procedure* 140 CFR 162. i and 21 CFR 191.10) is particularly relevant. According to the reference* cited above, aubxtance* which have an oral LVSO of SO mg/kg of body weight or let* or have a dermal LVSO of 100 mg/kg of body wexght or lex* are defined a* highly toxic to mcumal* and are examined further. The term 'oral LVSO' mean* that xingle oral do*e which i* lethal to one-hotf of the text population within 14 day*. The term 'dermal LVSO' mean* that do*e dermally abxorbtd in t4 hour* which i* lethal to one-half of the text population within 14 day*. 95 HONS 04723b Foa the protection oi aquatic tilt, *ubilances pnopoitd to bt classiiied ai 'highly toxic' according to the National Academy of Science* water pollution tanking sy&ten may bt considered far inclusion in the litt. Such substances art thou which ant toxic to aquatic lift ai measured by a H hour LC50 oi 10 mg/1 ok less. Tkt term ' LCSO' means that concentration o{ a Substance in water which in lethal to one-holi oi tht hit population in thi specified time period*. Teating method* *uch a* tho*t iound in 'Standard Method* <oa tht Examination oi Water and Wastewater,1 ISth Edition, part 231, 1971, or their equivalent will be considered adequate. "The itcond criterion concern* tht seriousnts* oi discharge* or potential discharge* oi the pollutant iron point *ouxce*. Relevant here art 4och factor* a* tht nature and extent oi toxic tiitet* a**odated with the pollutant, the extent to which diichargt* oi tht pollutant have been identifaed and the production, distribution, and uit pattern oi the pollutant. Vata must bt available irm welt documented fatld itudie* showing damage to important organism* irom discharge* oi the compound into water*, or technically suiiidert to show the material has tht potential to be environmentally harm{ul aiter being discharged irom point *ource* to the water." "Tht third criterion concern* setting eiiluent standards far pollutant* on the list. Tht fallowing art representative the categoric* oi data useful in itandard setting {o* each material. I. Toxicity to mm and other organisms; i. Carcinogenicity, mutagenicity, and teratogenicity data; 3. Transport paths oi the material in tht environment; 4. Sioaccumtation and bioconcentration; 5. Chemical, physical, and biological transformation* in tht environment; 6. Reliability and accuracy oi analytical procedure*; 7. Chemical characteristics; I. Production and industrial or cotmercial-utilization; 9. SouAceA oi the pollutant to water; 10. Environmental incidents attributed to the material I fash kilt*, etc,it II. Presence oi the material in the environment, residue levels in various organism*, ambient concentrations in rivers, lake*, etc.; 12. State and Federal regulatory requirement* concerning the material; 13. Classes and characteristics oi witters into which the material is discharged." 96 Q<t7 23? "The jouAth caitenion conctAni the ovenatt environmental e^ect o{ tht control mtakuKti avaitabtt, including tht ukt ol Ku^titut* pKoductk, and pokkibtt tiitctk upon ghound uxUtK ok otheK uwiMonmtntat media," Section 311(b) deal* with regulating the discharge of oil and hazardous substances: ''311(b) (1) The CongKtkk htAtby dtctaKek that it Ik tilt polity ol tht United Statek that t/ieAt should be no disch/utgtk oit ok hazardous kututancek into ok upon the navigable mttKS oi trie United States, adjoining shontUnts, ok into ok upon tht mXtKk of tht contiguous zone." There Is at the writing of this report no Toxic Substances Act administered by the authority of the Environmental Protection Agency which defines the tests which should be adhered to by manufacturers of polychlorylblphenyl replacements. The Agency Is now developing guidelines for such tests and Is consulting with Industry oo the matter. A.3.6 Test Techniques By Which Degradability Is Evaluated In this section we are concerned with the standards and tests which might apply to degradability of a compound In the absence of living organisms (physical or chemical degradation) or In their presence (blodegradablllty). We are not aware of standard tests for the evaluation of the purely physical or chemical degradation of transformer and capacitor fluids. One must seek such Information on a piecemeal basis and either design one's own experiment or make Inferences from experlmanta In the physico chemical literature. Inference la the source of much of our estimate of the safety of certain products. An example of the kind of experiment which Is rellad upon to provide Information on nonblological degradation la the study by Siegel and Stewart on the degradation products of silicones whan exposed to high energy radiation [U9l< The technique used by the authors was the exposure of a dimethyl silicone polymer to vacuum-ultraviolet radiation In a photolysis tube. At the conclusion of tha photolysis the products were drawn off Into a mass spectrometer Where analysis was made, and thence the quantum ylslds in ethane and methane and the energy transfer were calculated. These results when coupled with knowledge of the chemistry of formation of the silicones give a clue to the effect of sunlight upon silicones, namely that the aillconea yield degradable products. In a similar fundamental study of photolysis in the near ultraviolet of dlmethyalllconea, Delman.Landy and Simms [50] found from the use of two different activating lamps that If the ultraviolet radiation Is energetic enough and if oxygen is present, silanes are formed. These finding* were made under carefully controlled physical and chemical conditions. The conclusion of these results Is that In sunshine and air the silicones will degrads to sllanols (S1-0H structures) and tbence to silica and water. In the environment there Is also water present, and one would expect all the more the formation of sllanols. 97 HONS 047238 Attempts are under vay In Industry to provide more direct environmental testing of the dimethyl silicones to determine with certainty the degradation of these products hut the studies vill be long and difficult. There are, however, several standard methods of blodegradablllty measurement. Most of these depend upon the degradatlve activity of sewage sludge or selected bacteria. Processes range from the simple so-called River Die-Away test to the difficult contlnuoua-actlvatedsludge test [51]. This last Is specified by the law of at least one European nation for detergent degradability tests [52]. The river die-away test consists of mixing a quantity of natural river water with a known amount of the substance under study. Periodic sampling allows the Investigator to follow the rate at which the original substance decays. There Is also a well known, often used, batch activated-sludge teat. It Is slallar to the river dle-eway test except that a prascrlbed amount of activated eludge la added. The eludge or culture used may be made highly uniform and le commercially obtainable [53]. Sealcontinuous methods of sludge addition have also*been devised [51]. These are more likely to Involve pilot-plant scale equipment than the Mason Jars called for In the River Die-Away and hatch teata. So far aa we are aware the only teat for blodegradablllty which baa the stamp of approval of an industry-wide comdttee, la that for sulfonate blodegradablllty promulgated by the Subcommittee on Blodegredetlon Teet Methode of the Soep and Detergent Association [53]. This test, which defines whet le meant by "biodegradable" for the purposes of the soep and detergent Industry, le a detailed procedure for testing eulfonee by e modified aemlcontlnuoua activated-sludge method. Defined In the test are solutions and vsaaels to be used, design of aerator, source of uniform bacterial culture, and directions for sampling and rate of aeration. The Soap and Detergent Association test baa bean applied to the phthalate asters with results that were gratifying to producers of the phthalatee L55]. Appended to this section are two teste selected from the EFA Manuel of Methods for Chemical Analysis of Waters and Wastes 19T* [51*]* These tests were culled to Illustrate comon testa In the field. 96 MONS 0^7239 BIOCHEMICAL OXYGEN DEMAND <5 Day*. 20*C) ) . ' ' STORET NO. 00310 i 1. Scope and Application 1.1 The biochemical oxyfen demand teat (BOD) a used for determining the relative oxygen requirements of municipal and industrial wastewaters. Application of the test to organic waste discharges allows calculation of the afTect of the discharges on the oxygen resources of the receiving water. Data from BOD tests are used for the development of engineering criteria for the design of wastewater treatment plants. . 1.2 The BOD test is an empirical bioassay-type procedure which measures the dissolved oxygen consumed by microbial life while assimilating and oxidizing the organic matter present. The standard test conditions include dark incubation at 20*C for a specified time period (often 5 days). The actual environmental conditions of temperature, biological population, water movement, sunlight, and oxygen concentration cannot be accurately reproduced in the laboratory. Results obtained mutt take into account the above factors when relating BOD results to stream oxygen demands. X Summary of Method 2.1 The sample of waste, or an appropriate dilution, it incubated for 5 days at 20*C in the dark. The reduction in dissolved oxygen concentration during the incubation period yields a measure of the biochemical oxygen demand. 3. Comments 3.1 Determination of dissolved oxygen in the BOD test may be made by uae of either the Modified Winkler with Full-Bottle Technique or the Probe Method in this manual. 3.2 Additional information relating to oxygen demanding characteristics of waste waters can be gained by applying tha Total Organic Carbon and Chemical Oxygen Demand test* (also found in this manual). 4. ' Precision and Accuracy 4.1 Eighty-six analysts In fifty-eight laboratories analyzed natural water samples plus an exact Increment of biodegradable organic compounds. At a mean value of 2.1 and 175 mg/I BOD, the standard deviation was 0.7 and 26 mg/1, respectively. ' (EPA Method Research Study 3). 4.2 There is no acceptable procedure for determining the accuracy of the BOD test. 99 MQNS QH72HQ S. Reference* 5.1 The procedure to be ued for this determination is found in: Standard Methods for the Examination of Water and Wastewater, 13th Edition, p 489, Method 219(1971). 100 MONS 0472^1 DISSOLVED OXYGEN (Electrode) STORET NO. 00299 1. Scope and Application 1.1 The probe method Jor dissolved oxygen is recommended for those samples containing materials which interfere with the modified Winkler procedure such as sulfile, thiosulfate, polythionate, mercaptans, free chlorine or hypochlorite, organic substances readily hydrolysed ih alkaline solutions, free iodine, intense color or turbidity, biological floes, etc. 1.2 The probe method Is recommended as a substitute for the modified Winkler procedure in monitoring of streams, lakes, outfalls, etc., where it is desired to obtain a continuous record of the dissolved oxygen content of the water under observation. 1.3 The probe method may be used as fe substitute for the modified Winkler procedure in BOD determinations where it Is desired to perform nondestructive DO measurements on a sample. 1 1.4 The probe method may be used under any circumstances as s substitute for the modified Winkler procedure provided that the probe itself is standardised against the Winkler method on samples free of interfering materials. 1.5 The electronic readout meter for the output from dissolved oxygen probes is normally calibrated in convenient acale (0 to 10, 0 to 15, 0 to 20 mg/1 for example) with a sensitivity of approximately 0.05 mgfliter. 2. Summary of Method 2.1 The most comnfcn instrumental probes for determination ofcUssolvad oxygen in water are dependent upon electrochemical reactions. Under steady-state condi tions, the current or potential can be correlated with DO concentrations. Interfacial dynamics at the probe-sample Interface are a factor in probe response and a significant degree of interfacial turbulence is necemary. For precision performance, turbulence should be constant. 3. Sample Handling and Preservation 3.1 See 4.1, 4.2, 4.3,4.4 under Modified Winkler Method. 4. Interferences 4.1 Dissolved organic materials are not known to interfere in tha output from dissolved oxygen probes. '' 101 HONS 0*72** 4.2 Dissolved moronic salts arc a factor in the performance of dissolved oxygen probe. 4.21 Probes with membrane! respond to partial pressure of oxygen which in tum is a function of dissolved inorganic sails. Conversion factors for seawater and brackish waters may be calculated from dissolved oxygen saturation versus salinity data. Conversion factots for specific Inorganic alts may be developed experimentally. Broad variations in the kinds and concentrations of salts in samples can make the use of a membrane probe difficult. 4.2.2 The thallium probe requires the presence of salts In concentrations which provide a minimum conductivity of approximately 200 microrohos. 4.3 Reactive compounds can interfere with the output or the performance of dissolved oxygen probes. 4.3.1 Reactive ganes which pass through the membrane probes may interfere. For example, chlorine will depolarize the cathode and cause a high probe-output. Long-term exposures to chlorine will coat the anode with the chloride of the abode metal and eventually desensitize the probe. Alkaline samples in which free chlorine does not exist will not interfere. Hydrogen sulfide will interfere with membrane probes if the applied potential it greater than the half-wave potential of the sulfide ion. If the applied potential is lets than the half-wave potential, an interfering reaction will not occur, but coating of the anode with the sulfide of the anode metal can take place. 4.3.2 Sulfur compounds (hydrogen sulfide, sulfur dioxide and mercaptan*, for example) cause Interfering output* from the thallium probe. Halogens do not interfereTrith the thallium probe. 4.4 At low dissolved oxygen concentrations, pH variation below pH 5 and above pH 9 interfere with the performance of the thallium probe (approximately *0-05 mg/1 DO per pH unit). The performance of membranes is not affected by pH changes. 4.5 Dissolved oxygen probes are temperature sensitive, and temperature compensa tion is normally provided by the manufacturer. The thallium probe hat a temperature coefficient of 1.0 mv/*C. Membrane probes have a temperature coefficient of 4 to 6 percent/*C dependent upon the membrane employed. 5. Apparatus 5.1 No specific probe or accessory Is especially recommended as superior. However, probes which have been evaluated or are in uae and found to be reliable tit the 102 0 W**3 HONS Weston & Slack DO Analyzer Model 30. the Yellow Springs Instrument (YS1) Model 54. and the Beckman Fieldlab Oxygen Analyzer. 6. Calibration . *, Follow manufacturer instructions. 7. Procedure . Follow nianufacturer instructions. & Calculation ,, Follow manufacturer instructions. 9. Precision and Accuracy Manufacturer's specification claim 0.1 m*/l repeatability with tl% accuracy. *03 MQNS 0 A.3.7 References for Section A.3 1. Schmidt, H., and Schultxe, 0., (Liebig's) Annelen, l88l, p. 207, p. .238 2. Penning, C. H.,'Physical Characteristics and Comaerical Possibilities of Chlorinated Diphenyl," Ind. Eng. Chen. 1930, Vol. 22, p, ll80. 3. Clark, F. M.,"Nonflammable Dielectric Organic CompoundsInd, Eng. Chem. 1937, Vol. 29, p. 698. It. Clark, F. M., Trane. Electrochea. Soc. 193h, Vol. 65, 59. 5- Broadhurst, M. 0.,"Use ahd Replaceability of Polychlorinated Biphenyls." Environ. Health Perscect. 1972, Vol. 2, pp. 01-102. 6. Holden, A. V.,'Source of Polychlorinated Biphenyl Contamination in the Marine Environment." Mature 1970. Vol. 228, pp. 1220-1221. 7- Koeman, J. H., Ten Noever De Brauv, M. C., and Devos, R. H., "Chlorinated Biphenyls in Fish, Mussels, Birds from the River Rhine and the Netherlands Coastal AreaNature 1969, Vol. 221, pp. 1126-1126. 6. Jensen, S., Johnels, A. 0., Olsson, M-, and Otterlind, G.,"DDT and PCB in Marine Animals from Swedish Waters." Mature 1969, Vol. 22k, pp. 2l*T-250. 9. Zitko, V., Bull. Environ.. Contain. Toxicol. 1970. Vol. 6, p. U6U. 10. Veith, 0. D.,"Recent Fluctuations of Chlorobiphenyls (PCBs) in Green Bay, Wisconsin Region." Biviron. Health Peraoect. 1972. Vol. 1, pp. 51-62. 11. Kimbrough, R., CRC Reviews of Toxicology. Jan. 197b, p. bb8, Chemical Rubber Company, Cleveland. 12. Schveitser, G. E7, statement at the Wisconsin State Hearings on PCBs, Madison, Wisconsin, August 1975. 13. Stallings, D. L., and Mayer, F. L.."Toxicitiei of PCBs to Fish and Environmental Residues." Environ. Health Perspect. 1972. Vol. 1, pp. 159-16b. lb. Hansen, D, J., Parrish, P. R., Love, J. J., Wilson, A. J., Jr., and Wilson, P. D.,"Chronic Toxicity, Uptake and Retention of Aroclor 125b In Two Estuarine Fishes," Bull. Environ. Contam. Toxicol. 1971, Vol. 6, pp. 113-119. 15. "PCBs and the Environment," Interdepartmental Task Force on PCBs, Com-72-10bl9, National Technical Information Service, U.S. Department of Cousnerce, March 1972. 16. Kuratsune, M., "Yuaho , Characteristics and Long-term Effects," National Conference on Polychlorinated Biphenyls, Environmental Protection Agency, Chicago, November 19-21, 1975. 10b MQNS 047245 17. Dauppi, T. A., and Curria, C. C., Product Engineering. lpfcp, Vol. 20, p, 108. 18. Curria, C. C., and Smith, B. F.,"Flov Cbaracteriatica of Organopolysiloxane Fluid* and Greases,"Ind. Eng. Cbsm. 1950. Vol. 1(2, p. 21*57- 19. Fitiaimone, V. G., Pickett, D. L., Mllitz, R. 0.,and Zieaan, W. A., Trans. A.S.M.E, (19^6), Vol. 68, p. 365. 20. Scott, D. W., jT An. Chen. Soc. 19t6. Vol. 68 , 356. 21. Patnode, W., and Wilcock, D. F,, ibid., p. 358. 22. Fordham, S., The Silicone*. The PhiloaophicalLibrary, Rev York, ,1961 alao Moll, W,, Chemistry and Technology of the Silicone*, Academic Prtae, ReV York, .1968 23. ASTM Standard Method D 92, Annual Book of Standard Method* Part 1*0 American Society for Testing and Material*, Philadelphia, Pa., 1975* 2lt. Clark, P. M., Isolating Material* for Design and Practlc*. John Wiley A Son*, Rev York, 1962, pp. 136 and 320. 25- See for example "Dielectric Properties of Dov Corning Silicone Liquids," Issued by Dov Corning Corporation, Midland, Michigan. 26. Stock, A., and Boaieskl, C., Bar. 1916. Vol. 1*9, P< 111. 27. Kipping, F. S., Prop. Boy. Soc. 1937, Vol. 159A, p. 131. 28. McGregor, R. R., Slllconee and Their Uses. McGrav-Hill Book Company, Rev York, 1951*. 29* Link, C. , RTE Corporation -- personal comunlcatlon. 30. Duckett, D. A., Paper before the General Meeting of the Edison Electric Institute, Transmission and Distribution Conlttee, Minneapolis, Minnesota, May 8, 1975. 31. Morrison, R. T.,7ttd Boyd, R. R., Organic Chaml*try. Allyn A Bacon, Rev York, .1966 32. Munch, F. B., German Patent Disclosure Ro. 2,310,007,13, Sept. 1973, U.8. Patent Ro. 3,796,931*. 33. Munch, R. H., Monsanto Chemical Company, St. Louis, Mo. -- personal conunlcatlon. 31*. Munch, R. H., "Rev Capacitor Impregnants," Conference Paper presented at IEEE Pover Eng. Soc. 1975 Winter Meeting Session. 35. Report on MCS 1238, Obtainable from Corporate Medical Dept., Monsanto Chemical Company, St. Louis, Mo. 63166. 36. Graham, P. R.,"Phthalate Ester Plasticizers - Why and Bov They Are Used ."Environ. Health Perepect. 1973, Vol. 3, pp. 3-15. 105 MQNS 047246 37. Forster, E. 0. -- personal communication. 36. Rutkovskl, A. J., and Forster, E. 0., Presented at American Paver Society (IEEE) Winter Power Meeting, Hew York, 1975, also Proc. VII Int. Corf, on Electrical Insulating Materials, lost. Elec. Eng., Tokyo, Japan, 1971*. 39. Moffitt, A. E., Jr., Clary, J. J., Levis, T. R., Blank, M. D., Perone, V. B., J. Am. Ind. Hyg. Assoc.. 1975, Vol. 36, p. 633. I4O. Tanaka, A., Adachl, T., Takahashi, T., Yamaha, T., Toxleoloev 107S. Vol. I*, pp. 253-261*. !*1. Peters, J. V., Cook, R. M., Environ. Health Persnect. 1973. Vol. 3, PP- 91-91*. See also Rubin, R. J., and Jaeger, R. J., ibid., 1973, Vol. 3, pp- 53-59,and other papers from N.I.K.H. Sciences Conference on Phthalic Acid Esters, Sept. 6-7, 1972 in Environ. Health Peraoect. 1973, Vol. 3, passin. 1*2- Capacitor Fluid XFS-I1I69L statement on development of fluid by Dov Chemical Company and McOrav-Editon Company, Dec. 2, 1975, Dov Chemical Company, Midland, Michigan. 1*3- Environmental Impact Statement on 0CFS-l*l69L Capacitor Fluid. Dov Chemical Company, Midland, Michigan. ' 1*1*. National Academy of Sciences report on tbe Principles for Evaluating Chemicals in the Environment. National Academy of Sciences, Washington, D.C., 1975* 1*5. Registry of Toxic Effects of Chemical Substances, 1975 ed., U.8. Dept, of Health, Education and Welfare, National Institute for Occupational Safety and Health, Rockville, Maryland 20652. 1*6. Muk&l, N. , Lee, P. F., Oguri, M., Schepens, C. L., Can, J. Ophthalmol 1975, Vol. 10 (3). p. 391. 1*7. Perkin-Elmer Chromatography Newsletter, 197**, Vol. 3, p. 15. 1*6. "Polychloroblphenyls and the Environment." Interdepartmental Task Force on PCBs. Com.-72-10til9 National Technical Information Service, U.S. Dept, of Cossnerce, Springfield, Virginia 22151* 1*9- Siegel, 8., end Stewart, T.,"Vacuum Ultraviolet Photolysis of Polydlmethylslloxsne Gas Yields and Energy Transfer "J. Phys. Cbem. 1969, Vol. 73, p. 823. 50. Delman, A. D., Landy, M., and Sims, B. B., J. Polymer 8c1. 1969, Vol. 7. p. 3375. 51. Weaver, P. J., and Coughlin, F. J., 'Yfeasurement of Biodegradability," Amer. Oil Chcm. Soc. 1961*. Vol. 1*1, p. 738. 52. Publication 253/62 of the Federal Council of the German Federal Republic, 1962. 106 MQNS Q<*72<*7 53. Soap and Detergent Association, Amer. Oil Che*. Soc. lofis. Vol. 1|, p. 966. " 5I1. Published by U.8. Environaental Protection Agency, Office of Technology Transfer, Washington, D.C. 20U60. 55- Saeger, V. W., Tucker, I. 8. Ill,'Pbthalate Esters Ubdergo Ready Biodegradation," Plastics Eng. 1973. Vol. 29 (8), pp. h6-k8. 56. Gleason, M. It., ed, Clinical Toxicology of Coaaerclal l*th Bd., Villiaas and Wilkins, Baltimore, .1975 1 107 HONS Q47248 A. It The Scope and Influence of Government Regulations The purpose of this section Is to Identify the several government agencies which have potential regulatory power over new Insulating fluids, to describe the particular area of concern over which each exercises regulatory power, and to define what criteria and procedures are used to determine whether a new fluid falls within the purview of each particular agency or regulation. The eaphaals will, therefore, be on the regulations themselves; criteria and testing procedures which support or are cited in theae regulations Will he briefly identified. In Section A,3.2, these test techniques are sore thoroughly explored. A.li.l Environmental Regulations* Environmental protection regulations are developed and enforced by the Environmental Protection Agency (EPA) and by the various state departments of natural resources. The state agencies generally follow the Federal regulations, and they may In fact have operational responsibility for enforcing the Federal environmental regulations. Being more closely in touch with the local Issues and being under less complex operating constraints, the states can often act more rapidly than the Federal enforcement agencies. It is Important, therefore, that the state and Federal environment regulatory bodies act under rigorous, quantitatively definable criteria In establishing and enforcing their regulations. We will review the existing and pending Federal regulations, recognising that these will also probably he reflected in any state acts. Insulating and dielectric fluids are typically very stable compound! which have low vapor pressures and which, therefore, do not represent a significant air pollution problem. The primary environmental effect Is In water, and so the primary source of environmental regulation of such fluids is: . Public Law 92-500 (86 Stat. )816 "Federal Water Pollution Control Act Amendments of 1972" Three sections In this act are of particular importance for evaluating the Impact of regulations: 1. Bee. 307a "Toxic effluents." A proposed list and a final list of toxic substances were published by EPA in the Federal Register on July 6, 1973 (38FRI60UU)3 on September 7, 1973 (38FR2l3l*2), respectively. Criteria for selecting these substances were Included, thereby Indicating the standard* by *Section A. 3. It also contains discussions of Federal environmental regulations in terms of definitions of test techniques and criteria. 2See Section A.It.3 "Occupational health," for air quality criteria in the working place, ^Federal Register (FR), vol. 36, page l80blt. \ 108 HONS 047249 which new substances can be evaluated. The toxic substance list it not enforceable, however, until standards for allowable levels of these toxic substances are finally promulgated. Although standards were proposed on December 27, 1973, these have not yet reached final legal status. 2. Sec. 307b "Pretreatment standards." The Administrator of EPA ia authorised and directed to publish and promulgate standards for pretreatment of pollutants which could be Introduced into publlcally owned treatment works. 3. Sec. 311 "Oil and Hazardous Substance Liability." {spills, leakage, pouring hazardous substances into navigable waters of the U.S.). On August 22, 197**. an advanced notice was issued: "Vtsignation and dtttMiUnation ol Ktmovability ol hazardous substances {\om waltA." (39FR30*t66). In responge to this advance notice, written comenta were received and were incorporated into a proposed set of rules issued on December 30, 197? (b0F?59960). When promulgated, these rules will provide the basis of the haaardous chemical (including PCBs) spill control program. Key elements activated by these regulations will probably Include mandatory reporting of discharges, clean-up and damage mitigation, and civil penalties which may be assessed by both the Environmental Protection Agency and the Coast Guard. **. Sec. I<02 "Pollution discharge permits." This section empowers the regional offices of SPA to issue permits limiting the allovsble levels of pollutants in effluent discharges. Limitations on polychlorinated biphenyls have already been included in several permits. "Pollutant" is defined (in 8ec. 302) as effluents which "would intVl{VLt With tilt attainment on mainttnanct c j that uattn quality in a specific poKtion ol tht navigablt wattes which shall assWit protection ol public, mill Supplies, agaicultuAal and indastiUal tided, and tht protection and propagation o{ g balanced population oj *htlilish, iish and wildlilt, and allow rtcttational activities in and on tne wattk.........." In sddltlon to ths existing lsglslstlon cited above, Congreea is in the process of working on s Toxic Substances Control Act, which If passed would give SPA mors direct control on production and urns of identified toxic substances. A.*.2 Poisonous Ingredients in Foods The Food and Drug Administration (FDA), an agency of the Federal Department of Health, Education and Welfare, haa the responsibility for administering ths consumer protection standards established by ths Federal Food, Drug, and Cosmetics Act of 1938 with amendments (FTDCA) (U.8. Cods, Title 21). The various stste departments of public bealth cooperate in 109 MQN5 0472SO maintaining proper food standards, under authority of atata public health leglelatlon- Whereas FDA enforcement authority concerns only foods Involved in Interstate commerce (Bee. 703 and 70*t of FPDCA), the state may, of course, take local action. * "Poisonous substances" Include all substances documented to be harmful to human health. Thus, they may be specifically identified in PM regulations (as in the case of PCBs; see 38FRI8096, July 6, 1973) or known to be poisonous from other reliable sources such as "The Toxic Substances List" published by the Rational Institute for Occupational Safety and Health (see Section A.It.3 below). Likewise, tolerance levels are not specifically identified by PSA for each known poison, but rather this is Judged on a case-by-case basis, as specified in 8ee. 1*06 of PFDCA.1 Any new insulating or dielectric fluid which is identified by any Federal agency to be poisonous would thus come within PDA Jurisdiction. In relation to this, it should be noted that the PDA regulations on PCBs (38PRI8O96} specifically exempt PCB transformers tad capacitors; their being in sealed containers was an influential factor In thie decision. - In enforcing its regulations, PSA can request a manufacturer to recall an adulterated product, under threat of proeecution. It can, under court authority, eeite a shipment of adulterated food. And it can legally prosecute manufacturers of illegally adulterated foods. Actions are reported ins "FDA Weekly report of seltures, prosecutions, injunctions, field corrections and recalls," published weekly by the PM Press Office, Rockville, Maryland 20652. A.b.3 Occupational Health The Occupational Safety and Health Administration (08HA), a part of the Department Labor, has the responsibility "to OAAutt AO (OA. <u poiiibti tvuiy woKking nun and topmast in tht Nation Aait and healthiul woKtung condition*....* as stipulated ins Public Law 91-596 (8U Stat. 1590) "Occupational Safety and Health Act of 1970" Dielectric and insulating fluids could come within the scope of OSHA regulations in two ways; 1. During processing of the material by the capacitor and transformer msnufacturers.1 1Although levels were set for PCBs, in the July 6, 1973 regulations. 110 MQNS 047231 2. By ue* of til* capacitor* and transformer* in ot* closely adjacent to work areas. , In the Act cited above, the following responsibilities are defined: 1. The Secretary of Labor (l.e., OSHA) is to promulgate standards for toxic substances (Sec. 6). 2. The Secretary of Labor also Is empowered to inspect working places (Sec. 8) and to enforce the standards (Sac. 10, 17). 3. The Secretary of Health, Education and Welfare, through Its agency. The National Institute of Occupational 8afsty and Health (HI06H) Is to carry out research, develop criteria, and carry on training concerning health and safety In the working place (Sec. 20, 21, 22). Thus, NX08H establishes standards, while OSKA promulgates and enforces these standards. The following publications and standards have resulted regarding toxic substances: "Registry of Toxic Effects of Chemical Substances," 1975 Edition, HI08H, Rockville, Md. 20852, June 1975. . In this publication, a large number of toxic substances are listed, along with toxic dose levels, and the reference sources for these toxic doees. Pour PCBs are included. "Occupational Safety and Health Standards," 39PR23502, June 27, 197b. Table 01 lists contaminants, including chlorodlphenyl (b2| Cl); skin 8-hour time weighted average exposure not to exceed 1.0 mg/m^, and chlorodlphenyl (5b| Cl), 8-hour time weighted average skin exposure not to exceed 0.5 ag/m^. (These are currently listed In 29CTR 1910.1000). OSHA has developed draft technical standards establishing require ments for monitoring employe* exposure, medical surveillance, handling and use, training, record keeping, eenitation and housekeeping. Thee* are now available for consent (b0FR5bO33, November 20, 1975). The source of thee* standards le blCFR 50-20b.50 which cites: "Threshold Limit Values of Airborne Contaminants for 1968," Amer. Conf. of Govn. Induetr. Hygienists. The Rational Electrical Code (HEC) - 1971 (ANSI Cl-1971) has been Incorporated within OSHA regulations (29CFR 1910.308; see 39FR23502, June 27, 197b). Dielectric fluids for transformers end capacitors 111 Iher*for# fail vithln 08HA regulation* Insofar a* use of theee fluids Is affected by the NEC. (See Section A.5 of this report for further discussion of the NEC). / A. It. It Transportation The Department of Transportation (DOT) Is involved In both the use and the control of Insulating fluids In these tvo vays: 1* Use. High speed mass transit systems employ electric traction. The electric transformer Is a key Item. It Bust be small because of the else limitations on the transit cars, and fireproof in the event of an accident. Askarel1transformers are therefore universally used In present ground electric transit systems.1 Thus, DOT mey become a significant participant In the move toward both eafe and reliable techniques for continued use of PCBs and for substitutional use of nev Insulating fluids; however, no documentation regarding efforts by this agency to encourage development of improved transformers has yet come to our attention. ' 2. Control. The transportation of hatardous materials'Tall* within DOT'S regulatory power, as ldentlfisd in: ; 1*9CFR Parts 100-199 Transportation; revised as of October 1, 197$. The following sections are particularlypertinent to the insulating fluids question: '' 1. List of Hatardous Materials; sec.172.$ * a. lone of the PCBs, by any of their chemical or trad* name*, ie on the Hat. 1 b. Any substance which qualifies for the llet under definitions given in other section* must be treated ae If on the Hat. 2. Dielectric and Insulating fluids would he Identified as Class B poisons If they were found to be toxic. (See Sec. lT3.3b3, quoted on pp. 91, 92). The Japanese retained askarel In their electric rail cars even after their otherwise complete ban on PCBs; they apparently are now experimenting with a silicone substitute. 112 HONS 047253 3. Effect of list. Proper procedures for the transport of hasardous materials are stated in the following eectione*. Pt. 173 Shippers *173.344 Packing jo* etctil B poisons, liquid a] Closing and cushioning. Att tontaintAS tuit bt tightly and stcuxtly closed. Inside containen* nut be cuifctoned 41 preicrtbed, ok in any out when ntctSSOKy to prevent breakage or leakage. b) Outage. Outage jo* containen* oj Liquid poison jo* transportation by carrier* by Mill jrelgHt, Halt expreii, highway, ok water nut bt as joitrwm 1) Contains* suit not be entirety titled. Sujjictenf interior 4pace mult be tejt vacant to prevent leakage ok distention o{ containtA* due to tAe expansion oj tkt content* jrom inentast oj tejaptnatunt during tMuuit. t) The proper vacant spaee (outage) in a tank cok ok othiA shipping container. depend* on the. coti^aUtnt oj expansion oj tkt Liquid and the maximum Inentast oj tempe*otu*e to which it will be lubjected in tnan*it. Outage mult be calculated to the total capacity oj tht containeK. 31 Liquid potion mult not be loaded into dome* oj tank coni. 4) In tank ca/u, outage mult be calculated to percentage oj the total capacity oj the tank, i.t., *htll and dome capacity combined. Ij tht dome of tht tank cox dotl not pKovidt lujjicient outagt, then vacant ipace mult be tejt in tht *helt to sake up tht regained outage. 3] Tht outagt jo*, tank can* suit not be tell than 1 percent. 1] Mo cargo tank or cornpantment theneoj cued (ok the tnanspontation oj any liquid poison *hatl be compitlefy jetted; lujjicient ipace shall be tejt vacant in tvtny ea*t to prevent leakage jkom ok distention oj any luch cargo tank by expansion oj the content* due to Kite in temperature in tnanut, and such j*ee ipace (outage) shall be lujjtctent in tvtKy cale lo that Such cargo tank shall not become tntiKtly filled with the liquid at 130 *F. 113 HONS 0*725^ J 71.145 txtmptioni poitonou* Liquid*, Cla*i B. a] To'itonout Liquid*, eta** B, a* defined in 171.143, except tho*t fon which no exemption* one pnovidtd a* indicated by the "No exemption" itatement in 177.5 oi thi* chapten, on a* provided ion in 17J.354(c). 4m Lightly cloitd intidt containtn*, *t<mnely ciuhioned when nece**any to pnevtnt bntakagt and packed a* follow*, ant exempt {Aon ipecification packaging, mantling, arid Labeling nequinement*, except mat manking name of content* or outiidt containen it nequined fon thipment* via cannien by waten. Shipment* fon tnanipontation by highway cannien* ant exempt al*o fnom Pant >77 of thi* chapten, except 177.<17, and Pant 397 of thi* title. I] Jn glat* on eanthenmne containen* not oven ) quant capacity each, on in metal containen* on polyethylene bottle* not oven t gallon capacity each, packed in *tnong otuUide wooden boxt* on bonnet*. i 7] In gla** on eanthenwane containen* not oven I pint capacity each, on in metal on polyethylene containen* not oven I quant capacity each, packed in *tnong owUidt fibenboand bout*." The following sections are also or aoae relevance: 173.**1*< Pol eon material labele Pt. 17>* 17**.532 17*1.538 17*1.586 Rail Freight Loading other hazardous materials Rail freight; loading and storage chart of hazardous aaterlal Handling hazardous aatsrlals, by carriers by rail freight Pt. 175 Carriers by Rail Sxprsss Pt. 176 Rail Carriera In Baggage Service 176.702 Hazardous naterlale Pt. 177 177.821 177.81il 177-8*18 177.860 Public highway carriers Hazardous materials forbidden or Halted for trensportatlon Loading; poisons Loading and storage chart of hazardous materials Accidents or leakage; poisons Pt. 178 Shipping container specifications Pt. 179 Specifications for Tank Cara 111* mqns A. I*. 5 Solid waste disposal The Department of Health, education and Welfare (HIW) haa certain regulatory control on aolld vaate dlapoaal through the authority of the Solid Vaate Dlapoaal Act (PL 89-272 and amendments; aee 1*2 I.B.C., Ch. 39). In particular, HEW la to recommend and publleb guideline# and information on aolld vaate recovery, collection, aeparatlon and dlapoaal. Pacllltlea owed or controlled by the Federal Government must comply vl^h tbeae puhllahed guideline#. The dlapoaal of the PCB# end of solids contaminated by aakarela la hecominc increasingly difficult. Problem# aaaoclated vith di#po#al of nev fluid# should be anticipated at an early stage In their development; the Federal aolld vaate disposal regulation# form one set of criteria by vhlcb disposability of nev fluid# can be judged. II 115 HONS 047256 A. 5 The Scope end Influence of Insurance and Fire Code Requirements In addition to the various federal and state governmental regulations which might restrict the use of fluids In electrical equipment, one Must also make sure that such equipment does not conflict with Insurance and fire code regulations. The two are cloeeljr related and therefore can be most easily discussed together. The Rational Electrical Code (EEC) Is one part (volumd 6) of the 1975 Rational Fire Codes, issued by the Rational Fire Protection Association (RFPA). This cods ie developed end continually updated by a et of comsittees which la sponsored by RFPA end ie composed of representatives from manufacturers, users, firs insurance companies, Independent testing laboratories, and municipal and state fire aafety and regulatory agencies. As such, it Is an authoritative work universally recognised as s standard statement of eafe electrical fire practice. Although the IfEC is not in itself lav, it Is usually adopted with various levels of modification as the legal electrical building code. Equipment to be legally installed within the Jurisdiction of such s code must therefore conform to EEC. A further note on the EEC is thft it has been adopted In whole by 06HA ("Occupational Safety and Health Standards," 29CFF 1910.308 - Bee 39FR23502, June 27, 19TM and it thersfore has a very broad legal importance In Industrial facilities. 06HA regulations are discussed more extensively in Section A.4.3. As presently written, the IEC specifically refers only to mineral oils and mskarels as insulating flulda. Since no more general descriptions or definitions are given, one is led to infer that other fluids are excluded unless specifically identified in future editions. To get s new material listed In the EEC, the manufacturer must propose the desired inclusion to the Electrical Coordinating CoMittee of EEC, along with evidence substantiating the fire aafety of the material. Before approval, however, the cossnlttee would probably require testing and safety verification by an independent laboratory such as Underwriters Laboratory (UL) or Factory Mutual Engineering and Research (FMER). UL is an independent not-for-profit testing laboratory which carries out tests on products for manufacturers and makes "listing" or "classification" Judgment based on these tests: "Listing" - tbs product is deemed to meet the requirements of the EEC. "Classification" - s material will be given s flamnablllty clas sification, based on s scale between 0 (water) and 100 (diethyl ether); the procedure Is outlined In: "Tests for Comparative Flanablllty of LiquidsUL Standard Eo. 3b0. 116 HONS 047257 Whereas EEC is an Installation guide, local ordlnancas will often look to tha UL listing to verify that the product Bests NIC standards and therefore can be Installed as directed by the code. FMER is a service ara of the factory Mutual Systen of Insurance companies. It carries out testing of equipment and Issues "approvals" or "acceptances" based on these tests: "Approval" - the product Is deeaed to be safe and suitable for general applications. "Acceptance" - a particular Installation of equipment and materials sets fire safety standards. Such a safety test could be Initiated upon request by a manufacturer or by one of the FM Insurance companies. An Installation of electrical equipment must not only aeet fire ordinances but also Bust be covered by fire Insurance. The Insurance rates are generally set by the State Insurance CoMlsslon, but an Insurance company aunt have verification of the safety of the Installation before agreeing to write Insurance coverage. The insurance Inspector will therefore generally look for UL or FM acceptance, or to soae other Indication that the installation Beets NEC requirements. The Inspector sight also base his decisions on bis ccatpany1s rating of the requesting company and possibly on the users or manufacturer'a own tests. An experimental unit with a new Insulating fluid Bight for Instance be accepted for further field testing under this latter situation. If one unit within a larger installation does not meet standards, temporary approval may be granted.with the understanding that the substandard unit be upgraded to an acceptable level within a specified period. It should be noted that utilities are often self insured and are granted exclusion fron the local codes based on DEC. It Is the general practice of utilities to comply with EEC, however, and they usually work closely with local fire protection people to make electrical Installations safe. When utility earned equipment la Installed In uaera buildings, often the local code or Insurance requirements would nscsssltate that K8C practice be followed. USCOMM-NBS-DC 117 HONS 0^7258