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< APPENDIX B Use and Replaceability of PCBs Table of Contents II. III. IV. Dielectric Fluids A. Capacitors 1 . Advantages and Disadvantages of PCB in Capacitors. 2. Replaceability of PCB in Capacitors. 3. Extent of Capacitor Use. B. Transformers 1 . Advantages and Disadvantages of PCB in Transformers. 2. Replaceability of PCB Transformers. 3. Extent of Transformer Use. Industrial Fluids For Hydraulic, Gas Turbin*, and Vacuum Pump Uses. A. Hydraulic B. Gas Turbines C. Vacuum Pump Applications Heat Transfer Applications A. Advantages and Disadvantages of PCBs as Heat Transfer Fluids. B. Replaceability of PCBs as Heat Transfer Fluids. Plasticizer arm Miscellaneous Uses. A . Adhesives B. Textile Coatings C. Surface Coatings D . Sealan ts E. Printing s F. Fire Retardant ana Flame-Proofing e x p o sit io n s . G. Miscellaneous Applications. LI PLAINTIFF'S EXHIBIT Pas?' 58 5? CCC8C APPENDIX B Use and Replaceability of PUBs I . DIELECTRIC FLUIDS Dielectric (electrically insulating) liquids are important to the electrical industry for fillin g agents or impregnants in transformers, capacitors, and other devices. Besides their electrical functions, the liquids may also be used for cooling and arc quenching functions. De tailed discussions of dielectric fluid applications are available (l-L). A. CAPACITORS Generally, industrially important capacitors use liquid impregnated cellulose paper as a d ielec tric. The required properties of the liquid are: 1 . Non-flammability (important for preventing fire s, particularly in indoor u s e ). 2. Dielectric constant matching that of paper. A good match reduces electric field inhanogeneities, increases dielectric strength and lifetim e, and allows decrease in capacitor s iz e . 3. Low dissipation factor (reduces energy loss and destructive heat ing in a capacitor). h. Hii dielectric strength (prevents breakdown and allows decrease in capacitor s iz e ). 5 . High chemical stability (increases capacitor lifetime and s t a b ili zes its performance). 6 . Low vapor pressure (increases physical s t a b ilit y ). 7 . Inert decomposition products in an electric arc (prevents explosion or corrosion following breakdown). 8 . Low toxicity of the material and its decomposition products. 9 . Low cost. 1 . Advantages and Disadvantages of PCB in Capacitors The PCB capacitor liq u id s, commonly called askarels, are mixtures of chlorinated biphenyls and chlorinated benzenes. Several standard mixtures are specified by ASTM ( 5 ) . The askarel capacitor liquids and their de composition products are non-flammable. Thus their use in capacitors greatly reduces fire and explosion hazards. This characteristic permits economies where safety codes require fireproof enclosures for capacitors containing flammable liq u id s. D dielectric constant of the askarels is high ccnpared to other common dielectric liq u id s . Doubling the dielectric constant of the dielec tric allows a reduction by half in the area of the capacitor electrodes, and a significant saving in the cost of construction and installation. The dielectric constant of askarels closely matches that of the capacitor paper. L3 AOM 0 0 0 C 8 2 O TABLE 1 a r *-1. SUS 23*C 37 3 C 0* IW C Viv:ct*4y. cv 23 C 37 B*C 9IPO X Fl.nSpoml Mi- :up. *L A' ti!" Tip . All|/sii iKM pom. 1 Sp'i.lt 15 b ` C 25 C C n r l ol t > M . /C(/' C Iiermal C<M:K. Iq 1 r il/#c!('!VM*C/Cfr) 1 dlU/FrMMK'ri Ojii v) puini a: 76C miM. X Vu1it-I-ty. *qlu lu j Ouier.loc Mrengin k/ 1" !0 254 rml C lleitf'C CO-nUnt. 6il 111 10' Ml. 25*C 10' Hi P`` sip 'on l*rlor 69 Ml '.O' 111 100 C 1C Ml 2i ie f*i*.|i* i> *>!*** mi -------- - -- Unmhibiled tr>r{. M 58 2` IfPICAl PftOPtRTICS OF LIQUIDS -- Mireral Oil - - Opac or Pipe c*b> Oil Oil Heavy caLle 0*1 -- . .-- Pipe table Lipid Polybuienet Paper imprci'ii.mt 103* 38* 761* 60' 2365* 101* 1.201** 63* S.UOC ' 176* 9 79 146* C' -4` 6 0 BOB1 21 35 15*1 4* 0 - 85 t' 0 9074 10 196 1* 0 - 26 5- 0 928* :i 283 3* 0' - |7 8 0 926* 154* 0 01' - 4* U 1H2` 160' 0 01' -23' 0 870 0 0006 i C COO11* 0 076* 0 03031" 0 076* 0 000 30" 0 072* 0 000 30" 0 072* C 00078 0 00076 0 062' 32 5' 0 PCI'* >30' 0 C01'* >30* 0 001'* >30' >35'* >35" 0 001'* ?14'* 2 It'* 0 0005'* 0 0005'* > 1*10" '* >iic,r* . .. . C..p..i ilur liquid 3C0 OilG' 2.200* 252* 0 01* 17 0 '*05' 0 062' >35 * 22?'* 0 00051' > 1.10'* " _ A.lifd'j - io *? 30 31 41 51 31 32 bi >2 ) ' 3i ' l`*i 40 r.r.. 25 ii .6 ;/ ; i 3,i 56 *" 1 8 14o 1* 0 010 ir.aa 11 1 18 0 0001 o9 v 18 17 2 ?5 1c 3 * *.C2 2* o o:P pi.** O O lC m i' -3 5 5 -- 19 0 1 26 1 38 0 00073 0 00065 45 3 32 4t 4 it ! ' 192 8' 9* 1** .3i 'J i: *K 5 <.3 *4. - 70 0 0 . ! -15 1 54 0 000 70 0 030o6 0 067 275 0 >35 45 0 06 3 290 0 >35 57 0 03d ' 25 0 > 35 58 0 li*7 J 33 0 -15 56 0 05* .o3 0 '$i 50 0 001 *s51O'* 0 OCI '5*10' 0 001 *10' 0 L'Ol -*19" 0 001 5* 10' *000 Table 2 P iyrlcal and Other P ro p e r tie s of Lubricating Oils, Engine Oils, and Hydraulic Fluida p iu id O i n l c i l c i o a o o r Compound m il-m o Harmony 44 MLO-5731 HLO-7277 MLO-60-94 (C u lf) K>bii w e - io s HIL-H-40B3B MlL-H-5606A HIL-O- 5606( E s ta U n irte J-43) H tn o ra l 011 HN - Naphthenic H " M ineral BB M "- O il H a# P a ra ffin ic. deep dewaxed BB {(Kyi C ly co l Propylene C ly co l I'h y ltn c Clycol H o M t f M o - S t f 271 " " 520 " - 620 Nyvec 2 0 ( H j 4 I 1 ) tru e 902 ( S h e l1) Ucon 30111-260 U r o n 30MB - 2 0 0 - X Ucon L B - 6 0 Ucon LB-400-X JO l Water HouftHto-Safe 1010 M " 1033 M M 1113 M " 1170 H " 1130 C lycol V ater-Clycol B BB BB BB BB BB Ifa te rrC lyc o l and a d d ltlr a e Water-011 baulalon Polyalkylene C lycol BB BB BB BB BB BB BB BB BB BB BB BB BB BB BB BB BB BB V lic o a lty . ci 100*P 2I0*F S p e cific C re v tty (W ater*l) 37.2 8 7 .6 --- 14 M ineral O lla 5.8 9.8 -- -- 3.13 0.8 6 0 .8 8 --0.8 8 124 --** 8.74 to 10.2 ---- 0.92 ---- C i r c o l a and V o ta r C i r c o l a 8 .7 1 9 .6 2 .2 n/ 4 3 43.2 43.2 41 97.4 36 -10.7 -- 1 8 .2 13.0 32.2 49.8 62.8 --~ 16( 1 30 *P) 2 3 . 1( 1 3 0 *P) 2 9 . 8 ( 1 5 0 *P) -- 31 ----- Ptioeahate Catara 3 .9 8 .0 4 .1 3 .0 6 .0 *-1 .0 4 3 1 .0 7 3 1 .0 5 3 1.07 0 .9 3 ----- 1 .2 0 1.143 1 .1 6 3 1.13 1.143 P la ih Point *F P ire Point P ~450 ~ 40 --- 383 390 735 -- 193 ---- 430 --- 223 240 230 -- r -- -- -- -- 455 500 310 -- 233 300 600 323 -- 503 303 -- 433 490 670 680 680 690 680 Autol gnl r 1 o n J.^ Tem peratu ra r D e com p o niti T em peratu r *f 665(5) 680(5) -- 466(50) 700(27) 702, 67i(50) 470(50) 437(4) 637(2) -- 660(28) 725(30) ~ 6 2 0(3 9 ) --- 836( 38) 8 35(30 9 0 3( 38) 767(3) -- -- 750(51) 709(31.) 743( 38) 743(20) 633(38) 752(20) >1700(31) 1 0 7 0 .8 10( 30) >1200(31) 1020(3) >1200(51) -.. ------- -- ---- a 0M 0 0 0 C 6 Tabi 2 <Coa>t> ru n M LO -36* 582 H LO -U -6 K I KLO-16-611 MLO-57-9 C h e m ic a l C la a s o r Compound Octadecyl trld s c y l Sitano Dodscyl trld s c y l Silane Dldodecyl d to cty l Silan e Tatra undecyl Silane V is c o s ity , ca I00*r 210*F S p e cific. C ravlty (U a te r-I) 33.9 26.4 23.1 29.26 Sila n es (Cont) 6.8 5.6 5.0 6.11 ---- P la s h Point * 545 533 520 545 P ire P o in t r 595 575 553 600 Tatra ( 7-ethythaxyl)81llcata O rali t . r . l O ro n lta 6200 O ru n lta 8511 M I O -54-643 MIO-54-540 (Monsanto 0S-43) ML-34-856 (Hol 1Ingshead, 720730 Varal loba P-50 V aral lob P-44 bou C o r n in g 190 Dow C o r n i n g 400 Dow C o r n i n g 500 Dow C o r n i n g 550 Dow C o r n i n g 700 Dow C o i n i n g 710 MLO-59-V8 MLO-53-444 (CE 81406) MLO-59-287 (CE f-5 0 ) Tluoroluba P-3 Pydraul A-700 A r o c M o r -1248 A r o c l i l o r - 1242 A r o c l i l o r - 1254 Ethyl hexyl S ilic a te ( 2-thyIhcxyl) S ilic a te S ilic a te Eater as 851 O r o n tt e 6 131 P le a o l S ilic a te Eater as aa S i l i c a t e s and S l l i c o -- 31.75 24.3 ---- -11.14 6.11 ---- ------- SI 1leone M Polymethyl Siloxane Polymethyl Siloxane Polycth yl Siloxane Si 1leene Poly (m ethyl, phenyl) Siloxane Methyl Phenyl S ilic o n e 50X M ethyl Phenyl S i lic o n e (DC 256) p lu a 501 TKP A d ip a t e Tettacoproate 32 55 22.4 10.9 44.9 43 to 87 2.6 220 61.8 16 17 ----- -13.3 1.043 1.043 ---- 1.063 -- 1.112 -- HaloRenated S ilic o n e s and Hydrocarbons C hlorinated S ilico n e Chlorophenyl Methyl S ilic o n e P o ly tr lflu o r o c h lo r o s th y lene C h lorin ated Hydrocarbon Vet rselllorod lp he nyl T r lc h lo todi phenyl Chlorin ated Hydrocarbon -- 5 49.S 43.0 17.7 -- --3.0 3.2 -- -- -1.86 1.42 1.41 --- -383 390 340 325 315 550 550 260 255 470 600 305 320 -- -440 430 453 4 30 440 660 660 -280 --325 --- 380 710 -- --- -- 330 680 300 Hone 330 633 -- -- Au 10 1gii 11 1ocwf* D e c o m p o s i 1 1 Tem perature Tempt ra Cur r P 730(17) 730(17) 750(17) 7 b 0 ( 17) -. - ~ 3?0(12) 716(2) 710(50) 716(2) 703(2) 716(2) 9 0 U ( 31) 900(51) 860(38) 6I0( 38) 900(38) -9 40( 36) --- 6 38 ( 28) .. .. ... .. .. > 600(51) >600(31) --.. 740(23) -- 3 6 3 ( 13) 623(30) 786(2) -- 1203(12) 1200(31) *1103(12) 12 30( 30) ~ I0 8 3 (I2 ) 514(13) 6 30( 30) >623(31 ) ---- -- COCCd I exercized through companies which insure against fir e , u tilitie s which supply electrical power, and building codes. 3 . Extent of Capacitor Use Almost all industrial capacitors contain PCBs. In. 1968 95 percent of the U . S. production of capacitor liquids (2.L6 m illion gallons) were PCBs ( 9 ) . Two important types of capacitors are phase correction capaci tors on power lines and b allast capacitors for fluorescent lightin g. Non ballast industrial capacitors produced in 1967 had a value of $112 million ( 10) , and fluorescent lamp ballast capacitors produced that year numbered 2 1 .7 million units with a value of $ 1 5 .5 m illion ( 1 0 ) . In 1970 there were 50 .9 m illion ballast units produced with a value of $163 m illion ( 11). These ballast units are in extensive use inside buildings where non flammability is important. Phase correction capacitors are necessary on power circuits to correct for the inductive loading of much electrical power equipment. The amount of phase correction capacitance is ordinarily specified in kilovolt amperes of reactive current or kvars. Most power capacitors are rated at from 1/2 to 25 kvars so that the number of capacitors is very roughly the kvar value divided by 10 (1 2 ) . As examples of the extent of power capacitor use, TVA has 2-1/ii m illion kvars ( 1 3 ) , and a power company serving suburban New Jer sey has 3 .6 m illion kvars on their power lines with 1/2 million kvars on order (lii). The value of these capacitors is roughly $5 per kvar (lli). More than 20 m illion kvars of power capacitors were produced in 1970 (16) . The procurement lag for these capacitors is 1-1/2 to 3 years, and e s t i mates for redesigning new systems range from 3 to 10 years, according to power compary representatives to ASTM Committee D-27 ( l h ,1 5 ) . Extensive re-designing is anticipated i f distribution capacitors were required to use presently available non-PCB liquids. Askarel capacitors have been developed to the point that failures are considered negligible ( 13, 1 5 ). Several private sources reported extensive efforts to find replacements for PCB capacitor fluid s, but none reported having a good substitute. B. TRANSFORMERS Most power transformers contain a liquid to electrically insulate and remove heat from the core and windings. The properties required of these liquids are: 1. Non-flammability (required for indoor use and desirable in remote location u s e ). 2 . High dielectric strength (prevents breakdown and allows transformer size reduction). 3 . Low viscosity (promotes convective heat transfer). h. High chemical stability (allows higher temperature operation and reduces degradation of the transformer). 51 ADM 0 0 0 0 5 0 flammable liq u id . An annual report on such failures is compiled by the Edison Electric Institute (1 9 ). I I . INDUSTRIAL FLUIDS FOR HYDRAULIC, GAS TURBINE, AND VACUUM PUMP USES' A. HYDRAULIC Hydraulic fluids are liquids used as force transmitters (2 0 , 2 1 ). The characteristics o f a good hydraulic flu id are ( 2 0 ) : 1 . High lubricity (lowers heating and increases lifetime of moving components). 2. Stability (increases lifetime of use). 3 . Appropriate viscosity and high viscosity index (2 h ). i . Low pour point (necessary for material to flow at I cjw temperatures (25). 5 . Compatibility (prevents interactions with other conponents, for example, rubber s e a ls ). 6 . Good heat transfer (reduces local heating and large temperature gradients). 7 . High bulk-modulus (important for extreme pressure applications). 8 . Low volatility (necessary to prevent malfunctioning due to "vapor lock). 9 . Low foaming. 1 0 . Low thermal expansion. Aside from the implication of a more con,, stant volume over a wide temperature range, a low thermal e ^ a n s i o n iaplies a high viscosity index and the constancy of certain other properties with respect to temperature. 1 1 . Good dem ulsibility. 1 2 . Inhibitor (necessary to prevent oxidation of metals or rusting). 1 3 . Good fire resistance (very irportant in high temperature environments), lli. Low density (desirable in transportation, particularly airborne, applications). 15* Good dielectric properties (reduces arcing or short circuiting should the fluids come in direct contact with electrical components). 16. Non-toricity (reduces the danger to human beings from rupture of hydraulic equipment or Improper disposal and to maintenance personnel during transfer of these fluid s). Since most commercial hydraulic flu id mixtures are proprietary, it is d iffic u lt to obtain information with respect to their corposition. The results from inquiries with respect to PCB content have been sanewhat contradictory. No d e fin ite knowledge is available that PCBs are present i n commercial hydrau lic fl u id s . Since composition specifications of these fluids are usually not available to the p u b lic , PCB content should be established by chemical analysis. r1 PCBs are useful i n hydraulic fluids as lubricating additives in extreme pressure applications (26) and as pour point depressants. Although it is true that the pour point of oils may be lowered by extensive dewaxing, the use of additives is much cheaper. There are other inexpensive additives which are often used for these applications and which anpear to be adequate. For 53 I AC* CcCcSi rl- ,t viscosity index, low pour point, and oxidation and foaming resistance. Sample U. S. and U. K. military specifications are given in Table 3 (36). Usually, dibasic acid esters containing appropriate additives meet the above requirements. In the case of the turboprops, the same lubricant is usually used for both the turbine and.prop-drive gear. PCBs would seem to be useful as additives in gas turbine lubricants, but there is no evidence that PCBs are currently used for this purpose. Research along these lines has been done, and there is some indication that some PCBs have on occasion been added to gas turbine lubricants. The objection to PCBs and other chlorinated hydrocarbons is that they tend to be corrosive at the high temperatures reached in gas turbines. This corrosion is accelerated by decomposition of the PCBs and the forma tion of hydrochloric acid at high tenperatures. The corrosiveness of PCBs is a major deterrent against their use in these lubricants. TCP also has the desirable property of reacting with metallic surfaces at high tempera tures to form a protective coating. Jet engines are run for approximately 18,000 hours (37) between over hauls. The lubricants are not usually changed during this period; however, the appropriate "oil level" is maintained at frequent intervals. Immediately before engine overhaul the lubricant is drained and discarded. Unlike the situation with respect to hydraulic fluids used in commercial aircraft, there appears to be no general recycling facility for gas turbine lubricants (37). As a result of their increase in acidity and viscosity during use, recycling of gas turbine fluids would demand expensive redistillation and reblending. C. VACUUM PUMP APPLICATIONS (22, 23) Both mechanical and diffusion pump applications require fluids of one highly fractionated conponent. Accordingly, additives generally are not used. However, PCBs are used in pure form as a diffusion pump oil in commercial applications. The characteristics (38) of a good diffusion pump fluid are: 1 . Relatively high vapor pressure at operating tenperatures. 2. Low vapor pressure at room and lower temperatures. (The vapor pres sure imposes a lover limit on the ultimate vacuum). 3. Heat resistance (prevents cracking or molecular degradation at operating temperatures). lu Narrow vapor pressure range and freedom from contaminants such as absorbed gases and liquids with higher vapor pressures. (This requirement often implies the necessity of a narrow fraction). 5 . Oxidation resistance (important because air may enter a diffusion pump during operation either accidentally or through slow leakage). 6 . Nonhydroscopic (absorbed water increases pump maintenance and may contaminate the vacuum system). 7. Compatibility (must be compatible with pump and vacuum system components). 8 . Stability in the .presence of the vapor being pumped. Some of the pertinent properties of many diffusion pump fluids are given in Table h (3 9 ). The stability, oxidation resistance, appropriate vapor pres sures, and, in particular, the relatively low cost of PCBs make them a desirable choice for many industrial applications. Although the ultimate vacuum using & ADM 0 0 0 0 9 * :^ Table 4 Some Properties of Pumping Fluids fiufj Proprietary nottue Chemical nature %ii'fit Specific Ihtih gravity point (room temp.) (open * 0 Viicoiity ((M illion) at 20'C Appi ox. pour point (or ftreiin g point) *C Appro e. boitutg point nt 1 tore mC '.itiniiiii'it true nipatir pecunie itorr) A'.'icion A Apic/jn 0 A i under `fluid* Api(i>n U\V Apiciun C Apii'/on G Apicroti F\V Convoli 10 Convoil 2^ O-/I t)l!l)l pliilulalc l)i-2cthyl hexyl plilhalata OctoiJ v-nj Di-l-cltiyl heayl scbacate OcloilS Narco 1-20 Vmcoil-20 Di-nouyl plnhalale NarcoiMO Paraffinic hydrocarbons M C sll.lC O O C .ll:,), Ctll.lCO O C.Il), Ct llu (COOC.II,,), CJiaCOOC.ll,.), 414 461 m 114 441 ISO 210 400 2)5 371 411 419 Tri-crcsyl phosphate Tii-.xylenyl pliu>plutc Glycerol Viacoil-40 <01l,C*l!,),PO, (ClhOII).CJ1(011) 363 414 92 Mixed chlorinated diphenyls Aroclur 1243 Convaclor I Approx. C uli.C l, 2 Cloplicn A-40 M i J chlorinated diphenyls Aroclor 1254 Edwards (looslcr fluid A Approx. Ci, 11,0, J26 Njrcoil-10 Viacoil-10 Convador-12 Silicone D.C. or M.S.70I Silicone D.C, 703 Silicone D.C. or M S. 704 Silicone D.C. or M S. 704 Clophen A-50 As under `fluid* .Methyl pidysiloxancs (C lIJA iO K C llA iS iO iaC lIJjS i Teiiapln'iiyl (elruiucih/l (nstlovan Yi-.Mphcnyl triinelhyl tmiloxanc 130 170 4 146 Cornale * |0 01 V.R.T. fluid E Mixed 5-iin; polyphenyl clheri 447 Mercuiy 3 2006 0372 0 873 0 380 0871 091 0 86 1011 09S) 0912 0*971 111 114 1-26 1-43 1-34 1071 1-039 1066 1093 119 136 218 235 263 232 191 218 119 196 209 215 240 241 191 none 194 227 216 24) 288 -- 69 -1 2 100 -1 2 293 - 9 5 16 -1 2 147 -2 3 120 - 8 9 19 -7 1 73 -5 2 24 -3 6 105 160 1180 400 6000 -7 10 13 40 47 170 (25*0 2100 (23*0 M3 -40 -36 -38 -15 43 -389 190 in - * ( 20*ci 220 5 x 10 (741 O 223 io - l i t r o 255 4 x10 'C O O 210 2 k 10-* (20 C) 165 3 x 10** (?4*'0 150 6-7 x 10*1 (2n O 195 2-3 x 10 *1 (2h'C) 102 1-5 v 1 0 * 12 C> 204 1U-M20V) 215 10*(2u'C) 215 10* * (2G*C) 219 J x IO* *(25*Q 245 12) 3 6x 10*' ( I I O 1)7 1 3 x |0 * ( 2 u 'C ) 150 X 10 * (2U'Ci 173 7416 223 I O ' 1 2 0 0 254 J x 10-'* (25'C) 283 1-3 x | ( f " .`21*0 127 l - l x 10*' (Jd'C) lx* ADM C0009 toricity, a tendency to decompose to form highly corrosive HC1, a lower decomposition temperature than some alternate liquids (1x3) and relatively poor radiation resistance (UU) B. REPIACEABILIT? OF `PCBs AS HEAT,TRANSFER FLUIDS Increased risk from fire and explosion is a major disadvantage with most FCB replacement fluids. Other non-flammable fluids are: 1. fluoro carbons, which have low toxicity, high thermal stability, and in spite of high cost are used as convective or evaporative coolants ( l ) , 2 . water, which is quite corrosive, has a high temperature limit of 37LC and requires extremely expensive high pressure systems for its use above the atmospheric boiling temperatures and 3 molten salts and metals which, because of their resistance to radiation damage, are useful in reactor applications. Several liquids are more stable at high temperatures than the PCBs. Table 5 (U2) shows the decomposition point range of liquids in a variety of chemical classes. Few of these liquids are non-flammable, however, as can be seen from Table 2 . The phosphate esters, silanes, and aromatic ethers have high fire points (around 6 00F ), but they are flammable and it is not clear how high the fire point must be for a fluid to be safe in a high tem perature system, especially in the event of leakage into a furnace. The details of specific heat transfer applications are necessary to evaluate the suitability of FCB replacement fluids. IV. PLASTICIZER AND MISCELLANEOUS USES + A plasticizer is a material incorporated in a plastic to increase its workability and flexibility (L5,li6). The addition of a plasticizer may lower the melt viscosity and flow temperature (increasing the ease with which the plastic can be made to flow),or lower the elastic modulus (making the plastic softer) (L 6 ). Plasticizers are generally non-volatile liquids or low-melting solids. A major requirement of a plasticizer is that it have high compatibility* (mixes will to form a homogenous composition with useful properties) (L2) with the material being plasticized. Figures are given in Table 6 for the compatibility of some common plasticizers with some common synthetic thermosetting or thermoplastic resins (L 5 ). Other properties which are important when considering plasticizers are specific gravity, refractive index, color, odor, moisture sensitivity, vapor pressure (volatility), boiling range, stability (to light and heat) toxicity and cost (L 7 ). Of course, the properties of the final plasticized material are of prime importance. Certain plasticizers provide formulations with specific properties such as: 1. phthalate esters - general purpose. 2 . adipates and ozelates - low temperature flexibility. 3. highly aromatic esters - fast processing, strain and extraction resistance. L., epoxies - heat stabilization during processing. 5 phosphate esters and PCBs - fire retardant materials. + The information in this section about specific uses was obtained from Chemical Abstracts (1928-1969) and patent claims. The Task Force has no knowledge whether or not specific applications are in current production or use. * Note that the term "compatibility", used here, has a meaning very different ram its use earlier in this appendix. In the earlier case, compatibility meant that two materials could coexist without either being affected by the other. The present meaning is quite the opposite. 59 000098 AOK Table 6. Approximate Maximum Compatibility, phi, of Plasticizers with Various Resins JH>I) (Vltl., Illll UC 1ll!"lll|< 'l clt>lu4tiltu<t* C rltlllf'A ' n il ut* f t 11IIIIf1'*; MD'l.ilC rrllu l'c.ti tin lti!fc I m lj in ic r lilu iin . iliil m l I*t liig lt M y i.'iii m jti.lym i'i' alicllftt* in y lii' n -iii'i |m4yim iidi> . ^Milyi` >li'lx c|M&y f f j iin |tWii<4ir M'tiiM a lk y tl iv>iu* tm-Liiunu- lo in iM ilt y t it ivM iia |M>lyiirtlluiii n il tile ml n e ii;iii'iii' i i j i l n i *Tr.iiti inniL M.'i-onln ('h 1 liu tli'iiiitL Unimi ( '<<i|i. *T u J u u a i l lliilmt and I lait.-. I V I't.ll,.).,!-. Alll|>:ili - 1'lilli.tlyl j;lyi iiliilr' I'nlyi' i!|>- Hiilfimuiiilis amidi-i CK VM i E V. CYM !t ; tC `o ci X, T r* eVj cI* .0 3 3 33 3 G 4. | c* ^ A* V *3 .rb ., i? > *.* y iL :*:-u | H ci H .... jr JG Jr-'i c >KC 11 y ri 3 i C "C .VN J. % 1 'b r lit C1 M r~ ci 6 M h' $ s 1 a x M1. irr.iit U 2 ** *&i n ~.E* Stz 17 5o ew. CL. >* * i." o s a Tt ? # b 1 3 in u IIHI 10U |IHI M l 7.1 IIHI IlH! tu a IIHI GO IIHI bti a* lu o IIHI a:. IUU ao fill au an 5i IUU ii i a r. an i a a:. m i 25 ;n ii a:. a i IIHI IIHI IIHI IIHI :m IIHI IIHI M l 1 1 M l 11*1 1 1 a .i III au 7.5 l i III M l IIHI an IIHI li;:l a.i IIHI (INI Ml IIHI IIHI IUU IIHI IIHI Ml IIHI 3.i i i l 1 1 III 1 1 Ml Ml an IU.I a;. M l IUU au M l IIHI |<HI -Ml Ml an M l an an 1 1 i 111 i i 1 1l 1I i z.v a.i a i 7 i in i a i an h i 5 i a i a i an i;> au au i i i i hi a i a i a i <1' M l ii a. a;. a.i a,. M l M l a i i ii 1l a.i a i in a i * l i i i M i ; n Ml IIHI an ,`n IIHI |l.il n o 1 Ml 4U Ml i 41) au 7i 7 i Ml an l i Ml IIHI au 70 IIHI IIHI Ml 7 i MU IIHI IIHI IIHI 3"> l.i VII <11 III Ml 311 KO s .a i a:. Ml IIHI IIHI IIHI au Ml Ml Ml in ;m a.* III iii 1 a i 25 HR) IIHI a i in a.i a.i li 10 20 an au in 25 a.i ai Ml MJ Ml Ml Ml 7U 70 Ml 11i i HI 2 i a.*. 2i Ml i i 40 Ml an IIHI IIHI IIHI IIHI i n i IIHI IIHI 40 1 ;ii 4U IIHI IIHI 75 IIHI II n 3.1 1 IIKl Ml Ml i 7. 7.i III a.i Ml an Ml an Ml Ml 1 Ml au hi IIHI IIHI 7:i 7. HI 3.1 1 i <11 IIHI GO 7 V 75 IIKl IIHI IIHI IIHI IIHI IIKl lull IIHI IIHI Ml Ml IIHI in IIHI Ml 1 1 1 1 1 1 !H) 31) 1 i UNI Ml IIHI IIHI 1 1 IUU t Ml 25 Ml 30 in'! Kli .ill Ml IIKl Mil IUU Ml a i IIHI IIHI Ml Ml l i a a.i 2 i Ml a.i an HI 1 i Ml 40 1 i hi 3U 1 i 40 IKI 1 i Wl 7U 1 i I 25 a III an i au 1 i Ml a.. 2* i . an i in III i 25 i a i a:. 1 l Ml Ml Ml i Ml Ml l i a** Ml Ml 2 i 25 7U 7U an a.i r . 2 i 25 l.i iiii Ml Ml 1 1 2i ai ri ii 20 IU 25 15 Ml Ml a;. Ml :u Ml Ml riU Ml lu i a.i |U | in i i a.i + p a r t s p e r `tu n d red : 'C - Table 7. General P r o p e r t i e s of Some A r o c l o r s (PCB) M aterial Form im i cnlur Specific gravity D istillation range," *C (corr) Flash point," *C Fire point/ C Pour p o in t/ c Softening p o in t/ c n0 \*itft.!iflv *^ /-r 37. S T a s tre Ar.n-I.ir 1231 Aruclor 1232 An a ! or 1242 Arorlur 1248 Aruclur 1254 Amclur 1200 Arui-lur 1202 Arorlur 12tlH Aruclor 1270 Aroc!ur4105 A r o i l, ir r112 Aruclur 5 UK) A ruclur 2505 culurlrss, riubi'e oil 1. 1S2-1.102 ( 2 5 /l.t.5 aC ) itlinna! I'nlurlcsi, 1 .2 7 0 -1 .*jsn titolili oil (25/15.5T ) abituai eulurlcM, 1:181-1.31)2 mutiilu oil (25/15.5 T ) yellim-grccn tinted, 1 105-1 415 nmliilu oil (0 5 /1 5 .5 * 0 light yill'.w , vi.u-.ma 1 l!i5 -1.505 oil (0 5 /1 5 .5 * 0 light j i -IIkw , soft. 1.555-1.500 o lirti, rciin (90/15. A T ) I'tjlit 'i-ii.iiv, sticky, 1 572 1 .X I clear m i (90/15 5 T ) nhil.! tu ulT-ivliilc 1..M M -1 S it po*.l iIlT (25/25*0 hilt: i t ;, s* .illm u 1 1MI-I Olid p o in te r (2 5 /2 5 T ) tr;u ii| ::rci:t, y. |!.iw , 1 070 b rittle ru in (25/25*0 ) rlb m , .1r;:iM|).u cut, 1 170 s t i c k y rtriiii (25/25'C ) char, 1 070 le.-r, bri tile m in (2 5 /2 5 * 0 M a rk , u|ri<iil<r, 1 7.11 brilli; m in (25/25*12) 275 .120 2U0 325 52A :;oo 310-575 aOt-.'i'K) 3S5-I20 395-125 435 -150 1511-100 230 -320 '4 linn lltf) 21.1-300 (4 miti III;) 2M) il '.5 (5 inni Il-;) 111 150 152-151 170-180 l'J 3 -l`Ju none nune nunc nono mine mine 247 nane mine 170 -MS tini ir nune nane none nune none nune none >350 none nune crystals at rc -3 5 .5 1 .0 1 7 - 1 .O IS I . 620-!.022 14-51 3*> ! SI-52 -19 1.027-1.029 82-92 3M 5 -7 1.630-1.0:11 195-2!0 3i>-3: 10 1 .059-1.611 1S90-2500 4 M S 31 1.017-1.019 72-79 35-39 1.6 3 0 1 -1 .C517 s o -100 150-170* 249-300* 00- 00 1 0G+-1.007 40 40-52 90-150 (l:iO "C i 500-400 98-105.5 l.fiOO-l.Oli.i 00-72 A S T M l t - 2 0 (itu rL li> :il l. ' C l e v e la n d h' ii cii|i. * C le v e la n d u p c ii n i p ; n.-in: imlii'.ites nu f u r ("lint tip t u b o ib ii} ; t e m p e r a t u r e . * _\;S T M ' ASTM K-2.S. f S ay bull ( 'i n v e n t a i . ASTM l.' SS. * l*ial tin i .li*;its i n d i c a t e a p ru t i n t a te clilu rim * r . i i i 'f i i t , ie, Art.c u r 1221 i-m *.,::im a l u r i t 21 * ; <>* 1 Utili! putiti un auliti iliral imi. ADM 0 0 0 1 0 2 iS D. SEALANTS Sealing and caulking compositions include a wide range of compounis which can be used to seal joints or voids against water and water vapor, air and other gases, dust, sound, vermin, heat and cold (8 8 ) , Specialized applications require resistance to certain chemicals or atmospheric environ ments. PCBs can be used as..plasticizers in the formulation of putties from copolymers or ethylene-vinyl acetate or 3tyrene ( 8 9 ) . Hie products are non hardening, and resistant to moisture and frost and show good weatherability A non-sticky, non-hardening putty was also prepared from polysulfide mix tures which employs PCB as the p la s t ic iz e r . This putty gave good bonding to building materials and had good extrudability and shape retention (9 0 ). Elastic pavement or concrete sealing conpositions, used for traffic markings, were prepared from coal-tar-polysulfide mixtures which are plasticized with PCB ( 9 1 ) . A sealant, effective for concrete and asphalt applications, can be formulated from a mixture of poly sulfide, chlorinated rubber, and polyiso cyanate, and p lastic ize d with PCB (9 2 ). E . PRINTING Chlorinated biphenyls have been employed as part of the formulations used to prepare pressure-sensitive record (93> 9b) and colored copying papers (9 5 , 9 6, 1 0 2 , 103) , Hiey have been used to coat papers used i n thermographic duplicating processes (97-101) as well as in xerographic transfer processes (lO h , 1 0 5 ) . Solvent-free printing on polyolefin plastics can be accomplished by heating a mixture of low molecular weight m aterial, chlorinated biphenyl or terpene r e s in , and suitable pigments and tyes. Durable prints can be made on the surface of the polyolefin at the time of their thermoplastic shaping (1 0 6 ). Printing p lates, hard enough for high quality letterpress p rinting, and suf ficie n tly flexible for use as flexographic p lates, can be prepared from com positions containing a liq u id resin such as eposy, polyester, urethan, acrylic or vinyl with an excess of curing agent and PCB as the p lasticizer (1 0 7 ). The extent, i f ary, of current uses of PCBs i n printing application is unknown. F . FIRE RETARDANT AND FLAME-PROOFING COMPOSITIONS When PCBs are used as p la s t ic iz e rs , they inpart a certain degree of non flammability to the objects as described previously. However, for increased effectiveness in flame retardant applications, the PCBs can be admixed with various metal oaddes, Some flame retardant conpositions based upon these mixtures are: polyolefin yarns (1 0 8 ); organopolysiloxane sealants (1 0 9 ); thermoplastic poly (hydrosylethers) ( 1 1 0 ); fireproof panels made from starch which can be used for doors, flo o rs, c e ilin g s, and partitions ( i l l ) ; poly amides (1 1 2 ); and in fireproof fiberboards (1 1 3 ). Rigid polyurethane foams (llli-116) and hardboard compositions (1 1 7 ), when treated only with PCBs do not show any sig n ifica nt increase i n flame retar dance. G . MISCEILANEOUS APPLICATIONS The wide range of chemical and physical properties exhibited by the PCBs v(see Tables 6 and 7) make them desirable for an assortment of miscellaneous uses. Some of the more in t e r e s t i n g and non-conventional uses are as follows: 65 ACM CCClG^t v^ transformers would require considerable time and money for reengineering, manufacture, and application of substitute equipment. PCBs are useful i n hydraulic systems where leakage onto hot metal surfaces could cause a dangerous f i r e . Hydraulic flu id s can also be made with phosphate esters which are toxic and which w ill burn at high temperatures. Replacement of PCBs i n some hydraulic systans could increase loss of l i f e due to f i r e . Gas turbines require lubrication at high temperatures. PCBs can be used but tend to be corrosive. Phosphate ester lubricants seem better i n this respect. Chemical sta bility is more Important for high temperature lubricants than i s non-flammability. PCB fluids are useful i n diffusion booster pumps to produce moderately high'vacuums with relatively poor fore vacuums. Non-flammability is not especially important for d iffu s ion punp l i q u id s , and with a few possible exceptions alternative liquids are available Flammable heat transfer fluids present a fire hazard i f they leak into a fhrnace or onto hot surfaces. Ihe use of PCBs can prevent this danger. In some cases water is a suitable substitute at moderately high temperatures. Other heat transfer fluids are commercially available and i n use. Replace ment of PCBs i s satisfactory in seme, but may be dangerous In other heat transfer uses. The PCBs are good p lastic ize rs for use with adhesives, te x tile s , surface coatings, sealants, and copy paper. In some cases the PCBs act as fire retar dants. There are no particularly unique properties of PCBs for p lastic izer uses, and equally effective alternatives are generally available ( e .g . phos phate esters are often used as fire retardants). The extent of current use, i f any, in such applications has not been determined. \ 67 ADM 0 0 0 IC6 18 Private communication E . L . Raab, Manager, Insulation Systems Section, Power Distribution D i v ., General Electric Co, P it t s fie ld , Mass. 1 9 . Report on Power Transformer Troubles, 1 9 6 9 , Edison Electric Institute Publication No. 71-20, (1971). 20. "Introduction to Hydraulic Fluid s", R . E . Hatton, Rheinhold Publishing Co. (1962). 21. "Synthetic L ubricants", R. C. Gunderson and A , W. Hart, Rheinhold Publishing Co. (1962)., 22. W . Espe, Materials of High Vacuum Technology, V o i. 3, Per gamn Press, (1968). 2 3 . "High Vacuum Purging Equipment", B , D . Power, Rheinhold Publishing Co. (1966). 2h. Viscosity index. A high V. I . means a low viscosity-temper ature coefficient. 2 5 . The pour point is related to the lowest teiqperature a liquid can be : poured from a container. ASTM D 97-66 Standard Method of Test for Pour Point, American Society for Testing and M aterials, F h i l a ., Pa. 26. Boundary lubricant additives cling to metal surfaces fac ilita tin g good lubrication at high pressures. See r e f. 2 1, pp lb-21. 2 7 . "Fire Resistance of Hydraulic Fluids" ASU Special Technical Publication No. !i06 (1 9 6 6 ) . 2 8 . "Review of Ignition and Flammability Properties of Lubricants", J , M. Kuchta and R. J . Kato, Bureau of Mines technical Report AFAPL-TR-67-126 (1 9 6 8 ). 2 9 . l ASTM D901-70 Standard Methods of Testing Askarels. Secs. 1 8 , 1 9 . 30. National Bureau of Standards Report of Tests No. TG 10210-2158: FR 3695* 3 1 . See for exaiqple: Ref. 21, p 1 3 3 . 32. Reference 21, Chapter b. 33. Phosphate ester type l^draulic fluids are being recycled by: Eppi Pre cision Products, 227 Burlington A v e ., Clarendon H ill, H I . 3b. See for example: A . M . Dbry, E. A . Glass, and A . Zle tz, "Improved Non-flammable Hydraulic F lu id ", Bureau of Ships Report M67-1L (196*7). 3 5 . R e f. 2 1 , Chapter 5 . 36. Ref. 21, P 235. \ 37. Private caraminLcation, R. K. Crothers Maintenance Division, Federal Aviation Administration. 69 ACM c c c i o a 5 8 . Harry* Smith, U , S , Patent 3 *3 9 5 *1 3 2 , (Dow Chemical C o.) (1 9 6 8 ), 5 9 . Da-pid A . Frey, U, S , Patent 3 ,3 8 0 ,9 5 1 (Dow Chemical C o.) (1 9 6 8 ), 6 0 . T . P . Flanagan, U . S . Patent 3 ,2 2 0 ,9 6 6 (National Starch and Chemical Co.) (1965). 6 1 . R . P . Cox, J . L . Warner, and R . J . Sere, U. S . Patent 3 ,1 1 7 ,0 0 0 (S . I . Dupont de Nemours) ( 1 9 6 9 ) . 6 2 . P . Ruckstuhl, Ger. (East) Patent 1*0,927 (1 9 6 5 ). 6 3 . P . Prumier and J . Duthu, F r. Patent 1,1*02,172 (1 9 6 7 ). 61* P . Ruckstuhl, Ger. (East) Patent 37,967 (1 9 6 5 ). 6 5 . H . J . Eichel, U . S , Patent 2,988,1*61 (National Cash Register C o.) (1 9 6 1 ). 6 6 . H. G. J . Velthoven and H, J , W ienjes, Neth. Patent 1 0 9 ,0 2 5 (1961*). 6 7 . Bail K lin e, U . S. Patent 2 ,0 7 7 ,6 9 9 (E. I . DuPont de Nemours) (1 9 3 7 ). 68. ibid, U . S. Patent 2,077,700. 6 9 . G . L is tn a r , U . S . Patent 3,1*58,1*71 (Johnson and Johnson Co.) (1 9 6 9 ). 70 . ib id , U , S . Patent 3,277,01*6 (1 9 6 6 ). 7 1 . E r it . Patent 1 ,1 3 3 ,0 5 0 (E . I . DuPont de Nemours) (1 9 6 8 ), 7 2 . R . J . Jenkins and R . N. Foster, In d . Eng. Chem, 23, 1362-1365 (1 9 3 1 ). 7 3 . H. V. Maiorova, M. I , Karyakina, V , A , Kargin, Z. Ya. Berestneva, L. P. Malysheva, Lakokrasoch. Mater. IKh Primen, 3 , 17-19 (1 9 6 9 ). (C f. C .A. 7 1 , 62325j 1969). 71*. S . 7 . Yakubouich, N . Ta. Gicbkova, V . A . Zubchuk, and P . V . Kozlov Lako krasoch. Mater. IKh Primen 1*, Ii6 (1 9 6 6 ). (C .A . 6, l 8 8 2 0 f, 1 9 6 6 ). 7 5 . D. P . Spalding, F r . Patent 1 ,3 5 3 ,5 0 6 (Compagnie Franaise ThomsonHouston) (1961*) 76. B rit. Patent 1 ,0 2 0 ,0 5 3 (General ELectric Co.) (1966). 7 7 . D. P . Spalding, U . S. Patent 3,288,71*3 (General ELectric Co.) (1966). 7 8 . E. Kamp and Karl Jahn, U# S . Patent 3 ,3 9 3 ,0 8 7 (Monsanto Co.) (1968)*. 7 9 . H . Wells (Atomic Energy Res. Establishment, Harwell, England) J . Oip. Color Chemists Assoc. 1*8, ( l ) 28 (1 9 6 5 ). . 8 0 . R ef. 1*9, p 293. \ 81. Francis J . Whilby, B r it. Patent 1 ,1 3 8 ,9 7 6 (Standard Telephone and Cables, Ltd) January 1966. ADM 0 0 0 1 1 0 1 0 5 . B. B, Jacknow, J . H. Moriconi, and F . M. Palerndti, S . African Patent 6 ,8 0 3 ,5 6 0 (Rank Xerox, L t d .) January 196 9 . 1 0 6 . Hans J . Lenz, G er. Patent 1 ,1 9 9 ,2 9 0 (Hoechst Fabweke) August 1965, 1 0 7 . Daniel L . Goffredo, ti. S . Patent 3 ,2 6 9 ,3 0 8 , August 1966. 1 0 8 . B r it . Patent 1,126,1178 (Johnson and Johnson C o .) September 1968. 1 0 9 . Charlea A . Berridge, U . S . Patent 3 ,1 5 1,515 (General Electric Co.) October 1961. H O . R. H. Snedeker, U . S . Patent 3 ,1 0 5 ,1 9 9 (Union Carbide C o.) October 1968. 1 1 1 . D. L u r ie , F r. Patent 1 ,5 2 9 5 0 6 / June 1 9 6 8 . 1 1 2 . W , F , Busse, U . 5. Patent 3 ,1 1 8 ,2 6 7 (E . I . DuPont de Nemours) December 1968. 1 1 3 . R . G . Quinn, U . S . Patent 2 ,0 3 0 ,6 5 3 (International Paper Co.) February 1936. llii. H , Picchota, Kunst off-Rundschau, 12, (li), 191 (1 9 6 5 ). 1 1 5 . Paul E. Burgess, J r . , Carlos J . Hilado, and William R. Proops, Space M i l . Appl. Cell. Plast. Syst. Annu. Conf. Cell, Plast. D iv ., Soc. Plast. In d ., 12th, 1 9 6 7 , 3-C-1-3-C-10. 1 1 6 . Carlos J . Hilado. Paul E . Burgess, J r . , and William R . Proops, J . Cell. Plast, 1 ( 2 ) , 67 (1 9 6 8 ). 1 1 7 . T , Hirata, H. Abe, and Y , Rikui. Ringyo Shikenjo Kenkyu Hokoku, 1967, No. 200 1 5 5 . Cf C . A . 70 12779U (1 9 6 9 ) . 1 1 8 . H . W . Coover, J r . , and N . H. Shearer, Belg, Patent 652,653 (Eastman Kodak C o .) December 19 6 1 . 1 1 9 . Hans Schumann, Ger. Patent .1,298,158 (Deutsche Solvay-Werke) June 1969. 120. Rene Michael, Fr. Patent 1 ,5 3 2 ,1 1 5 , July 1968. 1 2 1 . H . T. Kemp, J r . . T . L . Statler, and E . E. Muellar, M itt. V e r. Deut. Emailfachleute ll (55, 15 (19 6 6 ). 1 2 2 . Rolf Bremer, Eberhard Rheinhold, and Hermann Fiebig, Ger. (East) Patent 6 6 ,7 1 2 , May 1 9 6 9 . 1 2 3 . Belg. Patent 6 9 6 ,8 2 0 (Establishment Marechal) October 1 9 6 7 . 1 2 1 . B r it. Patent 1 ,1 5 9 ,2 2 0 (Sigri Elektrograpit) December 196 ? . 1 2 5 . R. B . Trask, and Mark J . Smith, Fr. Patent 1 ,5 2 0 ,1 7 7 (Air Reduction Co.) April 1968. 73 ADM COCI12