THE EFFECT OF CARBON BLACK SURFACE PROPERTIES AND STRUCTURE ON RHEOMETER CURE BEHAVIOR* G. R. Corren Canor Corporation, Concorp Roan, Binuerica, Massacwuserts 01821 INTRODUCTION During the last few years, the oscillating disk Rheometer has become a generally accepted quality control tool in compounding laboratories throughout the rubber industry. Recently, the Rheometer was proposed! for characteriza- tion of the reinforcing characteristics of carbon black in rubber. The present paper has as its goals: (a) relating the experimental parameters obtained from the Rheometer trace to the analytical characteristics of carbon black, and (b) determining the effect of carbon black on the accelerated sulfur cure of rubber. The Rheometer consists of a biconical disk rotor enclosed in a eavity filled with raw rubber. The rotor oscillates through a small angle (usually 1° or 3°) and the torque required to produce these oscillations is measured continuously. The cavity is maintained at curing temperature. As the rubber cures, it stiffens and the torque required to produce the oscillations is inereased (Figure 1). Much work has already been performed in relating these traces to the kinetics of the cure reaction in pure gum compounds. It has been shown that the ob- served increase in the Rheometer torque (or complex dynamic modulus) at a given time ¢, AL,, is directly related to the crosslink density’, particularly if the measurements are done at relatively low frequencies of 3-10 epm. If one assumes that the crosslinking reaction follows first order kinetics, it may be shown that In — (AL,/ML)] = kat, ay where AL represents the maximum increase in Rheometer torque observed at full cure and ky is the rate constant for crosslinking reaction. A plot of Equa- tion (1) is given in Figure 2. We note from Figure 2 that it takes some time before Equation (1) is obeyed and a straight line is obtained. This induction period, tz, is related to scorch time, while the rate constant kz determines the time required to reach optimum cure. In addition to these parameters for gum compounds, other rate constants can be derived from rheometer curves providing that a suitable reaction scheme is assumed?. In filled compounds the presence of filler influences all three parameters mentioned earlier. It is important to understand how the proper- ties of the fillers influence the rheometer curves and parameters derived from these curves. Westlinning and Wolff? suggested that carbon blacks can be uniquely char acterized by their surface areas and ap-values, defined by ap = [AL,/AL,) — 1]/W, (2) * Presented at a meeting of the Division of Rubber Chemistry, American Chemical Society, Cleveland, Ohio, October 12-15, 1971. 129130 RUBBER CHEMISTRY AND TECHNOLOGY —_— _ ONE WEEK OLD RE-MILLED TORQUE, IN Les. 10 20 30 “0 0 TIME AT 29308, mins. Fig 1—Influence of aging and milling on rheometer torque curve. 50 phr HAF black in NR/CBS formulation. Rheometer set at 3° angle of oscillations. ac tg VALUE FoR cum “| oe 4 HT SLOPE ky 08 | FOR Gum PURE wa =a 45 phy REG. SAF 5 10 15 2% B.S. CURE TIME, eins. Evaluation of cure parameters from Rheometer torque curve in SBR/CBS formulationEFFECT OF BLACK ON CURE 131 where subscripts f and g stand for the maximum torque measured with filled stock and gum stock, respectively. W represents the weight fraction of filler in the filler-rubber mixture. We may note that this equation is similar in form to the Einstein equation for viscosity of suspensions, 7 = 40. (1 + 2.5 ¢), although the filler loading is given as weight fraction rather than volume frac- tion (Figure 3). One reason why this simple equation is obeyed could be the fact that the modulus is measured at a very low shear strain (ca. 15-20%) at relatively high temperature—conditions which reduce the effect of filler ac- tivity. However, the ap-value will be constant only if the filler does not change the cure efficiency, i.e., crosslink density. A graphical method for evaluation of p-values is shown in Figure 3. Since ap-values were shown to be independent of carbon black loading, level of cure, or curing system employed?, Wolff and Weatlinning proposed! that carbon blacks be graded according to four pa- EINSTENES ling) 11-25 se CARBON BLACK LOADING, aoe Fig. 3.—Graphical evaluation of av values in SBR/CBS formulation, rameters: (a) surface area, (b) a p-value, (c) induction period t4, and (d)cross- linking rate constant kz. The last three of these parameters are derived from the Rheometer trace. In the present work an attempt is made to separate and evaluate the effects of particle geometry and surface chemistry of carbon blacks on these three parameters. EXPERIMENTAL All rubber stocks were compounded in a Brabender Plasticorder at 80° C with the rotor speed set at 50 rpm and mixing cycle of 12 min. The compounded material was tested in the Monsanto Rheometer, Model MPV, operating at 10 rpm with 1° oscillations and at a temperature of: (a) 312°F for SBR N-cyclohexyl-2-benzothiazole sulfenamide (CBS) stocks, and (b) 298° F for SBR/tetramethylthiuram disulfide (TMTD) or NR/CBS stocks. The true132 RUBBER CHEMISTRY AND TECHNOLOGY TapLe I Comparison oF Stanparp anv Micro Dies Usine 4 Mopiriep SBR/CBS* Formuation Standard die Miero die tay ka, ta, key Sample min min AL or min min” AL ar Gum 0.162 43.4 169 0.170 21.9 — HAF. O18 77-4 96 0.146 440 2.26 ISAF 0.104 77.7 106 0.1290 44.4 2.27 * N-Cyclohexyl-2-benzothiazole sulfenamide. oscillation angle of the disk was found using an appropriate correction factor‘, In preliminary experiments an ASTM standard die, having a cavity of 1.50 X 0.400 inches, was compared with a micro-die, having the cavity of 1.40 X 0.150 inches. The ASTM standards? suggest operating the die rotor at 3° angle of oscillation, thus giving a maximum shear strain of 0.196. In order to keep the shear strain roughly of the same magnitude, the micro-die was used at 1° angle of oscillation, giving a maximum shear strain of 0.163. The two dies were then compared using the same rubber stock, and it was noted that the induction period in a standard die was longer by some five minutes due to the lower rate of heat transfer while the crosslinking rate constant, ke, and ap-value were lower than those observed with a micro-die (Table 1) It was decided to use the micro-die throughout this study in order to ensure good heat transfer through the sample and obtain more meaningful kinetic data. The formulations given in Table IT were used in the present work unless otherwise specified. The sample history (aging) was found to influence the shape of the Rheometer torque curve (Figure 1). However, excellent reproducibility was obtained if samples were re-milled immediately prior to the test. There- fore, all samples were allowed to rest 24-72 hours after compounding, and then re-milled prior to the Rheometer test. RESULTS AND DISCUSSION AL AS A MEASURE OF CROSSLINK DENSITIES IN FILLED RUBBERS The problem of measuring crosslink densities in filled rubbers has not been solved despite many studies. In pure gum vulcanizates, excellent correlations have been obtained between chemically estimated crosslink densities and equilibrium modulus’, or equilibrium swelling (¥',). Taste IL FORMULATIONS SBR/CBS* SBR/TMTD NR/CBS* SBR-1500 100 100 =a Natural rubber — 100 ‘Carbon black 50 50 Zine oxide 0 5.0 5.0 Stearic acid 3.0 3.0 Sulfur = 25 Santocure* = 0.45 TMTD 32 bee © N-cycloheryl-2-bensothiazole sulfenamide.EFFECT OF BLACK ON CURE 133 Unfortunately neither of these methods can be applied to filled rubbers. The equilibrium swelling is normally reduced (V, values numerically larger) by restriction to swelling imposed by carbon black’, but the value of this cor- rection cannot be estimated theoretically. Similarly, considerable difficulty exists in calculating crosslink densities from equilibrium modulus values of filled stocks since these measurements must be corrected for the hydrodynamic effect of the filler and rubber-filler interaction. Brennan and Jermyn® attempted to correct the observed modulus by a modified Guth-Gold equation, where filler volume was assumed to consist of the volume of (filler + bound rubber), while Mullins and Tobin? introduced a strain amplification factor to correct observed elongation of sample to an ff I was vee! Wy. Fro, 4,—Relationship betweon AL and Ve for natural rubber stock containing 50 phr of carbon black. Broken lines indicate points at constant curative level. assumed elongation of the rubber matrix. Unfortunately neither of these pro- cedures was fully successful. The increase in rheometer torque, AL, observed during cure has been used for estimation of crosslink density in pure gums with a large degree of success’. Other workers! have implied that this relationship holds also for filled stocks. In Figure 4 the relationship between AL and ¥; is shown for a number of vuleanizates filled with blacks differing in surface area, structure, and “ac- tivity”. Three distinct plots may be distinguished; (a) HAF (1500° C) gives the highest AL at a given V,, (b) MT blacks show intermediate behavior, and (c) HAF and ISAF blacks give the lowest AL at a given Vy. The data reported in Figure 4 represents AL-values for a number of for- mulations that differed in the curative concentration only. However, the same134 RUBBER CHEMISTRY AND TECHNOLOGY relationship was found to be true for partly cured samples of a given curative concentration, where AL was controlled by the time of cure. Let us assume that V, represents true crosslink density and AL is related to the 300% modulus of these stocks. Then at constant V, (ie., along line A-B in Figure 4) HAF (1500° C) would have to have a higher modulus than regular HAF stock. This is not true. A more reasonable alternative hypothesis is that AL represents true crosslink density. Thus, at constant AL (i.e., along line C-D in Figure 4) HAF (1500° C) would have a lower V, (or swell more) than regular HAF stock. This is very plausible since we know’ that regular HAF would restrict equilibrium swelling, while heat-treated HAF (1500°C) would offer no re- striction to swelling. In Figure 5 it is shown further that neither the curing system (e.g., sulfur- less TMTD or CBS) nor presence of oil influences the relationship between AL and V, for stocks containing 50 phr of ISAF black. cy % 4 ad = ot J noe eee A THTD , NO OW fm SANTOCURE , NO OIL or = 020OatOF02sCOSSSCSCaTSCB Vp « (n eyclobesane) Fia. 5.—Relationship between Vz and AL for different rubber formulations. Thus, qualitatively AL offers a better approximation to true crosslink density than V,. However, AL values would have to be corrected for filler loading before any quantitative relationships could be derived. EFFECT OF CARBON BLACK ON CURE EFFICIENCY In earlier studies it was noted that oxygen-containing groups at the carbon black surface exert a profound effect on the rate of cure reaction, ks, and the maximum inerease in torque, AL, when tested in a natural rubber formula- tion containing a CBS/sulfur curing system. However, no effect of surface groups on sulfurless TMTD cure was observed, and the rate constant ky was the same for all blacks. Thus, the effect of filler structure on ap-values can beEFFECT OF BLACK ON CURE 135, WREGULAR BLACKS GRAPHITIZEO BLACKS ° = ar) 10S BPA, €2/1009 Fic. 6.—Effect of filler structure on ap-values in SBR/TMTD formulation. best determined in a sulfurless TMTD formulation where all other effects are suppressed. A plot of ag-values as a function of dibutyl phthalate (DBPA) values for a number of regular and graphitized blacks in such @ system is given in Figure 6. No significant difference between regular and graphitized blacks is noted. As was pointed out earlier, the ar-values represent a ratio of increase in maximum torque for filled stock to that for pure gum. This ratio should be independent of the level of crosslinking* providing that the filler does not inter- fere with the cure reaction. In SBR/TMTD systems this is indeed observed and therefore it is confirmed that the relationship between ap-values and DBPA is also independent of cure level (Table III). ‘The ap-values for regular and graphitized blacks in a SBR/CBS formula- tion are plotted in Figure 7. The graphitized blacks have consistently lower ap-values. Since ar-values for graphitized blacks in the CBS formulation are nearly the same as those in the TMTD formulation, it appears that graphitized blacks do not affect the efficiency of cure reaction. Porter has shown by chemical analysis that carbon black improved the efficiency of crosslinking in natural rubber. The present results confirm his findings, since higher ap-values for the SBR/CBS system compared to the SBR/TMTD system can only be explained by assuming that, in the presence of regular carbon black, the effi- ‘Tape IL Errect or TMTD Loapina on ar Vatues in SBR-1500 Containing 50 pur ISAF Buack. TMTD, phr ALe AL, ar 28 37.8 IZA 2.42 32 42.7 19.6 2.36 36 46.3 21 2.39136 RUBBER CHEMISTRY AND TECHNOLOGY REGULAR BLACKS GRAPHITIZED BLACKS ° 7” ~” o 0 a aT DBPA, 62/1009 Fro. 7,—Effect of filler structure on ay-values in SBR/CBS formulation. Tanux IV Core Parawerers ror SBR-1500/CBS ForMvation Carbon black Total scida, tay hs, type meg/¢ CB aL min min“ or Gun - 178 217 0.117 - Graphitized blacks 0.0 0.131 0.65 ISAF-LS 0.0 0.121 1.94 ISAF 0.0 0.100 2.30 I8SAF-HS 0.0 0.119 2.30 MT. a 0.128 1.13 ISAF-LS 0.34 0.065 2.16 ISAF 0.68 0.058 2.56 ISAF-HS 0.48 0.062 2.72 HAF-LS 0.28 0.078 2.17 HAF-B-2 0.73 0.046 2.32 HAF-B-3 0.82 0.035 244EFFECT OF BLACK ON CURE 137 ciency of cure is improved in the former, and hence AL, is increased more than would have been expected from filler loading alone. The rate of increase in ag-values with DBPA values for all blacks is nearly the same for TMTD and CBS accelerated stocks, within the range of DBPA values of 80-140 cc/100 g. The Rheometer data have also been analyzed to derive the crosslinking rate constant, ke, as well as the induction period, ta, und we note that in each case (except MT black) graphitization increased the rate of crosslinking reaction and the induction time (Table IV). It is known! that heating carbon black at 1500°C decomposes most of the oxygen-containing eurface groups. Heating above this temperature results in changes of crystallinity and a fully graphitized form is produced at 2700° C¥, The observed changes in cure parameters of compounds containing carbon 10 06 2 phr SULFUR 1 phe SANTOCURE TOTAL ACIDS meg/s 1.67 phe SULFUR 0.83. phr SANTOCURE . 02 0.02 0.06 0.10 0.14 RATE CONSTANT kp , mins? Fia, 8,—Relationship between total acid concentration and rate constant ks for a series of trested HAF-LS blacks in a modified SBR/CBS formulation. black heat-treated to elevated temperatures must result from the removal of acidie surface groups. On the other hand, mild oxidation of regular blacks increases the concen- tration of oxygen containing surface groups and have an opposite effect on cure, It is found that the rate of cross-linking (ks) of rubber stocks containing regular, graphitized, or oxidized blacks is inversely proportional to the total surface acid concentration (Figure 8 and 9) for both SBR and NR/CBS for- mulations within a single grade of a black. We note that at a higher loading of curatives in SBR stocks another, nearly parallel, relationship is found between total acids concentration and rate constant k. Also some variations in the re- sponse are found with different grades of carbon black.138 RUBBER CHEMISTRY AND TECHNOLOGY 08 06 TOTAL ACIDS, meg/g o4 02 ° 0.02 0.06 0.10 014 RATE CONSTANT kp, mins, ? Fig. 9.—Relationship between total acid concentration and rate constant ks for a series of treated HAF-LS blacks in NR/CBS formulation. The efficiency of cure in SBR/CBS stocks as measured by ay, increases with increasing total acid concentration (Table IV), and thus a relationship exists between ap and kp (Figure 10). An opposite effect is observed inNR/CBS system, since here the cure efficiency increases with increasing values of rate constant kp (Figure 11), or decreasing total acids concentration. 20 260 1.6? phe SULFUR 240 (083 phy SANTOCURE os . 220 ~~. SS 2.00 20 hr SULFUR 110 phe SANTOCURE 190 ° oaz 008 0.10 one RATE CONSTANT a, mint Fro. 10.—Relationship between ar and rate constant, kz, values for a series of treated HAF-LS blacks in a modified SBR/CBS formulation.EFFECT OF BLACK ON CURE 139 ae T T T T T 230 190 | 4 er 170 -— /, 7 150 4 10 4 006 2.10 on RATE CONSTANT kp, mit’? Fig. 11.—Relationship"between ay and rate constant, ks, for a series of treated HAF-LS blacks in NR/CBS formulation. In other words, graphitized black produces a higher ap-value (i.e., cure efficiency) than the regular black in natural rubber, but a lower one in SBR. This influence of carbon black on cure efficiency has been further confirmed by chemical analysis! for polysulfide groups (Table V). EFFECT OF SURFACE GROUPS ON VULCANIZATE PROPERTIES It has been demonstrated above that carbon black can influence the effi- ciency of the crosslinking reaction, and thus the crosslink density at optimum. cure. Since many vulcanizate properties are sensitive to the state of cure, the Taste V Erect or ToTaL Acip CoNCENTRATION ON FORMATION OF Potysutripic Crosstinxs 1x SBR-1500" Surface Total Carbon black = DBPA, area, —acids, Ry, % Poly- type ec/100g m/e = meg/g = AL = min ® sulfides ISAF 11g ul 70 0.129 22.4 SAF 15 141 7 0.109 22.4 Experimental 155, 148 79 0.096 20.4 Experimental 183 238 82 0.084 19.0 * Contains 50 phr carbon black, 1.75 phr sulfur, and 1.2 phr N-cyclohexyl-2-bensothis- sole sulfenamide. * Measured at 3° angle of oscillations.140 RUBBER CHEMISTRY AND TECHNOLOGY Tap.e VI Errect or Totat Acip Concentration on Stress-Srraix Properties oF VULCANIZATES 300% Tensile Elongation Carbon black Modulus, strength, at break, Formulation type Psi psi % SBR/CBS 1700 3980 560 1980 3605 460 NR/CBS 1645 3955 515 1505 3725 510 changes in the efficiency of crosslinking reaction should be reflected in, e.., tensile properties. Since there is no reliable method for the absolute determina~ tion of crosslink densities in filled rubbers, it was decided to examine only the relative changes in tensile properties when regular HAF-LS black was replaced by an oxidized sample of HAF in both SBR and NR formulations accelerated with CBS. The results of such an experiment are given in Table VI. We note that the oxidized black in the SBR formulation gives a higher 300% modulus, lower tensile strength, and lower percentage of elongation at break. All these changes are consistent with the initial postulate that inSBR formulations, an oxidized black will increase the crosslink density. On the other hand, an oxidized black in an NR formulation gave lower 300% modulus, lower tensile strength and no change in percent elongation at break, All these observations would indicate a decrease in crosslink density on addition of oxidized black. EVALUATION OF CARBON BLACK STRUCTURE FROM THE MONSANTO RHEOMETER TRACE From the data reported so far, the following two relationships may be formulated : ka = f (acid cone.) @) and AL = f (filler structure, loading, and acid conc.) (4) and since Westlinning’s ar value? may be derived using Equation (2), it follows that: ap = (filler structure and acid cone.). (a) In order to test the above relationship we utilized data kindly provided by W. N. Unger and H. E. Toussaint’, These consisted of 45 sets of results (Table VII) obtained with carbon blacks with surface areas in the range from 30 to 210 m?/g. Each black was compounded in a modified SBR/CBS formula- tion (compare Table II) where the sulfur and CBS loadings were increased to 2.0 phr and 1.0 phr, respectively. The DBPA values, extrusion shrinkage, ar, and k; values were reported for each black. However, the Monsanto Rheometer was operated with large (standard) die, 3° angle of oscillations, and rotor speed of 3 cpm. Thus a direct comparison between these results and those quoted in earlier sections of this paper is not possible. ‘The curve fitting was subsequently performed using a regression analysis program on the IBM-—1130 computer. In the first attempt we tried to relate the ar values directly to extrusion shrinkage results and the equation for the bestEFFECT OF BLACK ON CURE 14 Taste VIL Rurometer Resuuts anp ANALYTICAL Data on A Range or Furnace Carson Buacks* S.A. Extrusion ASTM. hi, DBPA, shrinkage, classification m!/g cc/100 g or hy % N-110 120.1 108.6 19 0.201 36.5 N-110 109.0 20 0.210 36.3, N-166 135.6 16 0.198 35.4 N-195 80.4 36 0.347 49.4 N-219 94.8, 83 0.243 471 N-220 120.2 98 0.224 4L1 N-220 117.6 08 0.257 41.0 N-220 110.8 98 0.257 41.6 N-242 125.2 1d 0.289 40.0 N-285 128.7 19 0.248 37.6 N-285 16 0.277 38.1 N-294 37 0.144 43.6 N-204 48 0.139 43.6 N-326 74 50.0 N-326 70 50.7 N-326 63 50.7 N-326 56 SLT N-326 80 524 N-330 04 42.3 09 42.9 10 43.3 99 44.8 04 43. 43.4 eoooocses—°0 SSESSESEE BE SSRSS BERNESE PYPYNN PY NNNE NNN NNNNNNNNE NNER EEE NYNENE EE NNN 04 0. 43.4 12 0. 43.6 . 11 0.: 43.5 ib 09 0. 4 z 14 0.: x 09 0.294 4 x 08 257 3 758 14 277 42.2 70.8 18, 0.257 38.2 208.4 BA 0.089 34.4 32.8 17, 0.315 42.5 33.8 5 0.328 38,2 35.5 0.315 37.3 34.6 3 0.289 38.9 319 32 0.315 39.6 3L7 29 0.330 40.1 31.5 fie 0.328 39.8 3L7 31 0.328 37.7 32.0 37 0.330 39.1 32.1 21 0.347 41.1 32.4 17 0.198 38.7 * Data of Unger and Toussaint. See reference 14. fit was found to be E = 71.99 — 14.653 (ar); 6) the standard error of estimate was 3.3 and correlation coefficient was 0.696. A plot of observed extrusion shrinkage values as a function of the results cal- culated from Equation (6) is given in Figure 12. The straight line in that graph represents the 1:1 relationship. We note a considerable scatter of results, but142 RUBBER CHEMISTRY AND TECHNOLOGY three points (marked by squares) deviate by a particularly large amount. These points refer to three conductive blacks (N-472 and N-204) which had markedly different cure rates, ks, some 50% below the value observed with HAF type black. However, even without these three points, the scatter of data is broad. This result. was expected, since the present work suggests that the ar values depend on both filler structure and cure efficiency, which is empirically related to rate constant ke [Equation (4)]. Thus in the next attempt an additional independent variable kz was added to the regression analysis and the response equation for prediction of extrusion shrinkage from known values of av and ke was found to be: E = 97.0 — 23.39 (ar) — 3.61/(ar-ke). @ The line drawn in Figure 13 represents a plot of the above equation. The stan- dard error of estimate was 1.47 and the multiple correlation coefficient was0.949. The conductive blacks (N-472 and N-294) obey this relationship much better and a considerable improvement in the prediction of extrusion shrinkage from the Monsanto Rheometer data was thus achieved. CONCLUSIONS The rheometer torque curve contains valuable information about carbon black. The rate constant for the crosslinking reaction, kz, is decreased with in- CORRELATION COEFFICIENT=0.696 STANDARD ERROR OF ESTIMATE=331 CALCULATED EXTRUSION SHRINKAGE, % £ 0 rege Meee Eee ear aoe eee u 3 7% 0 «2 “ “6 as Ea 32 cy OBSERVED EXTRUSION SHRINKAGE, % Fic, 12.—Extrusion shrinkage. Obsorved values as a function of calculated values using ar only.EFFECT OF BLACK ON CURE 143 CALCULATED EXTRUSION SHRINKAGE. % MULTIPLE CORRELATION COEFFICIENT = 0.949 STANDARD ERROR OF ESTIMATE + 147 a re ‘OBSERVED EXTRUSION SHRINKAGE, % Fio. 13.—Extrusion shrinkage. Observed values as a function of calculated values using ay and ky. creasing surface acid concentration and can be used as a measure of the surface chemistry of carbon blacks. ‘The maximum increase in torque, AL, at a given filler loading (or a derived ap-value) is related to both carbon black structure and surface chemistry and its influence on the efficiency of the cure reaction. In CBS/SBR formulations the increase in crosslink density is proportional to the increase in total acid concentration, while in CBS/NR recipes the inverse relationship is observed. SUMMARY The cure behavior of SBR and NR compounds was examined using the Monsanto Rheometer. The three cure parameters—induction period (ta), rate of crosslinking reaction (kz) and maximum increase in torque (AL)—were derived from the Rheometer torque curves. The data so obtained were used to calculate Westlinning’s ar-values. It was shown that (1) k2 decreases with increasing total acid concentration at the carbon black surface and (2) the value of ae is related to the filler struc- ture and the crosslink density of the rubber matrix. It was also demonstrated that the crosslink density, as measured by AL, is influenced by the surface144 RUBBER CHEMISTRY AND TECHNOLOGY chemistry of carbon black. In SBR stocks the crosslink density increases with increasing total acid concentration, while in NR compounds the reverse is true, These findings were confirmed by examining the tensile properties of regular and oxidized HAF-LS black in SBR and NR compositions. Thus the effect of carbon black surface chemistry on crosslink density can be estimated, for a given recipe, from the value of ke. ‘An empirical relationship between the cure parameters (ae und k,) and filler structure (as measured by extrusion shrinkage) was derived and tested on a wide range of carbon blacks. This relation gives a much better correlation coefficient than the simple relation between extrusion shrinkage and ar alone. Thus by full use of the Rheometer data, the extrusion shrinkage or other struc- ture-related properties of carbon black filled stocks can be predicted. ACKNOWLEDGMENT The author wishes to express his sincere thanks to C. E. Magnuson and G. A. Kasten for their assistance in the experimental work. REFERENCES 18, Wolff and H. Westlinning, Rubber J. 150, 12, 24 (1968). 14. Y. Coran, Rosser Cuem. Tecunot. 37, 679, 689 (1964). 48, Wolff, Kaut. Gummi, Kunst. 23,7 (1970). + J. Vogt, Paper to DKG Meeting, Berlin 1968. “ASTM Method D-2705-T. L. Mullins, J. Appl. Polymer Sci. 2, 1 (1959). 7B. B. Boonstra and G. L. Taylor, Russer Cuem. Tecanot. 38, 943 (1965). 44, J, Brennan and T. E. Jermyn, J. Appl. Polymer Sei. 9, 2749 (1965). *L. Mulling and N. R. Tobin, J. Appl. Polymer Sci. 9, 2993 (1965). 1G. R. Cotten, B. B. Boonstra, D. Rivin, and F. R. Williams, Kaut Gummi, Kunat. 22, 477 (1989). 4M, Porter, Kaul. Gummi, Kunst, 22, 419 (1969). 4 W. D, Schaeffer, W. R. Smith, and M. H. Polley, Ind. Eng. Chem. 48, 1721 (1953). 4 W. D. Schaeffer, W. R. Smith, and M. H. Polley, Ind. Eng. Chem. 48, 1721 (1953). ‘3 B. Saville and A. A. Wataon, Rosser Cue. Tecanot. 40, 100 (1967). “ W. N. Unger and H. E. Toussaint, private communication.