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L IA22622 wafc. tsm& M. AZI-LIA EXPANDED RESEARCH PROGRAM Ame u c a n Zin c In s t it u t e , In c . SCHRADE r. RADTEI Director W Ru miA 60 EAST ilnd STREET NEW YORK 17, N. Y. inj |.io i Le a d In d u s t u e s As s o c ia t io n -j J 0 ! April 1, 1959 To All Members of the American Zinc Institute and the Lead Industries Association Gentlemen: Our Expanded Research Program sponsored by the producers of slab tine and pig lead, has bees Increasing continually In size and scope since its original Inception. It is believed that the time has been reached when the members should be notified of the progress of the Program and this is being accomplished by submitting to you a copy of our First Quarterly Report. The first report is sooevhat longer than subsequent reports vlll be; hovever, it vas felt advisable to provide you with background Information concerning the many projects that are nov under way. Additional reports vlll follow each quarter and we look forward to receiving your comments and suggestions. 0 /-i  wi -'.v-^.tAlw. >. - ' Li^zbZ3 . ^.. .. "*' .........eij L-iiJv ...;..J. ......................... : i j j S e AZI-LIA EXPANDED RESEARCH PROGRAM American Zinc Institute Lead Industrie* Association Cnrterljr Report Bo. 1 April 1, 1959 * ]S 1751.01 TABLE OF CONTENTS I. INTRODUCTION n. LEAD RESEARCH PROGRAM A. LF-15-59 B. LP-H-59 C. LP-9-59 D. LF-1G-59 E. LP-16-59 T. LP-11-59 G. Introduction - 1. IP-19-59 2. LP- 20- 59 3. LP-12-59 k. LP-lk-59 5- LP-21-59 6. LP-22-59 7. LP-23-59 Continuous Extrusion of Lend Cable Sheathing Study of Lead Base Alloys fibre Reinforced lead Lead Chemicals Investigation oi lead for Sound Attenuation Thermal & Spectral Balssivlty of Lead Compounds Lead In Ceramic Materials Effects of Lead Oxide In Porcelain Enamels lead Glares for Ceramic Vhltevare Bodies Wettability of Lead Glares upon Structural Clay Bodies Phase Relationships & Properties of Selected Ceramic Systems Development of Ultra lov Loss Ceramic Dielectrics fundamental Behavior of Lead In Glasses Study of ferroelectrlcs Containing Lead Compounds III. ZINC RESEARCH PROGRAM A. ZT 12-59 B. ZF-5-59 C. ZP-20-59 D. ZF-11- 59 E. ZP-1-59 f. ZP-13-59 G. ZF-L-59 H. ZP-18-59 I. ZB-22-59 finishing of Zinc Die Castings Development of Improved Zinc Die Casting Alloys Corroilon of Hot Water Storage Tanks Wet Storage Staining of Galvanised Sheets Exposure of Galvanised It Competitive Steel Sheet Zinc Anode Installations for Marine Tankers Improvement of Zinc Lithographers Pistes Development of Improved Dry Cell Battery Anodes Evaluation of Zloc Oxide Exterior House Paints ag.j"i it.'i mwi i i.umsuPW^--wssswiMwe turns* L IA22625 I* *i *. : J O I IKTRCPUCTIOM I Thl* is the first of the quarterly reports to be prepared and distributed as a part of the AZI-L1A Expanded Research Program. The purpose of these reports Is to summarize the progress achieved on the many research projects sponsored by the American Zinc Institute and the Lead Industries Association and to advise of re search initiated during the Intervening period. While the members of technical camelttees and subcoenittees are kept in formed of progress on the Individual projects with which they are directly coo cerned, it Is believed desirable to distribute on all-inclusive report such as this for the general membership of the Lead Industries Association and American Zinc Institute and cooperating organizations here and abroad. These quarterly icports will be general in nature, relating only progress achieved In the last report period with emphasis being placed on the general rather then the detailed accomplishments of the Individual research. This first report will also Include the objectives and some background information on each j program as well as a brief summary of projects In existence for sometime. The report will appear under two headings entitled, "Lead Research Program" and "Zinc Research Program". II LEAD RESEARCH PROGRAM 0 A. Continuous Extrusion of Lead Cable Sheathing - (IP-15-59) Partial support for development of an extrusion press capable of continu ously extruding lead cable sheathing alloys has been given to the John F. Robertson Company since May, 1958 and will continue through June, 1959 under present arrangements. Extruders now available are capable of producing pure and copper-Learing lead cable sheathing but have proven unsatisfactory for the arsenical and antlmonlal alloys. Lead Industries Association support partially covers supplies and labor to prove out extruding the press for arsenical and antlmonlal cable sheathing alloys. Press d-velopment, manufacture, and modifica tion have been financed by the Robertson Company. Prove-In of the press was accomplished using pure lead, and from this bace point, extrusion of the F-3 arsenical lead alloy was accomplished. Continuous production rates of 62 to 65 pounds per minute were obtained on pure lead corresponding to linear rates of l8 to 19 feet per minute of 2" 0. D. sheathing. T- 3 elloy could be continuously produced at a rate of 1*3 pounds per minute, corresponding to 12 to 13 feet per minute for 2" 0. D. sheathing. Samples of the sheathing taken during the run-in on F-3 alloy have been evaluated with respect to composition, tensile properties, and grain structure at the Anaconda Wire and Cable Company laboratories. Composition of the alloy waa maintained essentially constant after many repeated extrusion, melting, and freezing cycles. All samples of the sheathing were air cooled during manufacture so that strengths obtained were comparatively low. When treated and quenched to o -1- i I I 22b2b -- Mi*3dKMHMMkH^lubaMiraw 1 , simulate rapid cooling, strengths increased to normal values without signifi cant loss of ductility. Elongation was similar to those of sheathing ex truded on conventional hydraulic presses. Hie grain structure was similar to that of lead samples produced on screw-type presses, except that smaller grain size wan obtained. Shadow patterns on totgie-shaped flow lines were evident on either side of the top of the section whicu resembled, in appearance, the charge welds produced by a hydraulic press and die block but wtre not severe enough to restrict grain growth across them, and for this reason should not be harmful to mechanical performance of the sheathing. Bo streaks or pattens appeared that were attributable to alloy segregation. future work will consist of determining opsratlon conditions for the antimonial alloys and evaluation of the resulting sheathing with respect to composi tion, tensile properties, and grain structure. B. Study of Lead-Base Alloys - (lP-t-59) This research Is being carried out at Armour Research foundation under the supervlelon of C. R. Simcoe. The investigation began in July, 1958# and will continue until July, 1959 under the present agreement. It is believed that the poor creep and tensile properties of lead mitigate against its use in many applications and that Improvement of these properties in homogeneous alloys will produce new market areas, for this reason, a rigorous Btudy of lead alloys was believed necessary to uncover alloy systems showing potential for Improvement in this area. The objectives of thi6 program are two-fold, first, the existing state of knowledge concerning the physical and mechanical properties of lead is to be extended, and second, with this knowledge alloys superior to those now known are to be developed. Progress to date included a survey of available literature and, based on this, a number of binary lead-base alloys have been chosen for study. Pre liminary work will be directed toward a systematic evaluation of the recrystalli sation klnectlcs of the selected binary alloy compositions. Promising composi tions will be subject to further study. future work vl 11 consist of melting, casting, and cold-rolling of alloys followed by a study of rccrystalllzation klnectlcs at three temperature levels. C. fiber-Reinforced Lead - (lP-9-59) Research in developing fibers reinforced lead materials is being conducted at Armour Research foundation under the supervision of R. H. Reed. The in vestigation began sr January of 1959 and is expected to continue until January of i960 under the existing contractual arrangements. Hie objectives of this research are to develop lead-metal fiber composites which desicnstrate better strength and creep resistance than homogeneous lead 0 products, yet still exhibit the virtues of lead with respect to resistance to A - n.A f** LIA22627 chemical attach, nuclear shielding capacity, etc., ao that these inherent pro perties can be more universally applied in chemical and atomic energy industries. The poor creep performance of lead has mitigated against its use In many applica tions in these industries. The initial approach vill he to investigate methods of impregnating fibre metal mattes vith lead, and study strength and creep properties of these composites. The lead-vettablllty of various metal matte cdepositions vill be determined as veil as the effects of matte fibre content, sire, and yield strength on the mechanical properties of the lead containing ccoposltes. Work nov In progress consists of developing techniques to produce composites of lead and tin bronze felts. Good impregnation has been accomplished by im mersion of the bronze felts in charcoal-covered lead - l tin baths subject to mechanical vibrations. Pores have been found to open up In the composites on solidification, and methods of eliminating the porosity or healing the porosity by vorking are being investigated. D. Lead Chemicals - (IF-10-59) This phase of the research program is being conducted by Arthur D. Little, Inc. under the supervision of Dr. Morgan. Under the present contract, this pro gram covers a period of one year, beginning December 15, 1955. Th- fiid of lead chemicals should hold considerable promise for further commercial exploitation as sizeable tonnages of lead organic and inorganic salt* are used presently. A tvo-phase investigation has been initiated, both phases being carried out concurrently. One phase vill consist of a study of the funda mental chemistry of lead, its bonding characteristics in organic and Inorganic compounds and application of this knowledge in the synthesis of new compounds. The second part of the program will be an attempt to synthesize polymers and re lated complex structures, considering the commercial application for these materials. Progress to date includes a review of pertinent literature to plan the initial experimental effort. Underway is an effort to synthesize and polymerize styrl lead derivatives. A similar investigation is being carried out on the adduct of hexaphenyl di-lead and maleic anhydride, the synthesis of dicyclopentadlenyl lead and its polymerization by the ferrocene-type reaction or the maleic anhydride adduct. Z. High Spot Investigation of Lead for Sound Attenuation - (LF-16-59) This investigation is to be carried out by Bolt Berknek and Hevnan, Inc. The project will require little time, and the investigation is expected to be completed prior to the next quarterly report. Lead has long been known to possess excellent sound attenuation char acteristics, hut little use has been made of this Inherent property in archi tecture. The superiority of lead for sound isolation is manifested by the fact tlu>t one producer of passenger aircraft used lead-coated fabrics as a cabin -3* t .r'  re.i-r^Hn* *-- *-- LIA2262S Uai. lining to reduce the nolee level. In splt-e of the apparent velght penalty, lead vaa actually lighter in the final analyila because of ita accoustlcal efficiency. Thie contract la to be a feasibility study for employing lead products In architectural structures for sound Isolation. It i* to be exploratory in nature, pointing out the cost promising areas for the develcraent of aarkets for lead accoustlcal panels, encompassing: (a) A comparison of transmission loss of ccsmon architectural partition constructions vlth simple lead sheets. (b) A compilation of a list of possible applications In vhlch lead vlll be the most economical, the lightest, or the thinnest material vhlch vould satisfy the accoustlcal requirements. (c) Designing of a typical building partition employing lead. T. High Emission Lead Compounds - (IP-11-59) Ibis Investigation la being carried out via fellovshlp support at Bev Tort University under the direction of Professor I. Cadoff. Tellov E. Killer la per forming the laboratory vork during the academic year 1956*1959* The objective of this program Is to 6tudy the thermal and spectral emia6lvity of lead compounds. Eev advances in heat transfer and electronic de vices suggested the Investigation of the properties of lead compounds for use In these areas. The program consists of determining the emission spectra of the group of compounds, FbO, FtS, FbSe, and FbTe. The experimental procedure vlll be to de tect the radiation emanating from the samples by means of a Beckman 13-2 Infra red spectrophotometer. At roam temperature, vhere radiation Is negligible, the emission properties vlll be obtained from the absorption spectrum using toe re lation that emission must equal absorption In order for the sacq>le to remain at room temperature. Progress to date consists of procurement of the spectrophotometer, develop ment of techniques for obtaining roam temperature absorption characteristics, and sample preparation (l.e., thin vafera of the compounds) for transmission studies. It Is expected that test procedures vlll be finalised and preliminary data obtained by the next report period. 0. lead In Ceramic Materials - Introduction Research for furthering the role of lead In ceramics Is being carried out at seven universities on a fellovshlp basis. At present nine fellowships art being supported covering broad areas of Investigation of the effect of lead and its compounds In ceramic materials of all types. -k- w .INI tlHIO W? zq 5 9 1. University of Illinois - (lF-19-59) Two fellowships have been avarded under the direction of Dr. A. I. Andrews. A thesis covering the vork performed by Fellow D. Kessel during the 19571958 academic year has been submitted, and the vork Is surras riled below. Recent Interest In low firing temperature frits has been intensified be cause of the wider use of porcelain enamel on steel and aluminum for building panels. Lead orlde is an effective agent for reducing firing temperature, and therefore is of Importance for minimizing distortion and simplifying the coat ing process. The study was concerned vith 'Some Effects of Lead Oxide in Porcelain Enamels', particularly the effect of lead oxide on the recrystalllration at crystalline opaclflers in enamels end the reduction of reflectance produced by mill-added opaclflers due to solution in high lead enamel glasses. The plan of attack was to add lead oxide to existing enamel compositions rather than make an extended compositional study of lead oxide-bearing enamels. A litera ture survey and bibliography was Included. Tentative conclusions arising from this work were: l) additions of red lead to leadless enamel In general tend to decrease the acid resistance, but lead bearing enamels can be balanced to give acid resistance as Indicated by two lead compositions having excellent corrosion resistance; 2) crystallisation of opaclflers in enamels of high lead content is possible but reflectance of sin enamel, in general, decreases when lead oxide is used; 3) firing temperatures of enamels containing lead oxide as an additive will not be as low as lead oxide-bearing enamels specifically formulated to lave lov firing temperatures; *> solution rate of mill-added opaclflers in lead oxide-bearing enamels Is not very sensitive to heat treatment but prolonged heating periods or higher firing temperatures than normal cause rapid rate of solution; 5) color of enamels con taining lead oxide depended on compositions of the enamel, amount of lead oxide, and type of opacifying crystal. There was a tendency toward yellow coloration when lead oxide was added, but Uverlte, zirconium silicate, tin oxide, and recrystallized ZrOg produced white coatings with lead oxide-bearing enamels. Extension of this work is being carried on by Fellow R. C. Capek In the 1953-1959 academic year. Although a second fellowship s given to the University of Illinois, work has not been Initiated as yet. ; 2. Ohio State University - (LP-20-59) One fellowship under the direction of Dr. R. Russel, Jr. Vork on this fellowship was carried out by Fellow T. V. Latimer during the 1957'1956 academic year and Is being continued by him through the 1956-1959 aca demic year. -5- LI&2263 The objective of this study Is to determine the relative effects of vary ing compositions on the properties of typical lead glazes vhen tested as glass samples and to investlt'te the possibility of using this Information In the formulation of glazes having certain desirable properties vhen applied to typical ceramic vhltevare bodies. The first phase Is being carried out by studying: l) the system FbO AI2O3 - SlOg; 2) the effect of additions of ^03 to selected compositions of the above system; and 3) substitution of RO and RgO oxides for IbO In glasses of selected RO-AI2O3 - B2O3 - 8102 ratios. The effect of the above changes In composition will be determined vlth respect to thermal expansion, strain point, annealing point, hardness, solu bility In weak acids, and density. Information derived freo the above studies vlll be utilised In the formula tion of lead glazes for vhltevare bodies possessing desirable characteristics such as resistance to crazing,acid attack, abrasion, and adequate strength. A bibliography on lead glazes vms prepared. 3- Cleason Agricultural College - (LP-12-59) One fellovshlp under the direction of Professor C. C. Robinson. This Investigation Is being carried out by Tellov X. K. Macfarlane during the academic year, 195&-1959- Ihe vettablllty of lead glazes upon structural clay bodies Is being studied to develop glaze* having superior vetting characteristics. The approach selected Is to evaluate the effect of clay body composition, frit composition vlth respect to lead content, and firing atmosphere on the vettablllty of the frit. A base clay body composition has been selected and compositions vlll be varied by l) raising silicon content; 2) raising calcium content; and 3) lover ing Iron content, In each case holding the proportions of the other constituents constant. Pemco P-239 glaze composition vlll be used as a base, to vhieh vlll be added .1$, .30, and .*t5 equivalents of FbO. firing vlll be done In: l) a reducing atmosphere of carbon monoxide; 2) an oxidizing atmosphere of dry air; and 3) * second oxidizing atmosphere of air saturated vlth vater vapor (at 25C). it. Pennsylvania State University - (lP-lU-59) One fellovshlp under the direction of Professor f. A. Hummel. This Investigation Is being performed by Pellov J. Argyle during the academic year 195&-1959- -6- U 9 A bade study of the phase relationships In the ternary system* PbO - MgO and PbO - IA2O3 810g, Is being undertaken as veil as the thermal ex pansivity of the lead crystalline compounds of sllcates and phosphates, and the terntry compounds consisting of lead-aluminum- silicates and lead-boron-silicates. Primary attention is to be given to the thermal expansion measurements and the ternary phase system PbO - La2O3 - 8102- Vork so far completed Indicates that a ternary compound say exist In the eystem PbO - HgO - PgOj^ but this conclusion Is tentative pending further analysis and a survey of toe system FbO-HgO. The binary system FbO - L02O3 is being studied as veil as compositions on the Join betveen PbO - SiOg and lagO3 - SlOg. Tentative data Indicate the ex tent of liquid limlsclbll.lty in the ternary system and the possible existence of a ternary compound. 5. Rutgers University - (LP-21-59) Two fellovships under the supervision of Dr. J. H. Koenig. The object of the study ou both fellovships Is to develop ultra lov-loss ceramic dielectrics using ultra lov-loss glasses as binders for Vollastonlte or fused quartx for the main component. The vork vas started by Fellow H. M. Bunog during 1957-1958 academic year, and she Is continuing the vork during the present year with S. Sawoguchl. Vollastonlte and fused silica were chosen as the principle components of the dielectric body, because each Is known to have ultra-lev dielectric loss characteristics. Primary consideration has been given to developing glass binders vlth low dielectric losses. Theoretical considerations as to the cause of dielectric losses enter Into the realm of solid state physics. Most glasses contain 81-0 networks, and other positive Ions in the gloss compositions are bound to the Si-0 networks with rather weak forces which may be of Ionic or covalent character. Weakly bound ions are assumed to exist In shallow potential veils such that when an electric field Is applied to the glass there will appear dielectric pclaritatlon composed of electronic and ionic polarisation, P (elec) and P (ion) respectively. P (ion) Is due to the shifting of ions and P (elec) Is due to distortion of the ion's electron cloud. At lov frequencies P (ion) will appear, but as frequency Is Increased, P (ion) begins to decrease because It cannot follow the rapidly chang ing a.c. field. Around the frequency range where the dielectric constant begins to decrease, the P (lon) is out of phase with the applied field, and as a result, high dielectric loss appears. If ions are bound to the 61-0 netvork so that deep potential veils exist, then dielectric loss appears only at very high frequencies because the restoring force for the shift of the lon Is strong in the deep po tential veil and P (lon) Is maintained In phase ever a broader frequency range. Che component of P (lon) may appear at lov frequencies but disappears at higher frequencies because the rate of transfer of the lon causing this component Is so slow coa.>ared to high frequency applied fields that ion shifts ara not made. 7- y vn t j1 / 1 -s/ M.II, i^u w iu * LI A22632 V . Q 0 j ! Q Decrease of dielectric loss at radio frequency ranges Is the objective of the present research and from the above described theory of losses, this can be accomplished by producing deep potential veils for Ions la the 81-0 network. In general, deep potential veils arc realised If the valency and polarlsablllty rf the Ions are large. Lead Ions have valency twice that of sodium and the polari zability Is two to three times as large; hence the depth of the potential veil for lead would be considerably greater than that for sodium. Glasses containing lead can be expected to show a maximum dielectric loss at low frequency and very low loss at higher frequencies - the desired range. Experimental work conducted to date has Included the fabrication of dieleotrics using glasses composed of lead, barium, and bismuth Ions In the 81-0 net work as the binder for Wollastonlte components, and the evaluation of these dielectrics with regard to power factor, dielectric constant, and dielectric loss factor. Seven glasses were evaluated, varying the lead, barium and bismuth com positions, and results were compared to a standard binder glass having the alka line metals, sodium and potassium. In all cases, the elimination of sodium and potassium and the Inclusion of Ions foralng deep potential veils caused signi ficant decrease In the dielectric loss factor. All seven of these bodies have ultra lav dielectric loss, having a JA*-I-1C specification rating greater than L-7- The body having the lovest loss factor developed to date consists of 55^ (M2h8 Wollastonlte, 2C% fk ball clay, 15jt barium carbonate and 10Jt lead blslllcate. future vork will consist of evaluation of other compositions for producing extra low dielectric bodies, and studies of o'her applications where bodies having these characteristics may be used. Also the wider use of lead-flexed bodies will receive attention. 6. Alfred University - (LP-P2-59) One fellowship under the guidance of Professor C. Creene. Work Is being carried out in the present academic year by fellow C. Ideser. The object of this research Is to study the fundamental behavior of lead In glasses. Tne use of lead oxide has been of considerable Importance to the glass Industry primarily because of lt6 great solubility and fluxing action. Char acteristics ascribed to the presence of lead oxide In glass are high Index of refraction, large dispersion, low melting point, vide softening and working -.`nge, adaptable coefficient of expansion, resistance to devitrification, and high capacity to absorb radioactive energy. The many beneficial characteristics attributed to lead could lead to a broad program of Investigation If the effects of lead on each of these proper ties vere to be studied. To narrow down the field of investigation to that area or those areas vhere the greatest contribution can be made, an exhaustive literature study has been prepared. 7. University of California - (LP-2J-59) One fellowship under the supervision of Professor . A. Pask. -8- ex- LIA22633 *--' -------- --- . . air ->--------- ----------- -------------- ----------- - - -------- --- i 9 3tla research i* concerned vith a study of ferroelectric* containing land compound* vlth particular attention being given to Investigation of the le*4 oxlde-lroQ oxide system. A literature search 1* now being made, and from this will come final de finition of the program. l r a - TV -9- .N T IMI' <aw ww BT!T^r LIA22634 ^ -----r- -- - ------ ---------------- ---------'ll ir* -i>>"ii -- - -"- ......... ' ----- ----------- -** o ' J o 1 e III mtc RESEARCH PROGRAM A. Key finishes for Zinc Die Castings - (2M2-59) Research to Improve the corrosion resistance of chromium-plated sine die castings Is being carried out by BatteUe Memorial Institute under the super vision of Hr. Safranek. Work has been in progress since April, 1956 and vill be carried out until July, 1959, under the present agreement. Many plating systems have been evaluated during this period and tvo systems appear to produce corrosion resistance vhlch Is far superior to In dustrial chrome plating as it nov exists. Test panels have been exposed at tvo sites, some for over a period of fifteen months, and the superiority of these tvo systems la apparent. The first of these Is called the 'duplex nickel process", vhlch is a coaaerclally available system in vhlch bright nickel is deposited over dull nickel, affording superior corrosion resistance at areas of local defects In the chrome plating. The other system approaches this problem from smother standpoint, and Improved corrosion resistance la pre dicated on a defect-free chrome plating. This system has been tensed "bright, crack-free chromium". The evaluation of both these methods of Improving cor rosion resistance of zinc-based die castings has indicated that either method combined vith conventional practice vill produce a far superior product. Test panels vill. remain on exposure and nev panels reflecting improved, bright, crack-free chromium are being placed on test. Recent vork at Battelle has been concerned vith determining plating condi tions that yield improved, bright, crack-free chromium. The variables of chromic acid concentration, plating temperature, and current density, as veil as chromic acid sulphuric acid ratio, are being studied vith respect to con tinuity of the chromium plate. Information on these variables is desired to define vfcy some sets of plating conditions are better than others for plating corrosion protective chromium for the guidance of Industry In selecting the best over-all plating process. Studies of plating thickness have shovn that porosity of plating is de pendent eomevhat on thlcxnesa vhen plating conditions are such as to produce bright, crack-free chromium. Cracking of chrome plate vas found to be depen dent upon the plating bath temperature and to a lesser extent on the chromlesulphurie acid ratio and chromic acid concentration. Deposits made from baths operated at lJOof containing 15 oz. chromic acid concentration and a high chromic-sulfuric acid ratio vere found to produce superior films. One-year outdoor exposure tests have shovn that outstanding performance can be obtained from a system having .k mils of copper, .6 mils of bright nickel, and .08 alls of bright, crack-free chromium. 8ystems Involving copper, duplex nickel, and regular chromium, also shov good performance. These results corre lated veil vith those obtained from CASS (copper accelerated salt spray) and Corrodekote tests. It appeared that these tvo accelerated tests correlated veil vith outdoor exposure teats. 10- future work will be concerned with the study of plating bath variables on the continuity of chromium plate. Investigation of direct nickel plating on zinc die castings Is also being studied as a possible means of eliminating cyanide vaste disposal problems, further evaluation of the corrosion protec tion afforded by duplex nickel as veil as the combination of duplex nickel and bright, crack-free chromium, will also be carried out. B. Development of Improved Zinc Die Casting Alloys - (ZP-5-59) Ibis program Is being carried out In the research laboratories of the Rev Jersey Zinc Company under the direction of Mr. Anderson and, under the present agreement, will extend until february, i960. Vork to date has consisted primarily of a literature survey and setting up experimental equipment. The research to be performed will consist of a study of alloys which can be hot chamber die cast, and which may contain aluminum In the range of 5 to lBjt. The economic advantages of the hot chamber die casting pro cess have dictated that alloy development be conducted with this process In mind. Improvement In die casting alloys Is sought with regard to higher mechanical pro perties, wear resistance, creep strength, low temperature ductility, corrosion resistance, and themoexpan6itlvity. The zinc-aluminum system seems to be the most likely candidate for Improvement of these properties. Wrought zlncalumlnimi alloys have excellent ductility and toughness at room temperature, and It Is felt that use can be made of these characteristics to achieve the objec tives outlined above. The plan of attack proposed Involves proceeding In three major phases: (a) the development of test bar die suitable for this type of alloy, (b) the pre paration of die castings and evaluation of all reasonable alloy compositions (c) the more complete study, Including the establishment of at least approximate composition llmlt6 of any alloys of sufficient Interest vhich may be found in step (b). Such aspects as castabillty, corrosion resistance, platabillty, physical properties, and mechanical properties of promising alloys vlll be evaluated. C. Corrosion of Galvanized Hot Water Tanks - (ZP-20-59) This research Is being conducted at the Case Institute of Technology under the supervision of Dr. Weast: It has been In progress since July, 1958 and la to be continued, under the present arrangement, until July, 1959* The need for this research stems from the deterioration of the competitive position galvanized hot water tanks have suffered due to premature failure of tanks In critical locations throughout the country. Two factors which have led to this situation are believed to be the trend toward the U6e of soft water and higher operating temperatures. Whether these factors are Indeed related to the problem remains to be proved, but It Is apparent that some environmental change In conditions has caused, through early failures, a deteriorating market. The object of this research Is to obtain Information which will permit development of zinc alloys possessing Improved corrosion resistance to hot water. A plausible theory proposed to explain the corrosion of metals covered with a -11< T '* ni LIA22636 ^V.. 11 ... .. -- .v. wia. di* o O continuous film of corrosion products Is that theory concerned vlth the defect solid state. The basis of this theory Is that the corrosion rate of a metal covered vlth such a film vl 11 Increase as the number of defects In the film increases. Zinc oxide has been shown to be a metal excess compound In that It contains tine Ions located at Interstitial sites. Wherever tine Ions are so located, there Is an equivalent number _f electrons In the crystal, sad It Is the migration of these Ions from one Interstitial position to another which per* mlts continuous corrosion of zinc even though the metal Is coated with a pore and crack-free film. In this film, the diffusion rate of tine ions Is the cor rosion rate determining factor. The experimental work now in progress Is proceeding along two lines, rirst, photoconductivity studies and X-ray analysis of corrosion products obtained from alloys containing 99-99^ tine, 99-?% zinc, and 97-5^ tine with 2.aluminum In oxygenated distilled water are being uadertaxen. It has been found from this study that tine oxide was one of the corrosion products formed at all temperatures. At low temperatures, tine hydroxide and hydrated zinc oxide formed as well. At 68C, zinc oxide only was Identified. At 100C, there were at least three zinc oxide structures In evidence. One of these which formed 6lovly was colored black. The structures of the corrosion products formed at lower temperatures (20 to 30C) were unstable at high temperatures (80 to 100C) transforming to tine oxide. A second phase of the research Involves determination of conditions which influence the electrical potential of zinc with respect to Its environment with the object In mind of determining why the potential of zinc becomes so noble and to establish conditions under which this enoblement occurs. Previous research conducted at atmospheric pressure indicated that zinc became noble only In the presence of oxygen and bicarbonate Ions and that the presence of even reason ably small concentrations of chlorides or sulphates prevented this tendency. Slr.cezlnc corrosion products In vater always contain oxygen, the effect of pressure as a variable was Investigated, and potential studies were made In pressurized systems. It was found that 30 psig caused zinc to become .1 to .3 of a volt more noble than when the system was not pressurized. In some of these experiments, zinc became more noble than iron In distilled vater. Proa these data, there is Indication that the reversal of potential of zinc with re spect to Iron Is more common than predicted by research of earlier Investigators and that pressure is a variable that affects potential reversal. Future effort will be concerned vlth the pressure sensitivity of zinc corrosion in water as well as the development of alternate methods for minimiz ing the effects of potential Inversion and the investigation of a system po tentially capable of yielding long life regardless of geographic location and type of vater. D. Wet 8torage Stain of Galvanized Sheet - (ZP-11-59) This investigation is being carried out at Southern Research Institute under the supervision of Mr. Wilcox. The work has been In progress since Tebnmry, 1957 end under the present arrangements Is to continue until December, 1959* Research hu been primarily concerned vith three topic*! . The development of * rapid test procedure to detemlnethe suscepti bility of galvanized sheet to vet storage stain. b. The comparison of the developed test vith existing stack tests now used in Industry. c. The evaluation of various protective film*. Of the various tests that have been investigated, the one that wi found cost likely to yield results comparable to those obtained in stack tests con sists of immersion of galvanized samples in distilled wter and measuring veight loss of the sasiple after corrosion products have been removed. This test produces (juantltatlve results that may be valuable for differentiation of wt storage stain susceptibility. Previously used stack tests are not quanti tative to this extent in that the susceptibility to stain is measured by the time required to stain 50^ of the surface area. Correlation between the laznersion test and the stack test la still being carried out and for the most part has been found to be comparable. The com parison betwen the immersion method and industrial type method has been rude vlth untreated, chromate-treated, and organic-coated specimens, and these tvo methods have generally rated the actual performances of various samples in the same way, vith the exception that the chromate-treated specimens appear much better in relation to the organic-coated samples by the industrial method than by the immersion method. The immersion method it potentially of great valus ovlng to its reproducibility and speed. Recently susceptibility tests have been performed on treated and untreated galvanized samples submitted by ceven galvanized steel producert. Suscepti bility was tested by both the Immersion test and the induetrlal stack test. Among the untreated samples,there vas essentially no significant variation in corrodibility exceot that in one instance, vhere no aluminum vas added to tne galvanizing bath, susceptibility to wt storage staining vas somewhat less. All treated samples shoved coo* degree of protection. Hovever, three treated samples seemed, from most of the data, to be superior to the group of the other four vlth regard to cerroston resistance. A third phase of the research is concerned with determining the effective ness of various organic coatings in Inhibiting vet storage staining. Many pro ducts wre shown to be ineffective. Two materials were found to be relatively protective but it should be noted that chromate, as applied in the laboratory, and as applied ccemercially by one manufacturer oi galvanized sheet, shoved superior Inhibition to staining in the stack test than did the tvo organic coopounds. Performance In the immersion test by these chromate-treated specimen* vas not outstanding, hovever. future work vill be conducted to study an aging effect that sppears to de crease the protection of chrcroate films. This phenomenon vas recently found to be the cause of premature failure of same chromate film*, future testing of industrial galvaulted sheet vill also be performed as veil as electric diffrac tion experiments on the corrosion product knovn as black rust In order to identify the nature of the substance and develop Information as to its cause. I. Exposure of Competitive Sheet Katerlals - (ZP-1-59) Tests are under vay to compare the corrosion characteristics on continuous galvaulted steel, semi-continuous galvaulted steel, rolled tine, and alumlnlted steel, at rural, industrial, and industrial sea-coast locations. The specimens vere first exposed in March, 1958- Hie tine sheet end galvanised steel speci mens have darkened slightly since this date vhlle the alumlnlted specimens shear effects ranging from slight yellov staining near the edges to a sore general yellov stain, vith rust spots, on the lover side about 1/32'' diameter at the rural site. The first specimens vill. be tested for physical properties as soon as significant corrosion has occurred in any one type of material. f. Cathodic Protection of Marine Tankers - (ZP-13'59) This program consists of installation and evaluation of sine anodes for cathodic protection of Bo. 9 tank of Texaco Company's Bull Bo. 1*566. The applicability of zinc anodes In protecting tanks under sea voter ballast con ditions vill be determined In this study. The installation vas designed by Ebasco Engineering Services vto vere also responsible for the actual installa tion. At this time the installation is practically completed vith the excep tion that potential monitoring equipment is yet to be purchased and Installed. The tanker Is expected to be coundesloned and put Into service in May. 0. Improvement of Zinc Lithographers' Plates - (ff-k-59) This research is to be carried out under the technical supervision of the Lithographic Technical Foundation vith metallurgical support from Ball Bros., Illinois Zinc Co., end Matthlessen It Eegeler Zinc Co. The contract vas let in March of this year and, under the present arrangements, vill run for a oneyear period. It Is being financed by the Lithographic Technical foundation, the aforementioned companies, and the American Zinc Institute in a cooperative research venture. The primary objective of this vork vill be to improve the nonprinting areas of zinc plates by conversion of the surface to a state In vhlch it is highly hydrophilic. In the lithographic field, sietals are classified ss "nore Ink receptive than vater receptive" or "more vater receptive than ink receptive". Zinc is classified as one of the "ink receptive" metals, ttiese terms are relative since a lithographic plate must have both Ink receptive and vater receptive areas, (the Image and nonimage areas respectively). Of pri mary concern then, Is the Improvement of vster receptivity of Line plates. Another area of Investigation vill he the development of a surface treat ment on zinc vhlch vill enable the plates to be pre-coated vith a diarollghtaerisltlve material to produce a preeenaltlred lithographic plate or to he coated vith a vipe-ou type of dlaao coating. These coatings are being ueed widely la the llthogiaphlc field and at present can be used only on specially treated aluminum plates. -Ik- ' - - ' - _ - ` f------ LIA22639 Many possible approaches vill be Investigated for conversion of the non printing areas to make then vater receptive, and to enable tine plate* to be coated with dlazo. Among these are acid and alkaline anodizing systems, the "Anozlnc" process, and other cheaical surface treatments with phosphates, oxylates, and silicates. These treatments vill first be evaluated on a labora tory basis, and promising ones vill be field tested in actual production. Improvement of the mechanical properties of zinc plates by developing suit able alloys is also to be Investigated vlth the objective in mind of producing fine-grain plates vhleh have better printing characteristics and alloys vlth more creep resistance since one criticism of zinc pistes it that they stretch during long press runs. Ibis phase of the investigation vill be carried out by the three participating companies. Ball Bros., Matthlessen k Hegeler and Illinois Zinc Co. H. Zinc Bsttery Cans - (ZP-16-59) Recognizing the superior properties of zinc for dry cells, and the desire to continually improve the quality and performance of this pover package, the dry cell manufacturers and the fabricators of zinc sheet have Joined together in a cooperative program directed tovards the elimination of perforation of the dry cell container. The first step in the program is to establish a yardstick for evaluating the relative performance of zinc cans vhen exposed to media equivalent to that en countered in the completed dry cell. Evaluation of the "yardstick", or corrosion test is underway. Vhen this is completed, the chemistry of the cell as veil as the metallurgy of the container vill be studied. I. Exposure Tests of Zinc Oxide Containing Exterior House Paints - (ZP-22-59) This investigation Is being carried out vlth the extensive cooperation of the American Zinc Oxide Co., The Eagle-Picher Co., The Bcv Jersey Zinc Co., Shervin-Williams Co., and St. Joseph Lead Co- The objectives of this bcoad program are threefold: l) the evaluation of nev pulnt vehicle developments vith zinc oxide pigment; 2) the evaluation of zinc o:ide paint formulations v:th respect to zinc oxide content; and 3) evaluation of performance of zinc oxide fomulations vlth respect to mlldev resistance and com parison of performance vlth that of other paints containing chemical mlldevcldes. Thousand* of paint test panels have been exposed since August, 1958, at six sites representing different atmospheric conditions. These sites and their ea viroroent* are: l) Monaca, la. city smoke;?) Joplin, Mo. - mining; 3) Columbus, Ohio - sverage residential; U) Palnerton, Pa. - Industrial smoke; 5) Coffejnrille, Kansas - farm; and 6) Miami, Florid* marine and sun. The six-month exposure results of these sites vill be reported in the next quarterly report. - F. Radtks tor of Resea