FUNDAMENTAL STUDIES OF RUBBER BLENDS* P. J. Corse DuNLor RESEARCH CeNTkE, DUNLOP RUBBER Co., Lrp., Birsaxcuan, ENGLAND, INTRODUCTION, The range of rubbers based on petroleum hydrocarbons is necessarily limited. After exploring facets such as solution and emulsion polymerization, polymer production will probably be concentrated on several economic lines. All rubbers have shortcomings in one or more properties (see Table I). There are, therefore, technical reasons for blending, as it should be possible to obtain the right compro mise in properties on blending two rubbers. The difficulties experienced in processing some rubbers also necessitate blending. ‘There are also appreciable differences in price between rubbers emphasizing economie reasons for blends. Two examples serve to illustrate these considerations: (a) In tread compounds, the high abrasion resistance under certain conditions conferred by the use of cis-polybutadiene is desirable but the poor road holding and rib-tearing properties are not: thus blends with natural rubber and styrene butadiene copolymers are ustally employed; (b) ‘The resistance is high; accordingly, cation in white tire ‘There is a need to understand which polymers can be successfully blended and what underlying factors influence the result. This paper attempts to correlate the fundamental properties of rubbers used in blends with the physical properties of the resulting vuleanizates. It points out reasons why blends are seldom as good as one would expect theoretically by interpolation between the properties of their constit- uents and suggests ways of overcoming the deficienci GENERAL DISCUSSION How is compatibility, as applied to rubbers in blends, defined and measured? ‘Two hydrocarbon liquids are, under most conditions, mutually soluble in one another, i.e., they are miscible and exist in mixtures as one phase. For hydrocarbon rubbers, however, two phases are usually present. Many pairs of rubbers can probably never be truly compatible on a molecular scale, as has been indicated previously by phase contrast microscopy studies!, but on a slightly larger scale, and especially in cured technical compounds containing appreciable loadings of carbon black, may still function effectively as one phase. Using the glass transition temperature (7) of the blend as a test of com- patibility, for the work described in this paper, an incompatible blend is defined as one which always exhibits two or more values of 7, of the same values as the constituent rubbers used in the blend, A compatible blend is defined as one which has one T,, of intermediate value; it results from rubbers of similar solubility param- eter, but these do not neces always exhibit one T,. * Prosonted at a meeting of tho Division of Rubber Chemistry, American Chemical Society, New York, New York, September 14-16, 1966, 324STUDIES OF RUBBER BLENDS sor uanupoyy umnupoyy oY/amupayy IH Mold opnmoyize ouorpemg. sor Wa wT A yaty/ummipoyy UNpoP, NpOP, MOT seaans rang war “A anIpaW MOL "A way “A ‘WIPO, unppery aay A aa 10, SaMNdONY HOU ava, TVOEAL, wuIpO YL, unto ua aa manpe WH ‘umupayy, uas worsmneg, [sravy, Wa UNTO MOT aH ust “A BoA WH aoqqna ramen, Armqvonnsog souyysTsox LONP AD 20m 891 PPS 70M aouvpaor UosTIqy wduene sway, ysBuagys opsua, aouon oR326 RUBBER CHEMISTRY AND TECHNOLOGY There are several methods available for determining 7’. In the work described it has been measured dilatometrically or by means of a newly developed instrument, the Rolling Ball Loss Spectrometer. Dilatometer—Samples are usually in the form of standard compression set pellets, aleohol being used as the expansion fluid. The dilatometer bulb, after im- mersion in liquid nitrogen, is allowed to warm at 0.5 to 1° C/min, Our apparatus is selfrecording, the output from the thermocouple being fed to a recorder. An extension shaft fitted to the chart drive of the recorder drives a drum wound with a cord which causes a photoelectric detector head to follow the liquid level up the capillary tube of the dilatometer. A graph of alcohol level against temperature is therefore drawn and transition points are easily seen. Rolling Ball Loss Spectrometer-—Details of this instrument have been given elsewhere”. It is a compact device for following hysteresis losses in polymeric compounds by measuring the resistance of small balls to rolling over the surface of a testpiece. It is fully automatic and plots a graph of hysteresis loss as a function of temperature from — 100° C to +100° C. ‘Tasue II Sovuprury PARAMETERS AND GLASS TRANSITIONS Microstructure of butadiene units % Solubitity - Bound ——Dilatometrie parameter M12 %A,A styrene or 7, °0 3, (cated) aerylo- nitrile Polybutadiene All cis 0 100 _ —110 8.22 (extrapolated) Phillips oes, _ —106 8.21 Diene 88 _ 95 8.17 Emulsion a 79 — -85 8.13 Buna 85 a7 8 _ -72.5 8.06 High vinyl ne) _ —46 7.91 All vinyl 100 0 ae 25 7.78 (extrapolated) SBR SBR 1500 ao 23.5 —52 8.29 ‘Medium styrene—type I 2 2» 40 —32 8.41 Medium styrene—type IT 21 70 8 —20 8.47 (Emulsion BR. 2b 9 oe —85 8.18) (Polystyrene - — 10 +100 9.09) NBR Low nitrile NBR a 79 20 —88 8.98 High nitrile NBR 2 79 40 -12 9.92 (Polyacrylonitrile 100 +100 12.4) Miscellaneous Natural rubber - = - 68.5 8.25 Neoprene GNA ie - —43 9.26 EPR (50 molar % ie _ Pee —62 7.88 ethylene) Butyl rubber - - =_ 70 2.6STUDIES OF RUBBER BLENDS 327 Below the glass transition temperature, the rubber sample is in a highly elastic glasslike state. As the temperature increases, the rubber passes through a maximum hysteresis loss region at 7',, as viscous components come into play exerting a drag on the rolling balls. At higher temperatures, molecular motion becomes less difficult and the hysteresis falls. A desirable feature of the loss spectrometer is the sharp peaks produced, permitting determination of transitions in rubbers to within 1°o, RESULTS AND DISCUSSION Solubility parameters (6) of most of the rubbers used, calculated by the methods described by Brydson®, and dilatometric glass transition temperatures (T',) of vuleanizates are shown in Table II. These are compared with properties of process oils in Figure 1, ‘Those of the polybutadiene vulcanizates are influenced by micro- structure, T, increasing and 6 decreasing with higher vinyl content: SBR and NBR vuleanizates have values of 6 and 7’, which increase with higher bound styrene and acrylonitrile content. 100] % POLYSTYRENE 50° 50. 8 10 12 5 SOLUBILITY PARAMETER. Fra. 1—Comparison of solubility parameters and glass transition temperatures of polymers and oils,RUBBER CHEMISTRY AND TECHNOLOGY 328 av 16 sr'6 26k $8 1's ag 8 82's. °h 80 207-NMS/ST-NHS 08/09 &%— O- NES (pa Uopss08 Cae /overpeing) gI-NUS (o2/9e. : Se E80, 86/92 Sb (euerpeingsjod upg) qyg ee soqqny yey, o8L— ouetC/UES 24/89 og— SILT das 6— dN 9g UDICT s89— angxrur 0¢/0g g- Foe ouardyog s89— saqgng peasy spueiq e1qnedsiog (D0) ira SANTI 40 NostEVaNO_ OL ev WI wey, 9°6 98. a6 ws ies 99°6 996 8° ‘/siInsed Aoesu0Y “sg “D PUR AdUEIIEE “WD > “HA WORNIOS “09 sOqqNA 7 o4IJ, BUOISAITT ¢ “HAS WoNNIs 0p mMneONIE sds » ot s9- aanyxtu 09/09 e~ VND ouasdoayy $89— soqans pemye ver } 201— ‘WEIN/U 04/09 — WAN TTT Moy amEpOHL sor— ‘ouarpeyngAjod-e4) wr} L0o1- aumgxtur 0¢/0g sor- auapuyngdjod-s43) og— ‘MAN oar garg campy, a} r29- oamaxtur 09/0 oe— ‘WAN OTE yar wNpoyy $'89— soggnz eye, spuayq a[qrredwoouy (De) "LSTUDIES OF RUBBER BLENDS 329 Rubbers which differ appreciably in solubility parameter display two values of T, when blended as for the constituent rubbers. Some typical examples are listed in Table IIT. Blends of rubbers of similar solubility parameter can exhibit one T,, intermediate between those of the constituent rubbers. Tt will be concluded that to obtain the optimum compromise in the properties of a rubber blend it is best to use rubbers of closest similarity in solubility parameter, although even then a single T, may not necessarily result. For some purposes, how- ever, ¢.g., damping applications, as reported by Dunnom and deDecker, dissimilar solubility parameters and two TT, lead to the desired low resilience compounds. Such blends of dissimilar polymers are found to have dynamic properties which are characteristic of the component of higher T, at ambient. temperature but the lower 7’, component appears to dominate at high temperatures, ¢f. Figure 2, which shows dynamic resilience® curves for natural rubber, a medium low nitrile NBR and 60/40 natural rubber/NBR tread compounds. ‘To minimize hetereogeneity of rubber blends on a molecular scale and to ensure optimum distribution of compounding ingredients, especially carbon black, rubbers of similar Mooney viscosity are used. The value of so doing has been demonstrated’. Poor black dispersion leads to poorer physical properties in a vulcanized rubber, quantitative measurements’ illustrating this convincingly. In blends of rubbers 90) ~ wy gv z oe a a 3 77 NRINBR @ he : cS - 7 oT NBR x ° 50. 20 60 100, 140 TEMPERATURE °C Fig. 2.—Resilience at constant (20 kx) load ax a function of temperature. Natural rubber, Paracril ALT, and blend.330 RUBBER CHEMISTRY AND TECHNOLOGY two considerations result from this fact: good black disaggregation must be achieved, and the best possible black distribution should be ensured between the rubbery components which may differ in black affinity, best possible in the sense that optimum properties will not necessarily result from an equal concentration of black in the two components, ‘The different affinity of various rubbers for carbon black has becn demonstrated by electron micrographs of gelatin carbon replicas of torn surfaces of ASTM tear specimens. Carbon black particles are extracted by the gelatin during replication because the gelatin and filler interaction is greater than that of polymer and filler for the individual extracted particles. Fig. 3.—Electron micrographs of carbon shadowed gelatin replicas. Upper left: natural rubber tread stock, 50 HAF cured 45’ at 273° F. ASTM ‘Die B’ tear resistance at 21° C 33.2 Kg/0.1 in.; Upper right: samo, 63/ curo. Toar 30 Kg/0.1 in.; Lower left: samo, 65’ eure. ‘Tear 26.8 Kx/0.1 in.; Lower right: Shell isoprene rubber 305, similar tread stock, 55’ cure. ‘Tear resistance 18 Kg/0.1 in.STUDIES OF RUBBER BLENDS 331 In natural rubber (Figure 3) the number of carbon black particles extracted decreases with increasing cure time and is accompanied by a decrease in tear strength. A synthetic polyisoprene compound also shows a reasonable number of extracted particles and a moderate tear strength. Apart from these, the remaining synthetic rubber compounds (emulsion SBR, butyl and cis-polybutadiene— Figure 4) are generally similar with very little extracted black and low to moderate tear strength. One point of interest however, is that an oil extended cis-polybu- tadiene compound (30 phr aromatic oil) has superior tear strength to an un- extended compound and shows an amount of extracted black (Figure 4) inter- mediate between the levels for unextended cis-polybutadiene and natural rubber compounds. tread stocks. Upper left: SBR 1500, tear resistance 13.8 K@/0.t ‘per right: butyl, tear resistance 13.4 Kg/0.1 in.; Lower left: cis-polybutadieno, tear resistance 10.6 Kg/0.1 in.. = (30 phir) off extended cis-polybutadiene, tear resistance 14 Kg/0.1 in.332 RUBBER CHEMISTRY AND TECHNOLOGY ‘Tani IV Narunat Russer anp SBR 1712 Buenps* (Physical properties of vulcanizates cured 40 min at 141° C) Solution mix Dry mix A B GK-a Tensile strength, kg/em? 85 152 198 300% Modulus, kg/em* _ 17 135 Elongation at, break, % 270 357 430 ‘Tripsometer BS? Hardness 7 B56 67 Resilience, 50° C, % 48. 49.5 58 ASTM tear resistance, kg/0.1 in, ae C 14.5 24 2.0 100°C 10.6 13.7 13.9 Volume fraction of insoluble poly- 0.24 0.25 0.24 mer in swollen vuleanizate (V ,) Black dispersion, % Very uneven dis- Even loading 98 tribution * Formula: natural rubber (RSS 1) 50, SBR 1712 50, HAF black (fluffy) 50, mineral oll 5, zine oxide 4, stearle acid 1.5, antioxidant blend 1.25, sulfur 2.125, CBS. ‘These differences between extracted black particles for various polymers are interpreted in terms of optimum polymer and filler interaction. Maximum rein- forcement in terms of tear strength is thought to oceur not when filler and polymer interaction is maximal but at some value causing failure to occur at the interface between filler and polymer rather than within the bulk of the polymer. In contrast, where polymer and filler interaction is above the optimum value, areas immediately FiG. 5.—Micrographs of compositions of Table TV. Left: A, natural rubber last: mixed control, G4 mixer; right: B, SBR 1712 added last. ter: drySTUDIES OF RUBBER BLENDS 833 ‘Taste V ‘Duns 55 NF ann SBR. 1500 Brxxo* (Physical Properties of Vuleanizates cured 40 min at 141° C) Tray driod Spray dried Tensile strength, kg/em® 74 128 300% Modulus, ke/em? — 96 Elongation at break, % 240 383, ‘Tripsometer BS? Hardness 51.5 58.5 Resilience, 50° C, % 73.0 74.0 ASTM tear resistance, kg/0.1 in, 21°C 12.0 13.8 100°C 5.5 7.2 Swollen volume, (V,) 0.22 0.22 Black dispersion, % Uneven distribution 96 © Formula: Dione 55 NF 50, SBR 1500 50, HAF black 50, minoral oll 5, stearic acid 1, zinc oxide 3, antioxidant blend 1.5, sulfur 1.75, CBS 1.0. around the filler particles are of greater strength than the bulk of the polymer and are shunned by the advancing tear path. Further evidence on the effect of maldistribution of carbon black has been accumulated in experimental work involving solution mixing of rubber blends. This involves dissolving the rubbers in solvent (usually hydrocarbon) and adding a Gispersion of black and other compounding ingredients in the same solvent. Re- Fic. 6.—Comparison of tray dried (left) and spray dried (right) solution blond. 50 Diene 85 NF/50 SBR.334 RUBBER CHEMISTRY AND TECHNOLOGY moval of the solvent, usually by drying in trays, produces sheets of compound for subsequent curing. Table IV shows inferior physical properties obtained when blends of natural rubber and SBR 1712 were compounded in solution. For com- pound A, the SBR 1712 was compounded with all ingredients and uncompounded rubber was added with high speed mixing. For compound B, natural rubber was compounded with all ingredients and uncompounded SBR 1712 was added with SBR ---~ Ger P NR*DUTREX 20 - NR+DUTREX 55 cis BReDUTREX 20 -100. cis BR¢DUTREX 55, °o 40 80 12 OIL (PPHR} Fig. 7. Effect of extension with aromatic oils on the glass transition temperatures of SBR, natural rubber, and cis-polybutadieno tread compounds. high speed mixing. Comparison of columns A and B show that an improved black distribution is obtained when the natural rubber component is compounded sepa- rately, cf. Figure 5, and this is reflected in improved vulcanizate properties. These and other results indicate that SBR 1712 may have a faster uptake of black, because of either its greater affinity or the lower Mooney of the oil extended polymer.STUDIES OF RUBBER BLENDS 335 Solvent is usually removed from the solution compounded blends by tay drying. The poor results obtained for blends mixed and dried in such a manner, compared to those of a blend mixed in an internal mixer, are probably due to phase separation of the polymer on standing, accompanied by redistribution of the Taste VI Narurat Russer anp SBR Brenns (Physical Properties*) 50/50 NR/SBR 50/50 NR? 1500° NR/Duradene* ‘Tripsometer BS? Hardness 65 or 70 Resilience, 50° C, % 65 56 64 Tensile strength, kg/cm* 240 230 220 300% Modulus, kg/em* 160 155 160 Elongation at break, % 450 420 380 ASTM tear resistance, kg/0.1 in. 21°C 38 29 29 100°C 18 15 13 Cut growth, mm/h 0.21 0.58 0.17 Swollen volume, V,, in toluene 0.255 0.250 0.258 Power loss at 110° C BE’, kg/em? 70.4 on? 80.4 EB", kg/em? 4d 6.0 52 Resilience, % 82.3 75.7 80.6 Power loss at constant load, J/rev 0.97 1.40 1.01 “ All polymer 100, HAF 50, process oil 5, antioxidant 1 ° Zine oxide 5, stearic acid 2, CBS 0.5, S 2.5, cure 45 min, 273° F. © Zine oxide 4, stearic acid 2, CBS 0.75, S 2.3, cure 65 min, 273° F. “Zine oxide 4, stearic acid 3, CBS 0.75, 8 2.3, cure 45 min, 273° F. black. Spray drying provides a means of rapid removal of solvent and reference to ‘Table V indicates that for a 50/50 Diene 55 NF/SBR 1500 compound, the spray dried blend has better vulcanizate properties because of more even black distribu- tion (ef. Figure 6). Most of the preceding discussion has been concerned with carbon black but similar considerations also apply to other compounding ingredients, Zine oxide, for example, migrates! to the natural rubber phase in blends with emulsion SBR. Even in a compound based on one rubber, measurement of dispersion of sulfur by autoradiography? shows that the tensile strength variation is very much less when the sulfur is adequately dispersed. Our second conclusion, therefore, is that in addition to requiring that, rubbers of similar Mooney viscosities be blended, optimum properties require good disag-336 RUBBER CHEMISTRY AND TECHNOLOGY gregation of compounding ingredients and the right distribution between the com- ponents of the blend. Glass transition temperatures and solubility parameters of normal rubber process oils lie in the regions —45° to —90° C and 7.5 to 8.5, respectively (Figure 1). Polymer and oil combinations of similar solubility parameter are compatible, Hysreresis Loss (T/sec x 102) tho oO 126 OS o os . — OS ; | os Cone Min.@ Ut" “100 Temperature C Fic. &—Hysteresis loss of a blend of polybutadione and natural rubber as a function of temperature and cure time. eg. cis-polybutadiene and highly aromatic oils. Dissimilar combinations can give rise to two values of Tz, e.g., 2 medium nitrile butadiene acrylonitrile copolymer and naphthenic oil. Addition of large amounts of aromatic oil elevates the 7’, of both cis-polybutadiene and natural rubber (cf. Figure 7). Among other consequences, this leads to an improvement in wet skid resistance of tread compounds based on these rubbers.STUDIES OF RUBBER BLENDS 337 Oils also function by reducing Mooney viscosity, thus high Mooney rubbers can be oil extended for better mixing with low Mooney materials. There is, therefore, the possibility of using oil to bridge the compatibility gap which may exist between rubbers in a blend. Even when rubbers of similar solubility parameter and similar Mooney vis- cosity are used, optimum physical properties are not always obtained. Other im- portant considerations are curative requirements and rates of cure of the rubbers. It is recognized that if slow and fast curing rubbers are blended, eg., butyl and natural rubber, in general the former will be undercured and the latter will be over cured in the resulting vuleanizate. Migration of curatives before eure due to solubil- ity differences may worsen this problem. +O ——> Hysreresis Loss (Tse x 10%) 35° to: OS Os: Cure- Min.@ 138°C -l00. = = Temperature °C Fic. 9.—Hysteresis loss of a blend of polybutadiene and NBR as a function of temperature and cure timo. Such mismatch of cure rate should be avoided where another choice is available. Natural rubber and solution SBR are both relatively fast curing, but emulsion SBR is relatively slow. Table VI shows that advantages in physical properties result from matching the cure of the rubber components of a blend as in natural rubber and Duradene compared with a mismatch as for natural rubber and SBR 1500. All blends with one T,, contain rubbers of similar solubility parameter but the use of rubbers of similar 5 does not always lead to a blend having one 7. However, cure may be an important factor in these blends, as demonstrated below.338 RUBBER CHEMISTRY AND TECHNOLOGY ‘The rolling ball loss spectrometer shows sharp peaks at rubber transition temper- atures and is a more sensitive instrument than the dilatometer for study of the effect of cure. Figure 8 depicts the spectra of compounds of a blend of natural rubber and cis-polybutadiene—rubbers of similar solubility parameter—and Figure 9 cis-polybutadiene and a butadiene acrylonitrile copolymer—rubbers of dissimilar solubility parameter. At short times of cure, the cis-polybutadiene and natural rubber components show several resolved peaks which progressively merge as cure is increased. It is possible that sulfur bridges are formed between the net works of the rubber components leading to a pseudo single phase and on the basis of the definition in this paper, transition from incompatibility to compatibility. Cis-polybutadiene and the butadiene acrylonitrile copolymer are completely in- compatible, showing two separate loss peaks throughout the cure range. This behavior is not completely understood and is being further investigated. SUMMARY ‘To sum up our findings on the requirements for rubber blends with vulcanizate properties arithmetically interpolated between those of the constituent rubbers one needs: (a) Rubbers which have similar values of solubility parameter and which also yield blends whose vuleanizates exhibit a single glass transition temperature. (b) Rubbers of similar viscosity. (c) Mixing methods capable of giving good disaggregation of compounding ingredients and satisfactory distribution between the constituent rubbers. (d) Rubbers of similar curative requirement and cure rate and curative systems capable of giving interlocked networks. (e) Suitable choice of plasticizer, which may offset slight deficiencies in (a) and (b). There still remain many unanswered questions, which it is hoped will be answered in future research. ACKNOWLEDGMENT ‘This paper is a resumé of recent work on rubber blends carried out at Dunlop Research Centre, Birmingham, It encompasses the researches of several associates to whom my acknowledgments and thanks are due as also to the Dunlop Rubber Company for permission to publish. REFERENC! 1M. HL, Walters and D. N. Keyte, Trans. Inst. Rubber Ind, 38, 40 (1962), +1. ©. Chootham, Trans. Inst. Rubber Ind. 44, 156 (1965). 23. A. Brydson, Plastics 26(290), 107 (1961). «G. M. Barteney and G. 8, Kongarov, Vusomotekul Socdin. 2, 1602 (1960); Ruppex Cum. ‘TECHNOL. $6, 668 (1963) 5D. D. Dunnom and H. K. deDecker, Rubber Age (N.Y.) 97(8), 85 (1965). ®D. Bulgin and G. D. Hubbard, Trans. Inst. Rubber Ini. 84, 201 (1958). 1. HM. Leigh-Dugmore, Symposium on Mixing ‘Technique with Special Emphasis on Dis- persion, Falstecho, Sweden, May 1964. "B. B. Boonstra and A. I, Medalia, Rubber Age (N.Y.) 92, 892 (1963); ibid. 98, 82 (1968). ° 1, M. Blaunshtein and M. 1. Berman, Kauchuk Rezina 17, $1 (1958). B,STUDIES OF RUBBER BLENDS 339 APPENDIX Compounding Formulae for Table IT Polybuta- Natural dienes SBR NBR Rubber Polymer 100.0 100.0 100.0 100.0 Sulfur 1.75 1.75 2.0 2.5 Suntooure 0.8 1.0 1.5 0.5 Stearic acid 1.0 1.0 1.0 2.0 Zine oxide 3.0 3.0 5.0 5.0 Santoflex AW¢ 0.75 0.75 - - Santoflex IP* 0.75 0.75 ~ — ‘Nonox HFN: _ _ 2.0 1.0 HAF black 50.0 50.0 50.0 50.0 Process oil 5.0 5.0 5.0 5.0 Monsanto Antidegradant—6-ethoxy-2,2,4-trimethyl-1 ,2-dihydroquinoline. » Monsanto Antidegrad: v-phenyl-N’-isopropyl-p-phenylene diamine. © L.C.I, Antidegradant—Blend of arylamines’. Neoprene GNA—Polymer 100.0, Calcined magnesia 4.0, Zinc oxide 5.0, Stearic acid 0.5, MBTTS (Altax) 1.0, HAF black 35.0. EPR—Polymer 100.0, Dicup 4.0, Butyl—Polymer 100.0, Sulfur 2.0, MBT 0.5, Zane oxide 5.0, SRF black 40.0, Mineral off 10.0. ulfur 0.4, HAF black 50.0. ‘TD 1.0, Tellurac 1.0, Stearic acid 1.0, Compounding Formula for Table IIL Incompatible blends Natural rubber ‘Medium high nitrile NBR Medium low nitrile NBR cis-Polybutadiene MC Sulfur Santocure Stearic acid Zine oxide Nonox HFN Sundex 53" HAF black Suvaron|, | SS esssegg! ls: oe Seaxunon S| 8) SSesseasls BSy pene 8S | eeeebibss Compatible lends: Natural rubber/Solprene has 55 EPC; SBR/Diene has 60 ISAF, 17 Dutrex RT. Natural rubber Neoprene GNA Sulfur Santocure Stearic acid Zine oxide Lt. eale. mag. Sundex 53¢ ‘Nonox HEN HAF black * Rubber Process Oil—Sun Oil Co. gegnon Se SSSR ROS Be ee340 Polymer Sulfur Santocure Santocure MOR, MBTS TMTD Stearic acid Zine oxide Nonox HEN Santoflex AW Santofiex IP Process oil Dutrex 20 HAF black RUBBER CHEMISTRY AND TECHNOLOGY Compositions for Figures 3 and 4. IR 305 100.0 l1Eg SBR 1500 100.0 1.75 1.0 leg |ecery el 55565 s S Butyl 100.0 15 Eee cites ouem cis-BR, 100.0 1.75 0.8 eerie seeeecree Suh oe ° Daas ee ss ee na ae