Composites: Part A 36 (2005) 449460 www.elsevier.

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The effect of llerller and llerelastomer interaction on rubber reinforcement

J. Frohlich*, W. Niedermeier, H.-D. Luginsland
Advanced Fillers and Pigments Division, Applied Technology Advanced Fillers, Degussa AG, Harry-Kloepfer-strasse 1, Koeln 50997, Germany

Abstract The role of active llers like carbon black and silica has been studied in the rubber matrix for a better understanding of the rubber performance and the mechanism of reinforcement. In particular the inuence of basic properties of carbon blacks, such as specic surface area, structure and surface activity on the Payne-effect, was investigated with the Rubber-Process-Analyzer (RPA) which allows a testing of the strength of the ller network and the ller-polymer interaction in the green compound as well as in the vulcanizate in a wide range of shear amplitudes. A comparison between carbon black and the silica-silane system leads to further scientic ndings for the understanding of the dynamic behavior of lled rubber compounds. q 2004 Elsevier Ltd. All rights reserved.
Keywords: Carbon Black

1. Introduction Despite the fact that carbon black is not only the most widely used but also the oldest active ller in rubber compounds and that a huge amount of research work [1] has been carried out to characterize, describe and understand this kind of ller, the reinforcement effect in ller-loaded rubber is not satisfactorily explained. Since carbon black is an essential ingredient of most rubber formulations and has a considerable inuence on the performance of the nal product, it is important to know how rubber vulcanizates are affected by the nature of carbon black. The aim of this report is to give a deeper insight into the reinforcement mechanism of the carbon black ller system by analyzing the strain dependence of the complex modulus G* and the loss factor tan d. The Rubber-Process-Analyzer [2,3] (RPA, Alpha Technologies) allows a very reliable and detailed investigation of the dynamic behavior on a much easier and faster way than the common dynamic analysis of vulcanizates. The main focus of this work lies on the inuence of the nature of carbon black (loading, surface area, structure and surface activity) on the dynamic properties.
* Corresponding author. E-mail address: joachim.froehlich@degussa.com (J. Frohlich). 1359-835X/$ - see front matter q 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.compositesa.2004.10.004

2. Background Although the reinforcement of rubber by active llers is a well-recognized phenomenon the term reinforcement is not well dened. Briey it can be stated that reinforcement means the pronounced increase in tensile strength, tear resistance, abrasion resistance and modulus far beyond the values expected on the basis of the Einstein-Guth and Gold theory [4], taking into account the effects caused by colloidal spherical particles (hydrodynamic effect) and occlusion of rubber. The reinforcement of elastomers by llers has been studied in depth in numerous investigations [5] and it is generally accepted that this phenomenon is dependent, to a large extent, on polymer properties, ller properties and processing. Generally speaking, the primary ller factors inuencing elastomer reinforcement are: The primary particle size or specic surface area, which, together with loading, determines the effective contact area between the ller and polymer matrix. The structure or the degree of irregularity of the ller unit, which plays an essential role in the restrictive motion of elastomer chains under strain. The surface activity, which is the predominant factor with regard to llerller and llerpolymer interaction.

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fore increases the effective ller content leading also to a strain-independent contribution to the modulus. The llerpolymer interaction can be attributed to physical (van der Waals) as well as to chemical linkages or a mixture of both. In the case of the silicasilane system this interaction is formed by chemical linkages. (d) The stress softening at small amplitudes is attributed to the breakdown of the inter-aggregate association respectively to the breakdown of the ller network. This stress softening at small deformations, called Payne-effect [9,10], plays an important role in the understanding of reinforcement mechanism of lled rubber samples [11].

Fig. 1. Idealized form of a typical elastic modulus curve.

3. Carbon black characterization 3.1. Specic surface area

Most of the elastomeric components are deformed dynamically and specied dynamic properties are required. Therefore the effect of strain amplitude on the dynamic modulus was observed very intensively. The modulus of lled rubbers decreases with increasing applied dynamic strain up to intermediate amplitudes. A detailed study of the low frequency dynamic properties of lled natural rubber was carried out by Fletcher and Gent [6] and was later extended by Payne [7,8]. In cyclic strain tests the shear modulus can be simply expressed as a complex modulus G*: G*ZG 0 CiG 00 where G 0 is the in-phase modulus and G 00 the out-of-phase modulus. The phase angle d is given by: tan dZG 00 /G 0 . The addition of llers to rubber compounds has a strong impact on the static and dynamic behavior of rubber samples. Fig. 1 shows the typical behavior of the complex shear modulus of lled rubber samples versus dynamic shear deformation. Similar to the model of Payne, we see the strain-independent part of the modulus as a combination of the polymer network, the contribution from the hydrodynamic effect and the modulus resulting from the in-rubber structure. (a) The polymer network contribution depends on the crosslink density of the matrix and the nature of the polymer. (b) The hydrodynamic effectin this modelis nothing else than the effect of strain amplication, resulting from the fact that the ller is the rigid phase, which cannot be deformed. As a consequence, the intrinsic strain of the polymer matrix is higher than the external strain yielding a strain-independent contribution to the modulus. (c) The effect of the structure is attributed to the in-rubber structure, which can be understood as a combination of the structure of the ller in the in-rubber state (in-rubber DBP) and the extent of llerpolymer interaction. The in-rubber structure is the measure for the occluded rubber, which is shielded from deformation and there-

The primary particle size or specic surface area is characterized by different adsorption methods of specied molecules. The most widely used adsorption methods are based on [12]: (a) The iodine number, which reects a not true surface area, because it is affected by porosity, surface impurities and surface oxidation. (b) The cetyltrimethyl ammonium bromide (CTAB) method, which analyzes the so-called external surface area which corresponds to the accessible surface area of carbon black for an elastomer. (c) The BET nitrogen adsorption surface area, which provides the total surface area including porosity. (d) The Statistical Thickness Surface Area (STSA), which is an alternative technique for the determination of the external surface area. All these measures surface areas are affected in different ways by the nature of the carbon black surface and have not to correlate exactly with the actual occupied surface by an elastomer in a mixture. This should be kept in mind when physical properties are deduced from the surface area. 3.2. Structure The primary particles formed during the initial carbon black formation stage fuse together building up threedimensional branched clusters called aggregates. Highstructure blacks exhibit a high number of primary particles per aggregate, which is called a strong aggregation, lowstructure blacks show only a weak aggregation. These aggregates again may form loose agglomerates linked by van der Waals interactions. The empty space (void volume) between the aggregates and agglomerates, usually expressed as the volume of dibutylphthalate (DBP) absorbed by a given amount of carbon black, is described

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by the term structure of carbon black. It is assumed that the DBP absorption reects the total carbon black structure which comprises both aggregates and agglomerates, whereas the crushed DBP absorption test eliminates loose agglomerates and easily destroyable aggregates. DBP and CDBP absorption can be measured very precisely, but do not give any information about the shape of the aggregates. Furthermore the DBP value does not reect the actual structure of the carbon black inside a compound since the agglomerates change their shape during mixing. It is also not surprising that the CDBP value does not have to correlate automatically with the static dynamic behavior because the agglomerates are separated into aggregates by the shear forces during mixing and are not rstly compressed and then dispersed as simulated by the crushed DBP test. However the size as well as the shape of the aggregates, which are not characterized by DBP or CDBP absorption, are important primary carbon black properties and should be analyzed in detail. 3.3. Surface activity The third reinforcing parameter, surface activity, a poorly dened term, but widely used in the ller eld, can in a chemical sense be related to different chemical groups on the surface. Such are carboxyl, quinone, phenol and lactone groups. In a physical sense, variations in surface energy determine the capacity and energy of adsorption. The surface chemistry of carbon blacks has a signicant effect only on the vulcanization behavior of lled compounds. No direct correlation has been demonstrated between chemical groups on the carbon black surface and rubber related properties [1315]. In the case of carbon black the llerpolymer interaction is mainly of physical nature (physisorption). The surface activity can be inuenced by heat treatment. It is well-known that heat treatment of carbon blacks at temperatures ranging between 1500 and 2700 8C [15] profoundly changes the carbon black inuence on rubber compound properties. The result is a low level of bound rubber, a drastic reduction in high strain modulus, tensile strength and abrasion resistance. The explanation for this behavior is that during heat treatment the size of the nanocrystallites, building up the primary particles of carbon blacks, drastically increases and the arrangement of these
Table 1 Basic formulation Stage I E-SBR Carbon black Other chemicals: ZnO 3; stearic acid 2; wax 1 Stage II Batch stage I Stage III Batch stage II CBS Sulfur 100 60

Table 2 Basic mixing procedure Stage I 01 0 12 0 23 0 30 34.5 0 4.5 0 4.56 0 Stage II 0.2 0 25 0 Stage III 0.2 0 20 Intermix GK 1.5 N Polymers 1/2 carbon black, ZnO, stearic acid 1/2 carbon black, 6PPD, wax Sweep Mix Sweep Mix and dump Batch stage I Remill at 150 8C Batch stage II, accelerators, sulfur Dump and homogenize on an open mill

crystallites becomes more ordered. As a consequence the microstructure is totally changed and the number of highenergy sites, located at the edges of the crystallites, decreases drastically. This conrms the assumption that the surface activity of carbon blacks, as far as the capacity of the surface for adsorption is concerned, has its origin in the disordered arrangement of the crystallographic structure. Compared to the highly oriented pyrolytic graphite, the graphitic structure of graphitized carbon blacks still remains in a certain way imperfect [16]. 4. Experimental All investigations in the present study were performed with the rubber process analyzer (RPA); the method and the specic settings are described elsewhere [17]. All investigated rubber compounds are based on an emulsion SBR 1500 formulation according to Table 1. The mixing procedure is given in Table 2.

5. Results 5.1. Inuence of carbon black loading The inuence of the carbon black loading on the dynamic modulus of the green compound as well as of the vulcanizate can be seen in Fig. 2. The black N 115 was chosen as example, but in principle the behavior is similar for all grades of carbon black. The unlled rubber shows no indication of non-linearity in the green compound as well as in the vulcanizate. After adding the ller, the low strain modulus G0 rises more that the high strain modulus GN, resulting in a non-linear viscoelastic behavior, known as Payne-effect G0KGN. In both cases the overproportional increase of the Payneeffect with ller loading can be seen. This increase is caused by the formation of llerller interactions, which are formed with carbon black loading. This is due to the fact

1.5 1.5

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Fig. 2. Strain amplitude dependence of G* of N 115 at different loadings (a) green compound, (b) vulcanizate.

that the inter-aggregate distances become smaller with rising ller content, and therefore the probability for the formation of a ller network increases. The comparison of the G*-curves of the vulcanizate and of the green compound

for xed loading displays an increase of the Payne-effect G0KGN during vulcanization. The crosslinkage of the rubber matrix causes a parallel shift along the G*-axis, see Fig. 1. As a consequence, the carbon black aggregates must

Fig. 3. Strain amplitude dependence of tan d of N 115 at different loadings (a) green compound, (b) vulcanizate.

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Fig. 4. Strain amplitude dependence of G* (a) and tan d (b) of three grades with different surface area but similar structure.

reagglomerate respectively occulate during the vulcanization process, which is possible because of the low viscosity of the polymer matrix at high temperatures. The effect of occulation of llers in green compounds annealing them at intermediate and high temperatures is of the same nature and is well-known [18]. Fig. 3 gives the corresponding tan d-curves for the green compounds and the vulcanizates. At small and intermediate strains the hysteresis decreases with increasing ller content in the case of the green compound. The unlled sample exhibits the highest tan d level, which is due to the viscous nature of an unlled raw polymer. With increasing carbon black loading ller networking develops and stabilizes the viscous polymer uid yielding a diminished hysteresis behavior at small and intermediate strains. At high strains, when the ller network is broken down, the viscous polymer is no longer stabilized and the tan d rises drastically. The contribution of the breakdown of the llerller interactions to the hysteresis is not signicant in the green compound because of the already high level of tan d resulting from the raw polymer. The absolute values of tan d are considerably reduced in the vulcanizates due to the crosslinkage of the polymer matrix. The tan d-curve of the unlled sample indicates that there is essentially no hysteresis from the pure gum. Now it can clearly be seen that the hysteresis increases with carbon black loading. It can be stated that this hysteresis results from the breakdown of the increased ller network whose

disruption during straining dissipates energy. So the concept of ller networking yields a good interpretation of the Payne-effect both for carbon clack lled green compounds and vulcanizates, comprising the overproportional increase of the Payne-effect with ller loading and the increase by annealing. It should be noted that the existence of ller networking is not necessarily corresponding to the existence of a ller network which is percolated through the whole specimen. Fillerller contacts in local subnetworks are also denoted as ller networking and yield the Payne-effect. 5.2. Inuence of carbon black surface area Fig. 4 shows the RPA-curves of three carbon black grades with varied CTAB surface area, but similar structure (Table 3). First of all it can be recognized that the GN level at high strain is comparable for all grades. On the other hand the initial modulus G0 differs drastically from the variation
Table 3 Analytical characteristics of the blacks N 115, N 220 and N 339 CTAB (m2/g) N 115 N 220 N 339 128 111 92 DBP (ml/100 g) 113 113 121 CDBP (ml/100 g) 97 101 99

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Table 4 Analytical characteristics of blacks of the N 300 series CTAB (m2/g) N 326 N 330 N 347 N 375 81 82 86 95 DBP (ml/100 g) 71 102 124 113 CDBP (ml/100 g) 68 88 97 96

in surface area, the higher the surface area the higher the Payne-effect which corresponds to the extent of ller networking. The same tendency is displayed by the graph tan d versus strain. The inuence of the CTAB surface area on the formation of a ller network can be explained as follows: the primary particle size diameter decreases with increasing surface area. At xed levels of structure and carbon black loading, both the aggregate size and the interaggregate distance decrease with reduced primary particle diameter respectively increasing surface area [19]. The smaller the inter-aggregate distance the higher the probability for the formation of a ller network. Consequently, the extent of ller networking is more pronounced, when the surface area rises. 5.3. Inuence of carbon black structure In order to investigate the effect of the carbon black structure on the complex modulus two ASTM grades N 326

and N 330, which show strong deviations in DBP level, but almost identical surface areas (Table 4), were selected. In Fig. 5a, a comparison of the modulus curves of the blacks N 326 and N 330 demonstrates higher modulus values for the initial as well as for the nal strain deformation for the black with the higher structure. Strictly speaking the higher structure of the black N 300 imparts a parallel shift of the curve of the black N 326 to higher G* values. Two consequences can be stated: rst an increase in structure leads to an enhancement in high strain modulus; second, this increase is independent of the deformation and is also valid for small strain amplitudes. The parallel shift indicates that the Payne-effect G0KGN is not signicantly affected by structure. The expected increase of the Payne-effect by a higher structure might be compensated to some extent by a better microdispersion behavior. The macrodispersion for all samples is between 8 and 9 in the well-known Phillips dispersion rating. The inuence of structure alone on the modulus curve can be seen by changes of the high strain modulus, because it is not affected by surface area (see Fig. 4). The inuence of the surface area on the high strain modulus can be analyzed in more detail by adding the blacks N 347 and N 375 for comparison to Fig. 5a (Fig. 5b). Despite the fact that the surface area of N 375 is higher than for N 347 (Table 4) the G* level for the nal modulus is higher for N 347. The only explanation for this behavior is the higher structure of N 347. Studying the order of the blacks regarding the nal

Fig. 5. (a) Inuence of the structure on the dynamic modulus. (b) Inuence of four different blacks of the N 300 series on the dynamic modulus.

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Table 5 Analytical data of nanostructure (EB 171) and corresponding ASTM black CTAB (m2/g) N 234 EB 171 117 118 DBP (ml/100 g) 125 125 CDBP (ml/100 g) 102 103

Fig. 6. Complex modulus versus strain for graphitized (N 326 g, N 347 g) and untreated grades.

modulus it can be recognized that the order is in line with the DBP numberthe higher the structure the higher the nal modulus. As seen before, above 57% strain the carbon black network is destroyed to a certain extent, may be not in individual aggregates but in the form of unconnected subnetworks of carbon black, hindering the polymer chain movement upon straining. 5.4. Inuence of carbon black surface activity One of the objectives of this investigation was to determine the relative contribution of carbon black surface activity to the complex modulus curve. In order to judge the effect of surface activity two carbon blacks of different structure, but having comparable particle size and surface area, were selected for surface modication by high-temperature treatment (2700 8C) in a nitrogen atmosphere. Heat treatment is known to change surface properties without altering the particle size and structure to any important degree [20]. Thus, with the different structure levels chosen and the varying surface activity produced by heat treatment, the effects of these variables could be studied separately. Despite the fact of similar surface area and structure levels of graphitized and nongraphitized grades, the stressstrain behavior is distinctly different. At low strain amplitudes a stronger ller networking can be observed in the case of the graphitized blacks, whereas at high strain the complex modulus is signicantly lowered compared to the corresponding ASTM grade (Fig. 6). The deviations are so marked that any uctuation in DBP or CTAB number cannot cause these differences. As a consequence, these changes in complex modulus behavior can only be attributed to the lowering in surface activity for the graphitized carbon blacks. It can be argued that low surface activity results in a decreased interaction with the rubber phase, providing a reduction of the high strain modulus and therefore a reduction of the strain-independent part of G*. On the other hand,

llerller and llerpolymer interaction are competitive in a certain way. So it can be understood that for graphitized blacks, which exhibit a lower llerpolymer interaction, as seen before, ller networking should be more pronounced. This is conrmed by the higher Payneeffect for the compounds containing the graphitized grades. Up to now only a deactivation of the surface activity by heat treatment could be achieved and investigated. The novel nanostructure blacks, produced by a physical modication of the carbon black production process, are characterized by a high surface roughness and a large number of high-energy patches or sites equivalent to a high surface activity. The origin of the roughness found at the carbon black surface is explained by a reduced lateral extension of the nanocrystallites linked with a high degree of geometrical disarrangement. These crystallites build up the primary particles [2124]. The active sites of carbon black particles are attributed to the edges of the graphitic layers respectively crystallites [15]. Both facts, the reduced size of the crystallites, leading to a larger number of crystallites to form the same particle diameter, as well as the high degree of disarrangement, yield a large number of edges respectively high-energy sites. This conclusion is valid in both directions. It is wellknown that under heat treatment a growth of the crystallographic dimension (LA and LC) of the carbon black takes place at constant primary particle sizes. As consequence in particular the high-energy sites are reduced. These sites play a very important role in elastomer reinforcement [25]. The surface activity of the nanostructure blacks therefore should be higher compared to conventional ASTM grades. In order to investigate only variations in surface activity the ASTM black N 234, graphitized and non-graphitized, and the nanostructure black EB 171, with almost the same surface area respectively primary particle diameter and structure (Table 5), were chosen. In Fig. 7 the modulus curves of these three blacks show the expected trends regarding the differences in surface activity. The high surface activity of the nano-structure black results in high interaction with the rubber phase, preventing carbon black network formation and reducing the low strain modulus. The differences in high strain modulus are not so considerable for EB 171 compared to N 234. Nevertheless the trend of high strain modulus enhancement with increasing surface activity of vulcanizates containing an nanostructure black can clearly be seen.

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Fig. 7. Complex modulus (a) and tan d (b) versus strain as a function of surface activity.

As expected the tan d curve versus strain gives for all deformation distinctly lower values for the nanostructure black regarding the lower ller network, as a consequence of the strong mechanical/physicochemical interaction with the polymer resulting from the high surface activity. 5.5. Payne-effect of silica and silicasilane system It is well-known that silica as a ller itself shows a very strong ller networking due to poor compatibility to hydrocarbon rubber, its polar character and the ability to form hydrogen bonds [26]. In order to study this strong network two silicas with different surface areas (Table 6) were investigated in a solution SBR/BR formulation (Table 7) and compared to the carbon black N 234. The following explanations based on the so far obtained ndings for carbon black can be also applied to silica. As can be seen in Fig. 8, the llerller interaction of Ultrasil
Table 6 Analytical data of the silicas Ultrasil VN 2 GR, Ultrasil 7000 GR and the carbon black N 234 CTAB (m2/g) Ultrasil VN 2 GR Ultrasil 7000 GR N 234 125 160 125 DBP (ml/100 g) z185 z235 119

7000 GR with the high surface area of 160 m2/g (CTAB) is signicantly higher than the one of Ultrasil VN 2 GR (Table 7). Based on the G*-curve the following can be observed: The silica network starts to break down at higher strain amplitudes due to a stronger ller network formed by hydrogen bonds compared to carbon black. This breakdown takes place over a much wider range of amplitudes. The tan d versus strain curves reect the same tendency. In the case of the carbon black the maximum energy dissipation, due to the breakdown of the ller

Table 7 Solution SBR/BR formulation Stage I S-SBR Styrene 25% Vinyl 50% Arom.oil 37.5 pbw cis-1,4O96% 96

BR 30 Filler 80 Silane Only for silica 6.4 Other chemicals: ZnO 3; stearic acid 2; arom. oil 10; 6PPD 1.5; wax 1 Stage II Batch stage I Stage III Batch stage II DPG 2 CBS 1.5 Sulfur 1.5

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Fig. 8. Comparison of Ultrasil 7000 GR, Ultrasil VN 2 GR and N 234 regarding complex modulus and tan d.

Fig. 9. Shear modulus G* and tan d of vulcanizates in S-SBR/Br formulation of Ultrasil 7000 GR, Ultrasil 7000 GRCPTES and Uitrasil 7000 GRCSi 69.

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bounded rubber (in-rubber structure) given by chemical linkages between the silica surface and the rubber matrix via Si 69 and in the silica structure [28]. Thus it can be stated that an enhanced high strain modulus indicates a better llerpolymer interaction, this is also valid for carbon black. The effect of the lower ller networking can also be seen in the lowered tan d curve of Fig. 9.

6. Discussion 6.1. In-rubber structure As mentioned above in-rubber structure was interpreted as a combination of the effects caused by the real carbon black structure in the in-rubber state and the llerpolymer interaction. Medalia has proposed [29] that in a carbon blackrubber system the rubber which lls the void space within each aggregate is occluded and shielded from deformation and thus acts as part of the ller rather than as part of the deformable matrix. Due to this phenomenon, the effective volume of the ller is increased considerably and should of course enhance the high strain modulus signicantly. As can be seen for the graphitized black the modulus level of the vulcanizate at high strain is lowered compared to the non-graphitized one (Fig. 6). Due to the fact that the DBP number of the graphitized and non-graphitized blacks is on the same level, it can be stated that the structure in the in-rubber state is nearly ineffective, if the surface activity of the ller is low. On the other hand, without enough structure in the in-rubber state, the surface activity is also relatively ineffective (see Fig. 5, comparison of N 326 and N 330). Hence, it can be concluded, in-rubber structure is a measure for the occluded rubberrubber, which is unable to participate fully in the macrodeformation. The nature of surface activity in this context can be attributed to different featureschemical-type (silica silane), physical-type (carbon black) bondings or both.

Fig. 10. Proposed model for the llerller contacts, specic surface area high (1) and low (2), equal loading.

network, is reached at 57% strain, whereas even at 42% strain the maximum is not reached in the case of the silicas. The breakdown of the inter-aggregate bonding of the silica over a broad range of strain amplitudes indicates that the silicasilica interaction differs strongly from the van der Waals bonding of carbon black aggregates [27]. The hydrophobation of the silica surface by a monofunctional alkylsilane (PTES) makes the silica more compatible with the rubber matrix reducing the ller networking respectively agglomeration. This can be seen on the drastically reduced low strain modulus (Fig. 9). By adding a bifunctional silane TESPT (Si 69) instead of PTES not only an additional hydrophobation but also a chemical bonding of ller-to-rubber takes place. This is indicated by the once again lowered G* level at low strain and a higher G* level at high strain for Si 69 instead of PTES. The higher G* value at high strain can clearly be attributed to the

Fig. 11. Dynamic modulus G* and tan d vs. temperature in E-SBR (0.1% dynamic strain, 10 Hz, Gabo Explexor).

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As a consequence, the term in-rubber structure explains immediately the term of reinforcement, dened as modulus 300% divided by modulus 100% in a stressstrain measurement. Reinforcement is a measure for the strength of a ller to keep its in-rubber structure respectively to restrain the occluded rubber at increasing deformation. 6.2. Fillerller/llerpolymer interaction Silica alone is building up a strong ller network and shows a low interaction with the polymer. But if a bifunctional silane is used chemical linkages between the silica surface and the polymer are formed. Through the hydrophobation the llerller interaction is lowered. The bondings are of chemical nature, and therefore polymer segments cannot undergo surface displacements by molecular slippages. In the case of carbon black linkages between the surface and polymer chains are formed only by physical adsorption. In the past as well as in the present molecular slippages along the carbon black surface as well as adsorption and desorption mechanisms are still under discussion. Up to now, it appears almost impossible to clarify exactly the molecular mechanism of the llerller contacts. All experimental results known, those reported in this paper and results from investigations of the dynamic modulus as a function of temperature might be explained both by direct ller to ller contacts and llerller contacts which are separated by a very thin polymer layer with a thickness in the nanometer range. The existence of such an elastomeric layer between the particles could at least be conrmed by dielectrical investigations done by Goritz and Lanzl [30]. Therefore the authors prefer the idea of a thin polymer layer between the ller particles where the mobility of the molecular polymer chains is restricted to some extent due to llerpolymer interaction, depending on the type of the polymer and the ller to ller distance which is mainly controlled by the specic surface area and the ller loading (Fig. 10). In this case, the amount of overlapping areas containing polymer with lower mobility controls the hardness of the contacts and as a consequence the dynamic modulus and the hysteresis during breaking off the contacts under deformation. From a steady decrease of the chain mobility near the boundary of the ller surface one might expect a glass transition, which has an onset at elevated temperatures. This should especially be valid if the glass transition is measured under dynamic conditions at very low strains where the ller networking is fully active. Fig. 11 shows the dynamic modulus G* and tan d in dependence of the temperature and compares an unlled ESBR compound and a compound lled with 50 phr N 234 (0.1% dynamic strain, 10 Hz, Gabo Eplexor). As expected, an earlier onset of the glass transition of the carbon black lled sample can be observed in G*, whereas the position of

the tan d maximum is not affected. But is has to be mentioned that the measured effect is rather small.

7. Conclusion The present study was undertaken to give a more detailed analysis of the inuence of carbon black morphological parameters (surface area, structure and surface activity) on viscoelastic properties of lled rubber compounds. Using the Rubber-Process-Analyzer the phenomenon, reinforcereinforcement of active llers can be studied with high accuracy and repeatability. Two essential parameters of lled rubber are investigated with this apparatus. For the following conclusions two prerequisites have to be fullled: the crosslink density and the ller loading have to be constant. 7.1. High strain modulus (O30%) The complex modulus at high strain indicates the real inrubber structure of llers. The high strain modulus of carbon black lled compounds is enhanced only if both, the ller structure in the in-rubber state and the surface activity of the ller are high, which means that the in-rubber structure is high as well. Consequently, the in-rubber structure is composed of two parameters, the actual ller structure in the in-rubber state and the surface activity of the ller. The strong enhancement of the high strain modulus by incorporating carbon black into rubber must be attributed to the in-rubber structure, which is a direct measure for the occluded rubberrubber, which is shielded from the deformation of the matrix leading to an increase in effective ller volume. Surface activity in this context can be attributed to chemical-type, physical-type bondings or both. 7.2. Low strain modulus (/5%) The complex modulus at low strain, exactly G0KGN, indicates the llerller network. The higher the ller loading the stronger the ller networking is marked. Increasing surface area respectively decreasing primary particle size provide also a higher ller networking. Both ndings can be explained by the fact that the inter-aggregate distance becomes smaller with increasing surface area as well as loading and thus the probability of forming a network rises. Filler networking respectively the Payne-effect G0KGN is decisively responsible for the hysteresis level at amplitudes up to 10% strain. Therefore ller networking plays a major role in the dynamic properties of a tire, namely the rolling resistance, as well as in the electrical resistance. On the other hand, a higher surface activity leads to a decrease in ller networking due to a better llerpolymer interaction. It can be stated, if

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the afnity of the ller surface to the polymer is increased respectively decreased, a reduced respectively enhanced ller networking is the consequence. Therefore llerller and llerpolymer interaction are two competitive processes.

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