Influence of Carbon Black on Crosslink Density of Natural Rubber

Vulcanization and reinforcement are two important factors contributing to the properties of vulcanized rubber. In order to investigate the influence of carbon black (CB) on chemical crosslinking, three groups of samples with different crosslink densities were prepared. In each group with the same crosslink density, different amounts of CB were introduced. Data fitting showed that delta torque (ΔM = M _H–M _L, the difference between the highest and lowest torques during curing) in the cure curves of each group had a good linear relationship with CB load and extrapolation of the fitting lines almost intercepted the x coordinate at the same value, which indicated that CB had no influence on the chemical crosslinking of the rubber. To verify the above result, a series of nonfilled natural rubber (NR) vulcanizates with different crosslink densities were studied using equilibrium swelling and the swelling ratios were compared with those of corresponding CB filled rubbers with the same sulfur and accelerator amount. The results of both the equilibrium swelling and NMR relaxation parameter measurements showed that CB filled vulcanizates had higher apparent crosslink densities than those of unfilled ones due to the strong interaction between rubber molecules and the surface of the CB particles. The swelling ratios of filled rubbers had a parallel relationship with those of the unfilled ones which indicated that CB had little influence on chemical crosslink density introduced by chemical vulcanization.     

Mechanical and electrical properties of radiation-vulcanized natural rubber latex with waste eggshell powder as bio-fillers

ABSTRACT

This work investigated the mechanical, physical, morphological, and electrical (volume) resistivity properties of radiation-vulcanized natural rubber latex (RVNRL) with additions of waste eggshell (WES) powder, which contained primarily CaCO₃ (calcite). The results showed that increasing gamma irradiation doses from 0 to 30?kGy in 10-kGy increments led to decreases in the swelling ratio and elongation at break but increases in the crosslink density, tensile modulus at 500% elongation, and tensile strength of the composites. The results also suggested that increasing the WES contents from 0 to 2, 4, or 6 parts per hundred parts of rubber by weight (phr) in the composites improved the tensile modulus at 500% elongation, tensile strength, hardness (Shore A), and electrical (volume) resistivity. In addition, after undergoing thermal aging at 70°C for 96?h, the tensile modulus and hardness (Shore A) increased, while the tensile strength and elongation at break decreased. This work also compared the properties of WES/RVNRL with commercial CaCO₃/RVNRL samples at the same 4-phr content. The results indicated that both composites had similar tensile properties, implying possible replacement of commercial CaCO₃ with WES powder as an effective reinforcing filler in RVNRL.     

The Effect of Oil‐Extension on the Properties of TPI and TPI/SBR Vulcanizates

Trans‐1,4‐polyisoprene (TPI) with a Mooney viscosity of 120 was filled with 37.5 phr aromatic oil to prepare oil‐extended trans‐1,4‐polyisoprene (OETPI) by a dry oil‐extending process. The curing characteristics of TPI gum, OETPI gum, and TPI/SBR compounds were studied and the mechanical properties of vulcanizates were also investigated. The experimental results showed that the Shore A hardness, Mooney viscosity, and mechanical properties of OETPI gum decreased, compared with that of TPI gum. The modulus at 100% elongation, Shore A hardness, and tensile strength of OETPI vulcanizates also decreased, while the abrasion loss, compression heat build‐up, and compression set increased. Compared with TPI/SBR, the dispersibility of carbon black in OETPI/SBR compounds was improved. The mechanical properties of OETPI/SBR vulcanizates changed little, while the wet skid resistance and fatigue resistance was greatly improved.     

Morphology, mechanical, cross-linking, thermal, and tribological properties of nitrile and hydrogenated nitrile rubber/multi-walled carbon nanotubes composites prepared by melt compounding: The effect of acrylonitrile content and hydrogenation

The purpose of this work was to prepare nanocomposites by mixing multi-walled carbon nanotubes (MWCNT) with nitrile and hydrogenated nitrile elastomers (NBR and HNBR). Utilization of transmission electronic microscopy (TEM), scanning electron microscopy (SEM), and small- and wide-angle X-ray scattering techniques (SAXS and WAXS) for advanced morphology observation of conducting filler-reinforced nitrile and hydrogenated nitrile rubber composites is reported. Principal results were increases in hardness (maximally 97 Shore, type A), elastic modulus (maximally 981 MPa), tensile strength (maximally 27.7 MPa), elongation at break (maximally 216%), cross-link density (maximally 7.94 × 10²⁸ m⁻³), density (maximally 1.16 g cm⁻³), and tear strength (11.2 kN m⁻¹), which were clearly visible at particular acrylonitrile contents both for unhydrogenated and hydrogenated polymers due to enhanced distribution of carbon nanotubes (CNT) and their aggregated particles in the applied rubber matrix. Conclusion was that multi-walled carbon nanotubes improved the performance of nitrile and hydrogenated nitrile rubber nanocomposites prepared by melt compounding.     

Influence of Zinc Oxide Amount on Cure Kinetics of Sulfur-Vulcanized Natural Rubber

A kinetic cure model with induction, curing, and postcure periods, based on cure characteristics of Natural rubber/sulfur/N-t-butylbenzothiazole-2-sulfenamide (NR/S/TBBS) system, was chosen to simulate the cure reaction of this system. Cure-curves reflecting the evolution of crosslink density were recorded as a function of curing time for NR compounds using a rubber processing analyzer (RPA). The data of experimental cure curves were nonlinear fitted with the chosen model and the kinetic parameters were determined. The results showed that the simulated curves fit well with the experimental curves. The incorporation of zinc oxide changed the cure mechanism of this system. The concentration of activated sulfurating agents, A ₀, increased with increased zinc oxide amount. With the increase of zinc oxide amount, the activity of crosslink precursors decreased slightly (k ₂ decreased) which had little influence on its activation energy. The activity of crosslink degradation decreased with the increase of zinc oxide amount from 1 phr to 2 phr. Higher zinc oxide load had no further contribution to crosslink density and reversion resistance. Parameter ψ, representing the competition between reactions of activated crosslinking precursors to form crosslinks and to form dead side-products, decreased significantly when zinc oxide increased from 1 phr to 2 phr. Higher zinc oxide load (from 2 ～ 4 phr) induced a slight increase of ψ, especially at higher cure temperature.     

Influence of Accelerator Content on Cure Kinetics of Sulfur-vulcanized Natural Rubber

Based on the cure characteristics of the NR/S/TBBS system, a kinetic model with induction, curing, and post-cure periods was chosen to simulate the cure reaction of this system. Cure curves reflecting the evolution of crosslink density were recorded as a function of curing time for NR compounds using a rubber processing analyzer (RPA). The cure curves were then non-linear fitted and the kinetic parameters were determined. The results showed that the simulated curves fit well with the experimental curves. As the concentration of activated sulfurating agents, A_o, increased, the activity of crosslink precursors increased (K₂ increased), while the activity for crosslinks to degrade decreased (K₆ decreased) due to shortening of the sulfur chain both in crosslink precursors and in crosslinks, leading to the improved thermal stability of NR vulcanizate at elevated temperatures. Increased accelerator amount also increased the competition of the reaction to form crosslinks over the reaction to form dead by-products, which improved the efficiency of sulfur. Reaction activation energy E₂ and E₆, calculated from K₂ and K₆ through the Arrhenius equation, showed that E₆ is higher than E₂. The increase of accelerator dosage led to the decrease of E₂ and increase of E₆, which explained the phenomenon of improved anti-reversion.     

Properties of Natural Rubber Vulcanizates/Nanosilica Composites Prepared Based on the Method of In-situ Generation and Coagulation

Using the characteristics of silica sol dispersing well in water and easy formation of silica gel when the silica sol is heated, by mixing a system of concentrated natural rubber latex and silica sol, the silica sol can in-situ generate SiO₂ particles when heated. After coagulation of the mixed system, natural rubber/nanosilica composites C(NR/nSiO₂) were obtained. The composites C(NR/nSiO₂) and their vulcanizates were studied using a rubber processing analyzer (RPA), dynamic mechanical analysis (DMA), and scanning electron microscopy (SEM). The influence of silica contents on the C(NR/nSiO₂) vulcanizates mechanical properties, cross-linking degree, Payne effect, dissipation factor (tanδ), and the particle size and dispersion of SiO₂ in NR were investigated. The results obtained were compared with the NR/SiO₂ composites based on traditional dry mixing of bale natural rubber and precipitated silica (white carbon black). The results showed that when using a sulfur curing system with a silica coupling agent (Si69) in C(NR/nSiO₂), the vulcanizate had better mechanical properties, higher wet resistance, and lower rolling resistance than those without Si69. In the composites C(NR/nSiO₂) and their vulcanizates, the SiO₂ particles’ average grain diameter was 60 nm, and the good-dispersion of the in-situ generated SiO₂ in the rubber matrix were a significant contribution to the satisfactory properties of C(NR/nSiO₂) composites and their vulcanizates.     

Thermoplastic Elastomers Based on Natural Rubber/Polypropylene Blends: Effect of Blend Ratios and Dynamic Vulcanization on Rheological,Thermal, Mechanical,and Morphological Properties

Thermoplastic elastomers (TPEs) based on natural rubber (NR)/polypropylene (PP) with different blend ratios were prepared and studied. The TPEs were obtained by dynamic vulcanization of NR/PP using a sulfur (S)/N-tert-butyl-2-benzothiazolesulphenamide (TBBS) and tetramethylthiuram disulphide (TMTD) curative system during processing in the melt state in an internal mixer equipped with cam rotors. Rheological, thermal, mechanical, dynamic, and morphological properties of the TPEs prepared were investigated. Based on this study a mechanism for the NR crosslinking was proposed where the sulfur vulcanization occurs through radical substitution in the forms of polysulfide bridges. The dynamic vulcanization process increases the stiffness of the NR phase in the TPEs and modifies the rheological and thermal behavior of the system compared to the behavior of the basic material PP. The crosslinked NR particles restrict the spherulitic growth and the regular arrangement of the spherulites of PP phase, decreasing the crystallinity degree. On the other hand, a reduction of mobility of the chain segments was also observed and, consequently, an increase of the T_g values. NR/PP TPEs with high content of NR showed superior mechanical performance compared to the uncrosslinked NR/PP blends in terms of tensile strength, Young's modulus and hardness. An increase of approximately 320% in Young's modulus values was obtained for the NR70/PP30 TPE compared to NR70/PP30. Morphological studies revealed the formation of large aggregates of NR domains in NR/PP TPEs which increased in size with an increase of the rubber content.     

The effect of accelerator contents on the vulcanizate structures of SSBR/silica vulcanizates

Physical properties of rubber compounds are affected by the filler–rubber interaction, filler dispersion in the rubber matrix, and cross-link structure formed during vulcanization. In particular, the cross-link structure is closely related to the physical properties of vulcanizates and has been analyzed using the swelling test and Flory-Rehner equation. However, the relationship between the structure and physical properties of vulcanizates cannot be explained by the cross-link density obtained using these methods. The cross-link density obtained from the swelling test is a complex result of the filler–rubber interaction occurring during the compounding as well as the chemical cross-link structure formed by sulfur during the vulcanization. Moreover, the rubber vulcanizates that use silica need to be separately analyzed for each factor as its physical properties are affected more by the filler–rubber interaction than by carbon black. Therefore, this study determines the factors that contribute to the total cross-link density of vulcanizates into chemical cross-link density and filler–rubber interaction via quantitative analysis using the swelling test results and Flory-Rehner and Kraus equations. The vulcanizates used for the analysis were carbon black-filled and silica-filled non-functionalized SSBR compounds with varying cure accelerator for each filler loading. Their chemical cross-link density was measured and the effect of the filler–rubber interactions on their mechanical and dynamic viscoelastic properties was investigated. Furthermore, the relationship between the structure and physical properties of rubber vulcanizates was elucidated.     

Influence of the silanes on the crosslink density and crosslink structure of silica-filled solution styrene butadiene rubber compounds

The effects of three silane coupling agents, triethoxy(octyl)silane (TEOS), bis[3-(triethoxysilyl)propyl]disulfide (TESPD), and bis[3-(triethoxysilyl)propyl]tetrasulfide (TESPT) on the filler-rubber interaction, crosslink density and crosslink structure of the silica-?lled solution styrene butadiene rubber (SSBR) vulcanizates were studied. High dispersion silica, 7000GR, was used as the ?ller, and the loading range was varied from 0 to 60 phr. Crosslink density was measured by the swelling method. Experimental results showed that Kraus plot can be applicable to the silica-filled SSBR vulcanizates to separate filler-rubber interaction from the measured swelling data. Filler-rubber interaction increased by increasing sulfur rank in the silane as TEOS < Silica without silanes < TESPD < TESPT. Sulfurless silane, i.e. TEOS, only worked as a covering agent for hydrophobating silica surface. Silica without silane show high filler-rubber interaction than TEOS system because chain-end functionalized SSBR was used in this study. Unfilled system showed similar amounts of poly, di, and mono-sulfidic crosslinks. On the contrary to this, all of the silica-filled vulcanizates showed high mono-sulfide contents due to longer cure time.     

Effect of complex inter-site couplings on the excitation energy transfer in the FMO complex

The laser irradiation effects on surface, structural and mechanical properties of zirconium (Zr) have been investigated. For this purpose, Zr samples were irradiated with Excimer (KrF) laser (λ ≈ 248 nm, τ ≈ 18 ns, repetition rate ≈ 30 Hz). The irradiation was performed under the ambient environment of oxygen gas at filling pressure of 20 torr by varying laser fluences ranging from 3.8 to 5.1 cm^-2. The surface and structural modification of irradiated targets was investigated by scanning electron microscope (SEM) and X-ray diffractometer (XRD). In order to explore the mechanical properties of irradiated Zr, the tensile testing and Vickers micro hardness testing techniques were employed. SEM analysis reveals the grain growth on the irradiated Zr surfaces for all fluences. However, the largest sized grains are grown for the lowest fluence of 3.8 J cm^?2. With increasing fluence from 4.3 to 5.1 J cm^?2, the compactness and density of grains increase whereas their size decreases. XRD analysis reveals the appearance of new phases of ZrO₂ and Zr₃O. The variation in the peak intensity is observed to be anomalous whereas decreasing trend in the crystallite size and residual stresses has been observed with increasing fluence. Micro hardness analysis reveals the increasing trend in surface hardness with increasing fluence. The tensile testing exhibits the increasing trend of yield stress (YS), decreasing trend of percentage elongation and anomalous behaviour of ultimate tensile strength with increasing fluence.     

Comparison of Mechanical Properties and Rheological Behavior of Trans-Polyisoprene/Polypropylene and Ethylene Propylene Diene Rubber/Polypropylene Thermoplastic Vulcanizates

The degree of dynamic vulcanization, mechanical properties, rheological behavior, and the ageing-resistant performance of trans 1,4-polyisoprene (TPI)/polypropylene (PP) and ethylene propylene diene rubber (EPDM)/PP thermoplastic vulcanizates with a blend ratio of 60/40 were investigated comparatively. The results showed that TPI had fully dynamically vulcanized when mixed with PP in the Hakke mixer chamber (175°C, 60 rpm) while EPDM had only partly dynamically vulcanized due to its saturated main chain backbone. With increased sulfur content, the torque at the end of the curing curves of the two thermoplastic vulcanizates (TPVs) increased in the curing characteristics measuring process as the degree of crosslinking increased. Comparing the two blends, TPI/PP-TPVs were possessed of a better mobility, a little lower tensile strength and tear strength, a little higher 100% modulus and hardness, and much lower elongation at break. EPDM/PP-TPVs had better ageing-resistant characteristics due to EPDM's saturated main chain backbone.     

Effects of the Synergy of Hardness and Resilience on the Akron Abrasion Properties of SBR Vulcanizates

The hardness (H) and resilience (R) of rubber vulcanizates were combined together in this paper, named as hardness–resilience product (H⁴R), and its relationship with the Akron abrasion loss was investigated using various styrene-butadiene rubber (SBR) vulcanizates possessing specific hardness and resilience characteristics as samples. For the unfilled SBR vulcanizates with different chain microstructure, possessing high elastic resilience and low hardness, the results showed that their Akron abrasion loss had a good linear relationship with the log(H⁴100R). This linear relationship also occurred when these SBRs were filled with 50 phr carbon black. For two particular types of SBR, after being filled with different fractions of carbon black and aged for different times, all their Akron abrasion losses (including unaged, aged for 24 h, and aged for 48 h) also had a good linear relationship with the log(H⁴100R). However, this linear relationship weakened for one of the SBRs after being aged for 48 h. In the high H⁴R region (the carbon black fractions being 60 and 70 phr), the data obviously deviated from the fitting curve due to the high hardness of the aged vulcanizates. However, after being filled with 50 phr of various kinds of carbon blacks, the relationships between abrasion loss and log(H⁴100R) were also approximately linear, with the correlation coefficient of the fitting curves being 0.99966 and 0.99878, respectively, for the two types of SBR.     

Enhancing mechanical properties of prevulcanized natural rubber latex via hybrid radiation and peroxidation vulcanizations at various irradiation doses

At present, there are three popular vulcanization processes being used in natural rubber latex industries, which are sulfur, radiation and peroxide vulcanization. Sulfur vulcanization produced products with superior mechanical properties compared to radiation and peroxide vulcanization. This paper discussed the effect of gamma irradiation dose on hybrid radiation and peroxidation vulcanizations in improving the mechanical properties of radiation vulcanized natural rubber latex (RVNRL). Latex compounding formulations are developed based on 2.5?parts per hundred rubber (phr) of hexanediol diacrylate (HDDA) as the sensitizer, 0.1?phr of tert-butyl hydroperoxide (t-BHPO) as the co-sensitizer and 2.5?phr of Aquanox LP antioxidant. The RVNRL was prepared and irradiated at various gamma radiation doses of 2, 4, 6, 8, 10 and 12?kiloGray (kGy). The rubber film obtained from irradiation at 6?kGy had tensile strength, modulus @ 500% and modulus @ 700% of 27.0, 3.0 and 11.0?MPa, respectively, which is more than 37% increment compared to the control film. Besides, the crosslink percentage of the rubber film showed 4% increment from 90% to 94%.     

Degradable Bioelastomers Prepared by a Facile Melt Polycondensation of Citric Acid and Polycaprolactone-diol

Citrate-based bioelastomers have great potentials in various biomedical fields. An appropriate selection of diol monomers could tune their properties to fulfill different application requirements. Herein, polycaprolacone diol (PCL-diol) was selected as the diol monomer to fabricate poly(caprolactone-diol citrate) (PCC) degradable bioelastomers by a one pot melt polycondensation coupled with subsequent thermosetting or post-polymerization. The catalyst-free polycondensation reaction was confirmed by Fourier transform infrared (FTIR) spectroscopy and ¹H nuclear magnetic resonance (¹HNMR) spectroscopy. The properties of the PCC elastomers were explored by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), uniaxial tension tests, dynamics mechanical analysis (DMA), water-contact angle and in-vitro degradation measurements. The results showed that the molar ratio of monomers and thermosetting conditions had significant effects on the ultimate properties of the PCC elastomer. By regulating monomer ratio and thermosetting temperature the crosslink density ranged from 32?±?6?mol/m³ to 292?±?18?mol/m³, the tensile strength ranged from 171?±?28?KPa to 977?±?112?KPa, Young’s modulus ranged from 252?±?36?KPa to 1737?±?212?KPa, ultimate elongation ranged from 70?±?9% to 260?±?32%, the static-water-contact-angle was in the range of 65.4?±?1.8?～?91.0?±?0.9° and the weight loss of the PCC elastomer in phosphate buffered saline (PBS) (pH =7.4) was in the range of 30?～?100?wt% after 8?weeks degradation. An elastic and compressible, porous scaffold was fabricated via a salt leaching method, which has potential use in soft tissue grafts.     

Natural rubber nanocomposites using polystyrene-encapsulated nanosilica prepared by differential microemulsion polymerization

In this study, nanocomposites of natural rubber (NR) and polystyrene (PS)-encapsulated nanosilica were prepared by latex compounding method. The nanolatex of PS-encapsulated silica was synthesized via in situ differential microemulsion polymerization. The resulted hybrid nanoparticles showed core-shell morphology with an average diameter of 40 nm. The silica hybrid nanoparticles were subsequently used as filler for the NR nanocomposite. The properties of NR were found to be improved as a result of the incorporation of PS-encapsulated nanosilica at 3 and 3-9 parts per hundred rubber (phr) for tensile strength and modulus at 300% strain, respectively, except the elongation at break, and up to 9 phr for flammability. The results from dynamic mechanical analyzer showed that the elastic properties of NR near the glass transition temperature increased with the inclusion of increasing concentration of the PS-encapsulated nanosilica, causing by the semi-interpenetrating nanostructure in the NR nanocomposites.     

Effect of curing temperature,fibre loading and bonding agent on the equilibrium swelling of isora-natural rubber composites

Isora fibre-reinforced natural rubber (NR) composites were cured at 80, 100, 120 and 150°C using a low temperature curing accelerator system. Composites were also prepared using a conventional accelerator system and cured at 150°C. The swelling behavior of these composites at varying fibre loadings was studied in toluene and hexane. Results show that the uptake of solvent and volume fraction of rubber due to swelling was lower for the low temperature cured vulcanizates which is an indication of the better fibre/rubber adhesion. The uptake of aromatic solvent was higher than that of aliphatic solvent, for all the composites. As the fibre content increased, the solvent uptake decreased, due to the superior solvent resistance of the fibre and good fibre–rubber interactions. The bonding agent improved the swelling resistance of the composites due to the strong interfacial adhesion. Due to the improved adhesion between the fibre and rubber, the ratio of the change in volume fraction of rubber due to swelling to the volume fraction of rubber in the dry sample (V_τ ) was found to decrease in the presence of bonding agent. At a fixed fibre loading, the alkali treated fibre composite showed a lower percentage swelling than untreated one for both systems showing superior rubber–fibre interactions.     

Concept of the Fourth-Generation Neutron Source in Dubna

The principles of designing a subcritical neutron-multiplying system with reactivity modulation, which can be used as the target in a superbooster with a linear proton accelerator, are described. Calculations demonstrate that the output neutron-flux density of a pulse can be expected to reach 10¹⁷ cm^–2 s^–1 at maximum and 2 × 10¹⁴ cm^–2 s^–1 on average. The pulse duration of thermal neutrons can be 200–300 and 20–30 μs depending on the moderator and the corresponding pulse duration of the proton accelerator.     

Interactions Between an Ionic Liquid and Silica,Silica and Silica,and Rubber and Silica and Their Effects on the Properties of Styrene-Butadiene Rubber Composites

An investigation of the effect of an ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate (BMI), on the properties of silica reinforced styrene-butadiene rubber (SBR), aimed to correlate the interactions between the ionic liquid and silica, silica and silica, and silica and rubber with the macro-properties and microstructure of SBR and SBR/silica vulcanizates is described. The interaction between the ionic liquid and silica was characterized by differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR), the interaction between silica and silica was characterized by a rubber processing analyzer (RPA), and the interaction between rubber and silica was characterized by the bound rubber content. The FTIR analysis revealed that BMI can react with the hydroxyl groups on the surface of silica, improving the compatibility between the rubber and silica. The RPA and bound rubber testing indicated that the interactions between silica and silica particles were weakened and the interaction between silica and rubber increased with the incorporation of BMI into the SBR rubber. The bound rubber content showed a maximum with a BMI content of 3 phr. At the same time, the dispersion of silica in SBR was improved with the incorporation of BMI. With the increase of BMI content, the curing rate was greatly improved and the crosslink density increased. BMI also increased the tensile strength and abrasion resistance of the SBR vulcanizates. Most important, the BMI significantly improved the dynamic properties of the rubber composites, especially the wet-skid resistance and rolling resistance. However, excessive BMI (beyond 3 phr) acted as a plasticizer and was detrimental to the mechanical properties, resulting in a decrease of tensile strength and abrasion resistance.     

Structure of vinylester networks: A rubber elasticity study

Five networks based on a diglycidylether of bisphenol A-dimethacrylate prepolymer of molar mass 1100 g· mol^?1 crosslinked with 35%, 40%, 45%, 50%, and 55% styrene mass fractions were characterized by Fourier transform infrared spectroscopy, cross-polarization/magic-angle spinning, nuclear magnetic resonance spectroscopy, styrene extraction, and rubber elasticity measurements. Various structural models were built up from the available analytical data, and their crosslink density was compared to the experimental data derived from rubber elastic moduli. Globally, network models based on a purely statistical approach but taking into account the incomplete cure conversion make it possible to predict the trends of modulus variations. The kinetic data on copolymerization show, however, that the material is diphasic, one phase being composed of the vinylester network and the other of practically pure polystyrene. We tried to take this heterogeneity into account in modulus predictions using a simple mixture rule, but the method failed for high styrene mass fractions (s ? 0.45), for which the experimental modulus value is about 50% higher than the predicted one. The results suggest the existence of a morphological transition for a critical styrene weight fraction between 40% and 45%.