FILLER-ELASTOMER INTERACTIONS. PART VII. STUDY ON BOUND RUBBER SiecrRieD WoLFr, MENG-J1a0 WANG, AND Ewe-HonG TAN Denussa AG, INoRGANIC CHEMICAL PRODUCTS DIVISION, APPLIED RESEARCH AND ‘PECHNICAL SERVICE FOR FILLER AND TRURHER CHEMICALS, KALSCHEURENER StRASSE 11, W-5030 HORTH, FEDERAL REPUBLIC OF GERMANY ABSTRACT SBR compounds were filled with 17 carbon blacks covering the whole range of rubber grades and tested for bound- rubber content, It was found that the bound-rubber content of a polymer at high loadings is higher for large surface- area carbon blacks. On the other hand, the bound-rubber content per unit of interfacial area in the compound (specific ‘bound:-rubber content) decreases with increasing specific surface area and filler loading. This observation was interpreted in terms of interaggregate multiple molecular adsorption, filer agglomeration, and change of molecular weight of rubber during mixing. When the comparison was carried out at eritical loading of a coherent mass, the specific bound- rubber content was found to be higher for the high-surface-area products which are characterized by high surface ‘energies. The critical loading of coherent mass of bound rubber also shows a strong surface-area dependence, indicating {that large particle carbon blacks give high critical loadings. The measurements of bound rubber at high temperatures for earbon-black-flled compounds and in an ammonia atmosphere for silica-illed compounds suggest that bound rubber is caused essentially by physical adsorption INTRODUCTION Bound rubber, sometimes termed filler gel, is a phenomenon which was described as early as 1925! and since then has been widely studied. It has long been recognized as an important factor in the mechanism of rubber reinforcement, and it is often considered to be a measure of surface activity. Several reviews? deal with the mechanism and factors affecting the formation of bound rubber and its influence on rubber properties. A comprehensive survey of recent investigations on bound rubber was given by Dannenberg.” Generally speaking, bound rubber is a parameter which is simple to measure, but the factors which influence the test results are very complicated. It was reported that the filler- polymer interaction leading to the formation of bound rubber involves physical adsorption, chemisorption, and mechanical interaction. As far as the filler is concerned, bound rubber is not only affected by the physicochemical characteristics of the filler surface, but also by filler morphology. With regard to the polymer, both the chemical structure of the molecules (saturated vs. nonsaturated, polar vs. nonpolar) and their microstructure (configuration, molecular weight, and molecular-weight distribution) influence the level of bound-rubber content. Moreover, bound rubber also shows a dependence on the processing conditions of the compound, such as mixing and storage times. Furthermore, there are factors during the measurement itself which determine the bound-rubber content, e.g., the nature of the solvent, and the temperature of extraction. Results reported in publications are, therefore, sometimes contradictory, depending on the compound composition and preparation, as well as on the test procedures. Bound rubber is thus a phenomenon which, although well known and the subject of numerous publications, is still a matter of controversy. ‘The objectives of this study are: 1. To investigate the effects of carbon-black morphology and loading on bound rubber and to establish the relationship between bound rubber and filler surface energy, using a wide range of commercially available carbon blacks. 2. To investigate the nature of polymer-filler interaction in bound-rubber formation, using measurements at high temperature as well as in an ammonia atmosphere. EXPERIMENTAL Seventeen carbon blacks ranging from N110 to N762 were used in this study. Relevant analytical data of these carbon blacks are listed in Table I. A precipitated silica, P1 (Ultrasil VN2, Degussa AG), with a nitrogen surface area of 134 m?/g was also included for comparison. 163164 RUBBER CHEMISTRY AND TECHNOLOGY Vou. 66 Taste 1 ANALYTICAL PROPERTIES. Surface area, Surface area, DBPA, —_ DBPA (24M4), Carbon black Nz, m?/g__ CTAB, m'/g__mL/100g___mL/100g N1LO 139 123 44 106 NI21 124 116 132 107 220 2 106 us 98 N234 124 15 125 101 N24 115 106 124 99 N326n 78.1 79.2 71 65. NB26t 67.1 68.7 79 67 N330 80.0 82.1 103 90 N339 88.6 87.1 121 97 N37 813 380.9 124 96.5 N375 99.1 92.9 44 95 N539 415 42.3 113 80.5 BBO 39.9 40.7 122 84.5 N660 35.3 378 92 75 N683 39.7 40.6 136 90 N762 30.2 B21 68.5 57 N765 33.3 34.9 121 76.5 To eliminate the disturbing influence of gel in the raw polymer, the compounds were prepared using gel-free SBR (SBR 1500, Mooney viscosity at 100°C: 50, supplier: Hills AG, Germany). NR (SMR 5) was used only for the high-temperature measurement of bound rubber. Carbon-black loadings ranged from 0 to 50 phr (at intervals of 5 phr) for the reinforcing carbon blacks and from 0 to 80 phr for the semireinforcing blacks Compounding was carried out in an internal mixer (Werner & Pfleiderer GK 4 N) using a single-stage mixing procedure and a batch size with a fill factor of 0.67. Polymer, carbon black, and other ingredients (without curatives) were mixed for 4.5 min and dumped at a temperature of 145-155°C. Care was taken to ensure good dispersion of the filler in the elastomers. The solvent used for the bound-rubber determination was toluene. All compounds were stored at room temperature for one week before extraction. For the determination, 0.2 g of compound was cut into small pieces of approximately I mm? and placed into a stainless: steel, wire mesh cage of known weight. The cage was then immersed in 25 mL of solvent for seven days at room temperature, and the solvent was renewed after three days. After extraction, the rubber and the cage were dried for one day in air at room temperature and then for 24 h in an oven at 105°C. The percent bound rubber of the polymer, Ry, was then calculated according to the following equation: Weg — Wmy/(my + my)) W[my/(my + mp)] Rn x 100, wo where W, is the weight of carbon black and gel, m, the weight of the filler in the compound, ‘m, the weight of the polymer in the compound, and W the weight of the specimen. For the investigation of the influence of temperature on bound rubber, the extraction temperature was varied between room temperature and 100°C. Xylene was used as a solvent to facilitate this measurement. In this case, the cage with 0.5 g compound was placed in a double-neck flask assembled with a condenser and jet for nitrogen protection. The quantity of solvent used was about 75 mL. When no coherent mass remained in the cage, the suspension was collected and separated with a centrifuge at 12 000-20 000 rpm at room temperature It was then washed with solvent at room temperature and centrifuged. This process wasBOUND RUBBER 165 repeated five times. The filler with possibly remaining polymer was finally collected and dried, first in air and then in a vacuum at 105°C until a constant weight was obtained. After drying, the samples were analyzed by TGA to determine the respective amounts of polymer and filler. For the measurements in an ammonia atmosphere, the cage with the sample was placed in a beaker containing the solvent under ammonia atmosphere for extraction at room tem- perature, RESULTS AND DISCUSSION BOUND RUBBER AT ELEVATED TEMPERATURES, In order to understand the nature of the interaction between polymer and filler in the formation of bound rubber, measurements were carried out in xylene at temperatures ranging from room temperature to 100°C. In the case of natural rubber with N330, no coherent mass could be obtained at temper- atures exceeding 80°C. Bound rubber could not therefore be determined by conventional test procedures. The results can be interpreted as follows: 1. Bound-rubber formation is a purely physical phenomenon. If it were a chemical process, bound rubber would not decrease at 80°C. 2, Oxidation, causing molecular-chain breakdown, could be a factor leading to the decrease in bound-rubber content. To clarify the effect of temperature on bound rubber, further tests were carried out using SBR and 50 phr N330. SBR was chosen because it is gel-free and is relatively resistant against oxidation. To further limit the oxidation process, the experiment was carried out under a nitrogen atmosphere, and an antioxidant was added to the solvent. Figure 1 shows the results of this test. Below 70°C, only a slight reduction in bound rubber with increases in temperature is observed. Above 80°C, as with natural rubber, no coherent mass is obtained, causing a dramatic decrease in bound-rubber content. 40 35 SBR - N330 CARBON BLACK 30 25 20 15 Bound rubber, % 20 40 60 80 100 120 140 Temperature, °C Fic. 1.—Round rubber as a function of the extraction temperature for N330; +» polymer content meas TGA.166 RUBBER CHEMISTRY AND TECHNOLOGY Vou. 66 To determine whether any polymer was present on the carbon-black surface in the non- coherent mass, the solvent containing the carbon-black dispersion was collected and cen- trifuged at room temperature. The analysis for polymer content remaining on the carbon black was conducted using TGA. The results are marked in Figure 1 by the plus signs. As can be seen, even in the noncoherent mass, some polymer still remains on the carbon black surface. The amount of polymer decreases rapidly, however, with temperature. Since oxi- dation has been minimized, the residual bound-rubber content at elevated temperatures can either be due to chemisorption or a readsorption of polymer on the carbon black during the separation and washing process conducted at room temperature. Kraus and Dugone,' in their study of carbon-black adsorption in an SBR solution, found that the adsorption/de- sorption process is characterized by considerable hysteresis. It can therefore be concluded that the residual polymer determined by TGA cannot be due to chemisorption alone. On the basis of the above observations, it can be postulated that bound-rubber formation of conventional carbon blacks with polymers, at least with natural rubber and SBR, is mainly if not entirely a physical process. This is in agreement with studies conducted by Ban and Hess et al." who found that the greatest part of the carbon-black surface (in an HAF/SBR system) was free of polymer after extraction and concluded that carbon-black-polymer interaction was essentially physical in nature. MEASUREMENT OF BOUND RUBBER WITH AMMONIA TREATMENT To confirm that polymer-filler interaction leading to the formation of bound rubber is essentially caused by physical adsorption, bound rubber determinations were carried out at room temperature in an ammonia atmosphere using silica/SBR and HAF/SBR compounds. The results are listed in Table II. In the case of silicas, bound rubber is reduced from 20.5 to 3%. This indicates that, for silica, bound rubber is mainly caused by physical adsorption, since ammonia treatment is known to cleave physical linkages between silica and polymer.® In the case of carbon blacks, the picture is quite different. The bound-rubber content is only slightly affected by ammonia treatment. One possible interpretation of the above results could be that the stronger interaction between carbon black and polymer cannot be weakened by ammonia, whereas polymer-silica interaction is much weaker than the interaction between silica and ammonia. This is in line with observations made in swelling measurements of carbon black and silica vulcanizates"* in which swelling increased tremendously for the silica compounds after ammonia treatment, but had little effect on carbon-black vuleanizates. CRITICAL LOADING OF COHERENT GEL. In this investigation, it was found that for some carbon blacks, especially those with low surface areas, a coherent gel cannot be obtained below a certain level of loading. This is Tante I EFFECT OF AMMONIA TREATMENT OX BOUND RUBBER OF Fie SBR ComrounDs, SOLVENT: TOLUENE Filler Treatment __Bound rubber, % Carbon black N330 = 22.4 + 0.2 Carbon black N30. ammonia 20.8 + 0.3 Silica PL = 20.5 + 0.2 Silica PL ammonia 3.0 + 0.4" ‘*Noncoherent mass, data measured with TGA (see text).BOUND RUBBER 167 obviously due to the inability of the bound rubber to develop a network capable of holding carbon black and rubber together. The lowest possible filler loading at which a coherent mass can be formed and where no carbon black is dispersed in the solvent can be defined as the critical coherent loading."* This critical level of loading can easily be derived experi- mentally from a plot of bound rubber vs. loading as shown in Figure 2. As illustrated in Figure 3, the critical coherent loading, Cou, decreases with increases in surface area. The reasons for the high critical loading of low-surface-area carbon blacks are probably the greater distance between particles as discussed later and the low surface energy, neither of which favor the formation of a three-dimensional gel network. ‘THE EFFECT OF FILLER MORPHOLOGY ON BOUND RUBBER Bound rubber is shown in Figure 4 as a function of carbon-black surface area at 50 phr loading. Total bound rubber content increases with increasing carbon-black-surface area. ‘This seems to be obvious since carbon blacks with larger surface areas have a greater in- terfacial area with the polymer per unit volume of compound at the same loading. This phenomenon has been known for a long time®*"®"” and has recently been reconfirmed by Dannenberg’ in a study using different types of rubber. ‘The carbon blacks in Figure 4 differ not only in surface area, but also with regard to structure, which covers the full range of rubber-grade furnace blacks. It can be observed that the carbon blacks with high structure, N121, N234, N242, N375, N339, N539, N550, N683, and N765 show higher values than their normal and low-structure counterparts such as N10, N220, N330, N326, N66O, and N762. This suggests that the carbon-black structure, next to surface area, is also an important parameter affecting bound rubber. For carbon blacks with similar surface areas, high-structure carbon blacks generally have a higher bound-rubber content. This confirms the observations made in the past." Several explanations were proposed in this regard: 1, The probability of multiple molecular-segment adsorption is greater for high-structure carbon blacks.” 2, Low-structure carbon blacks have a more ordered graphite layer structure leading to lower surface activity." ‘SBR-N765. Solvent: toluene Bound rubber, % 0 20 40 60 80 100 Loading, phr Fig, 2.—Determination of the critical coherent loading, Cow168 RUBBER CHEMISTRY AND TECHNOLOGY Vou. 66 SBR-carbon blacks. Solvent: toluene In Cea, phr 20 40 60 80 100 120 140 CTAB, m/g Fro, 3.—Critieal coherent loading as a function of CTAB surface area for various carbon blacks in SBR. Carbon black 50 phr. Solvent: toluene Bound rubber, % 0 20 40 60 80 100 120 140 160 CTAB, m?/g Fig, 4.—Bound rubber as a function of CTAB surface area for various carbon blacks at 50 phr loading in SBR.BOUND RUBBER 169 3. High-structure carbon blacks are more easily broken down during mixing, thus creating new active surfaces which are considered to be “facile new free radical sources” " for poly- mer-filler bonding,’ Multiple molecular-segment adsorption seems to be supported by an electron-microscope investigation of bound rubber. Ban and coworkers,"' in their study of EM micrographs of microtome samples in which the sol was extracted by benzene in a vapor extractor, found that rubber remained in the concave regions after extraction and that it was nearly totally absent in the convex regions of the surface. If the high bound-rubber values of high-structure carbon blacks are related to multiple molecular-segment adsorption, this would lead to lower interface effectiveness and therefore less bound rubber per unit surface. This cannot be confirmed by the investigation of bound rubber per unit surface of carbon blacks with different structures, as will be discussed later. ‘The rubber in the concave region could be due to the retraction of the polymer during sample Preparation. It is difficult to imagine that the rubber molecules are not spread over the whole carbon black surface in the swollen rubber and that these molecules should all be concentrated in the internal voids of the carbon blacks. It seems reasonable to explain the low surface activity of low-structure carbon blacks by a more ordered graphite structure, but on the other hand, measurements of surface energy have shown that neither the dispersive nor the specific components correlate with structure.” It is therefore highly probable that the breakdown of the high-structure carbon blacks may be largely responsible for their higher bound-rubber content. Several authors’! presented evidence showing that the primary s blacks undergoes a significant breakdown during mixing. Ban and Hes: in their EM inves- tigation of carbon black recovered by pyrolysis of the vuleanizate and the carbon gel, showed that the breakdown of the aggregates was significant and that this phenomenon was even more pronounced in the case of high-structure carbon blacks. It is understandable that the structure breakdown of carbon black could have two con- sequences: 1. An increase in the filler-polymer interface leading to higher bound rubber content, as mentioned earlier. 2. Greater surface activity of the freshly built surfaces and, hence, greater adsorption ability. ‘There is considerable evidence to support the assumption of high surface activity of the fresh surfaces. Serizawa et al. recently investigated the carbon gel of natural rubber by pulse NMR with the spin-spin relaxation time, t2, and found that the surface activity was reduced after introduction of oxygen groups and that the mobility of the molecular segments in the loosely- and tightly-bonded rubber phase increased. This means that the surfaces freshly formed during mixing have a greater ability to adsorb rubber molecules. ‘SPECIFIC SURFACE ACTIVITY OF CARBON BLACKS ‘The total bound-rubber content is dependent not only on the filler surface activity, but also on the interfacial area between filler and polymer in the compound. With regard to the surface activity of the filler, meaningful information can only be obtained by normalizing the bound rubber per unit filler surface. Figure 5 shows a plot of bound rubber per 100 m? s a function of carbon-black surface area at 50 phr loading. Although the experimental points are slightly scattered, it is apparent that the surface activity, expressed as bound rubber per unit surface, decreases with increasing surface area of the carbon blacks. The bound rubber per unit interface of semireinforcing carbon blacks is nearly twice as high as. that of reinforcing types. This is in good agreement with observations made by Dannenberg.” O'Brien et al!” arrived at similar conclusions. Dannenberg attributed this phenomenon to the easier accessibility of large aggregates for the adsorption of molecules. He believed that low-surface area carbon blacks possess a higher surface activity because of the lower temperature of carbon-black formation in the170 RUBBER CHEMISTRY AND TECHNOLOGY Vou. 66 Carbon black 50 phr. Solvent: toluene No39 Sena7s eNi21 Bound rubber, g/100m? O 20 40 60 80 100 120 140 160 CTAB, m2/g Fic, 5.—Specific bound rubber as a function of CTAB surface area {or various carbon blacks at 50 phr loading in SBR. furnace process. Furthermore, he pointed out that high structure, and hence large particles, are more easily broken down during mixing, thus exposing new active surfaces. As mentioned above, the breakdown of aggregate structure could explain the high bound-rubber content of high-structured carbon blacks at equal surface area. It is, however, difficult to explain such great differences between the different grades. But the high surface activity obtained for low-surface-area carbon blacks, derived from bound rubber, contradicts the results from surface-energy measurements. The results of inverse gas chromatography at infinite dilution’? show that the dispersive component of surface energy, yz, of low-surface-area carbon blacks is much lower than that of carbon blacks with high surface areas. In addition, the investi- gation of the adsorption-energy distribution as reported in Part VI of this series shows that the concentration of low-energy sites may not vary significantly between the carbon blacks, but that the number of high-energy sites is much higher for small-particle carbon blacks. ‘The easier accessibility of large-particle carbon blacks to adsorb rubber molecules could explain the differences observed in Figure 5, but this explanation does not hold true in the light of the considerable dependence of surface activity on filler loading. Figure 6 illustrates the dependence of bound rubber per unit surface area on CTAB surface area at different loadings. The basic trend is similar for all loadings, but it can be observed that the decrease in bound rubber per unit surface with increasing surface area is more pronounced at higher degrees of filler loading. Therefore, if bound rubber per unit surface is taken as a measure of surface activity, then its high load dependency would be very difficult to understand. One possible interpretation for the lower bound-rubber content per unit surface of large- surface-area blacks could be due to the change of the molecular weight of rubber. It is generally believed that molecular weight of rubber may decrease during mixing resulting from the scission of rubber chains at mechanical action, especially at high temperature. ThisBOUND RUBBER 171 Bound rubber, g/100m? SBR - CARBON BLACKS 0 20 40 60 80 100 120 140 160 CTAB, mig Fic. 6.—Specific bound rubber as a function of CTAB surface area for various carbon blacks and loadings. effect could be enhanced by the incorporation of carbon black. Another reason may be mul- tiple-segment adsorption which leads to a reduced effectiveness of the filler surface to form bound rubber. It is possible to imagine that, once a segment is attached, the whole molecule becomes part of the bound rubber. In the case of multiple-segment adsorption, two or more active sites are occupied by the same molecule without increasing the bound rubber. Multiple- segment adsorption can also take place between neighboring aggregates (interaggregate mul- tiple-segment adsorption), as shown schematically in Figure 7. In addition, it has repeatedly been demonstrated that the carbon-black aggregates interact, which results in the formation of a secondary network (agglomeration). It is believed a - Single attachment b- Multiple attachment ¢-Inter-particle attachment Fic, 7.—Schematie diagram of the concept of multiple segmental adsorption,172 RUBBER CHEMISTRY AND TECHNOLOGY Vou. 66 that in a system where filler-filler interaction is strong and filler-polymer interaction is weak, for example, silica in hydrocarbon systems, the secondary network is built via direct contacts (hydrogen bonding).”* In the case of systems with strong polymer-filler interaction, this may lead to an immobilized rubber shell on the filler surface.®”s" In such cases, the secondary structure is probably formed by a joint shell mechanism. Nevertheless, by which- ever mechanism the secondary structure is formed, the bound-rubber content per unit surface, calculated on the assumption that no contacts exist, would be underestimated. Moreover, multiple attachments and the formation of secondary structures are highly dependent on surface characteristics and on the distance between aggregates. With regard to the surface characteristics which influence the formation of a secondary network, Wang, Wolff, and Donnet” introduced a factor, S,, which indicates the ability of fillers to agglomerate in hydrocarbon rubbers. This factor is related to the specific interaction of polar molecules on the filler surface. A high value of S; reflects a greater ability of the filler to agglomerate. For most carbon blacks and most of the polar probes, however, S, is almost a constant. It is therefore understandable that the interaggregate distance in carbon- black-filled rubbers has a predominant influence on agglomeration. The distance between aggregates is also an important factor with regard to multiple-segment attachment, é.., the shorter the distance, the higher would be the number of interaggregate multiattachments. The distance between filler aggregates in a compound is dependent on the degree of loading and on aggregate size. Based on the occlusion of rubber and according to the concept of Medalia® postulating that each aggregate consists of uniform, randomly connected nodules, Wang, Wolff, and Tan® recently proposed the following equation to estimate the distance between aggregates, Ja: 8000 (yg: 9g-19 — 1814 2S (ke 8 1" where p is the density of the carbon black and k a constant dependent on the type of packing. For loose cubic packing, k is 0.806, and for face-centered cubic packing, i.¢., the most dense packing, k is 0.905; k is 0.85 for normal packing as in the present case. In this equation, 8 is an expansion factor which is the ratio between effective volume fraction of the carbon black, éay, and the actual volume fraction, . This factor can be calculated from Medalia's® or Kraus’ equations, respectively. In most cases, the equation derived by Wang, Wolff, and Tan, which is based on the value for crushed DBPA and the random packing of equivalent spheres, is better suited for this purpose: (2) p - det - 2.0181DBPA + 1 o 1.59 Equation (2) shows that 84, decreases with filler loading and surface area. As small- particle-size carbon blacks have comparatively large surface areas, the interaggregate dis- tance of such blacks at equal loading will be shorter. As discussed above, the bound-rubber content per unit surface of such blacks will, therefore, be underestimated. Equation (2) includes the effect of DBPA, i.e., the higher the structure, the smaller will be the distance. In comparison to CTAB, the effect of DBPA on 4,, is much smaller. If the distance between aggregates has an effect on bound rubber per unit surface, this, effect should be reduced as loading decreases. As can be seen in Figure 8 for a sample which formed a coherent mass, the bound rubber content per unit area shows a linear correlation with the logarithm of weight loading (phr). The value of bound rubber content per unit surface extrapolated to critical coherent loading, at which multiple attachments per unit surface can be assumed to be similar for all blacks, the filler aggregates can be assumed to be free from effects of agglomeration, and the difference in change of molecular weight of rubber for different compounds during mixing can be assumed to be similar, is the specific bound-rubber value for each carbon black. Figure 9 shows a plot of the extrapolated specific bound rubber against CTAB surface area of carbon blacks. It can be seen that, to a first approximation, the extrapolated specific (3)BOUND RUBBER 173 SBR - N220. Solvent: toluene Bound rubber, g/100m? ° 2 4 In (100xmt/mp) Fic. 8 Specific bound rubber as function of the logarithm of loading (phr) for N220. bound-rubber content increases with surface area. This is in agreement with results obtained from surface-energy measurements and their energy-distribution functions, showing higher surface energy for small-particle blacks. Figure 10 confirms the above assumption, illustrating that the specific bound-rubber content at critical coherent loading is, to a first approximation, directly proportional to the dispersive component of carbon-black surface energy, 7. 1.6 SBR-carbon blacks. Solvent: toluene 1.4 1.2 08 0.6 Specific bound rubber, g/100m? 04 0 20 40 60 80 100 120 140 160 CTAB, m?/g Flo, 9.——Extrapolated specifc bound rubber as a function of CTAB surface area for various carbon blacks,174 RUBBER CHEMISTRY AND TECHNOLOGY VoL. 66 1.8 E16 SBR-carbon blacks. Solvent: toluene Bee B 14 S B12 2 Eo4 5 3 3 2g 08 3 a Go 06 0.4 0 200 400 600 hy mui? Fic. 10.—Extrapolated specific bound rubber as a function of y¢ for various carbon blacks. APPLICATION OF FE PLISKIN-TOKITA EQUATION Based on the assumption that a layer of bound polymer is formed on the filler particle, Pliskin-Tokita® derived the following equation, Rp= AZ) +G, «@) where Rp is the volume fraction of bound rubber in the polymer, f the fraction of filler surface exposed to the polymer sol, G the fraction of gel in the gum, ¢ the thickness of the bound-rubber layer. For gel-free polymers such as SBR, where G = 0 and = 1, a plot of bound rubber against pS¢/(1 ~ ¢) should result in a straight line, the slope of which would represent the thickness of the bound-rubber layer. ‘The application of the above equation to a semireinforcing carbon black shows that, except at very low loadings where the concentration is too low for a coherent mass to be formed, excellent agreement with Equation (4) was found. This is also in agreement with results obtained by O'Brien et al.,"” who found similar results with GPF carbon blacks. The application of Equation (4) to all reinforcing blacks is, however, problematical. Figure 11 illustrates bound rubber as a function of pS#/(1 — 4) for N330, and no linear relationship is ‘observed. Since the slope of the line connecting the origin with any other point is equivalent to the thickness of the bound-rubber layer at any given loading, the thickness will decrease with increasing loading. This behavior is typical of all reinforcing carbon blacks. Obviously, one cannot conclude that surface activity decreases with increasing in loading. This phe- nomenon is due to the fact that, by the derivation of Equation (4), a uniform layer over the whole surface is assumed. Multiattachments of rubber molecules between aggregates and agglomerations were not taken into account. Similar observations were also made by O'Brien and coworkers.'” Using five carbon blacks ranging from SRF to ISAF at 50 phr loading, they found that the bound-rubber layer thickness calculated for HAF and ISAF was lower than for carbon blacks with lower surface areas.BOUND RUBBER 175, ‘SBR - N330. Solvent: toluene Bound rubber, % ° 20 40 60 80 100 $0 S/(1-9). ma/em* polymer Fis, L1.—Pliskin-Tokita plot for N330. They attributed this to the agglomeration of the aggregates which reduces the value of fin Equation (4). Contrary to Pliskin-Tokita who used three reinforcing carbon blacks at different loadings to obtain a straight line, the Pliskin-Tokita plot of seventeen carbon blacks with different surface areas and loadings does not give a linear relationship (Figure 12). The bound-rubber layer varies from 4 to 8 nm, suggesting that the linear relationship depends on the concen- tration and characteristics of the carbon black. Itshould be emphasized that bound rubber is indeed a valuable measure of surface activity. Nevertheless, when the bound rubber per unit interface or the thickness of the bound-rubber 40 Bound rubber, % 8 SBR Solvent: toluene 20 40 60 80 PPSI(1-P). me/em? polymer Fin, 12.—Piskin-Tokita plot for various carbon blacks at different loadings.176 RUBBER CHEMISTRY AND TECHNOLOGY Vou. 66 layer are used to characterize the surface, other factors such as agglomeration and inter- aggregate distance should be taken into consideration. CONCLUSIONS In a systematic study, encompassing seventeen commercially available carbon blacks, bound-rubber determinations were carried out at different filler loadings and under different test conditions. The following conclusions can be drawn from this investigatio 1. The temperature dependence of bound rubber and the decrease in bound rubber for silica/SBR compounds after ammonia treatment show that the polymer-filler interaction involved in the formation of bound rubber is essentially a physical phenomenon. 2, The critical coherent concentration below which no coherent mass is obtained increases with decreases in carbon-black surface area. 3. The total amount of bound rubber increases with loading and surface area of the carbon blacks. 4. The bound-rubber content per unit surface decreases with increases in surface area and, in the case of fine carbon blacks, also with increases in loading. It is postulated that the above effects are related to the change of the molecular weight of rubber during mixing, to multiattachment of molecules between aggregates, and to agglomeration. 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