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.     

Insights into the Reinforcement of Butyl Rubber by Carbon Black and Silica with the Aid of Their Dynamic Properties

Carbon black (N234) and silica (Vulksail N) with a silane coupling agent Si-69 were chosen as reinforcing fillers in butyl rubber (IIR). The rheological behavior of the IIR compounds and the dynamic mechanical properties of IIR vulcanizates were investigated with a rubber processing analyzer and dynamic mechanical analysis (DMA) to examine the filler dispersion in the rubber matrix and the interaction between filler and matrix. The data indicated that the N234 filled IIR compounds had more filler networks than those filled with silica. Filler networks first appeared at 30 phr N234 and 45 phr silica with silane coupling agent Si-69. The interaction between N234 and IIR was far stronger than that between silica and IIR. However, the silica Vulksail N filled IIR had better wet-grip and lower rolling resistance compared to the carbon black-filled IIR should IIR be chosen as a substitute of styrene-butadiene rubber (SBR) in tire tread. The reinforcing factor, R, R (related to the difference in tan d peak height at T_g for the filled and nonfilled rubbers), also demonstrated that the N234-IIR interaction was stronger than for the silica. IIR with 30 phr N234 exhibited the largest tensile strength, 20.1 MPa, for those vulcanizates examined. The tensile and tear strengths of N234 filled IIR were higher than those of IIR with similar amounts of silica. Thus, it was concluded that N234 is a more active reinforcing filler in IIR than silica (Vulksail N) even with a silane coupling agent (Si-69).     

The Effect of Epoxidized Natural Rubber and Two Kinds of Organoclay upon Molecular Interaction,Structure and Mechanical Properties of (Styrene-Butadiene Rubber/Acrylonitrile-Butadiene Rubber/Organoclay) Nanocomposites

Epoxidized natural rubber (ENR50) and two different kinds of organoclay (C30B and C15A) were used in blends of styrene-butadiene rubber (SBR) and acrylonitrile butadiene rubber (NBR) and their effects upon interaction between phases, morphology, and mechanical properties of the blends were investigated. The compounds were characterized by means of Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), atomic force microscopy (AFM), field emission scanning electron microscopy (FE-SEM), and differential scanning calorimetry (DSC). The obtained results showed formation of hydrogen bonding between the compounds ingredients due to incorporation of C30B, especially in presence of ENR. AFM and FE-SEM analysis revealed good dispersion of the nanoparticles in the polymer matrix upon addition of ENR as well as better dispersion of C30B than C15A in the NBR phase. XRD results showed a greater expansion of the silicate layers by simultaneous use of organoclay and ENR Incorporation of organoclay alone or in combination with ENR in the blends caused shifting of the SBR T_g toward the NBR T_g. The tensile properties of the blends showed improvement by using nanoparticles in the presence of ENR.     

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.     

Preparation and Characterization of Two Types of Cyanate Ester-epoxy Resin Interpenetrating Network Matrix/Butadiene-acrylonitrile Rubber Composites

Two types of butadiene-acrylonitrile rubbers (i.e., carboxyl randomized butadiene-acrylonitrile rubber (CRBN) and hydroxyl terminated butadiene-acrylonitrile rubber (HTBN)) have been used for modifying an interpenetrating network of cyanate ester (CE)/epoxy resin (EP) (70/30). The toughness of the matrix can be improved effectively with addition of rubbers. The values of impact strength (11.6 KJ/m²) show a maximum for the CE/EP/HTBN (70/30/8) blend. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results show that CRBN and HTBN have a different dispersion state in the CE/EP matrix. CRBN aggregates to form regular spheres with a size of about 1 μm. HTBN disperse homogeneously with its size of the nano-level (about 10 nm). Fourier transform infrared spectrum (FTIR) and differential scanning calorimetric (DSC) analysis shows that the CRBN has higher reactivity than HTBN. The thermal gravimetric analysis (TGA) results shows that T ₁₀ (temperature of 10% weight loss) of the CE/EP system decreases with the addition of rubbers. For the CE/EP/CRBN system, both T ₃₀ (temperature of 30% weight loss) and T ₅₀ (temperature of 50% weight loss) are lower than neat CE/EP. However, for the CE/EP/HTBN system, both T ₃₀ and T ₅₀ are near to neat CE/EP. Different reactivity and compatibility between the rubbers and CE/EP matrix is the main determining factor for the thermal stability of the blends.     

Characterization of Filler-rubber Interaction,Filler Network Structure,and Their Effects on Viscoelasticity for Styrene-butadiene Rubber Filled with Different Fillers

For styrene-butadiene rubber (SBR) compounds filled with the same volume fraction of carbon black (CB), precipitated silica and carbon–silica dual phase filler (CSDPF), filler-rubber interactions were investigated thru bound rubber content (BRC) of the compounds and solid-state ¹H low-field nuclear magnetic resonance (NMR) spectroscopy. The results indicated that the BRC of the compound was highly related to the amount of surface area for interaction between filler and rubber, while the solid-state ¹H low-field NMR spectroscopy was an effective method to evaluate the intensity of filler-rubber interaction. The silica-filled compound showed the highest BRC, whereas the CB-filled compound had the strongest filler-rubber interfacial interaction, verified by NMR transverse relaxation. The strain sweep measurements of the compounds were conducted thru a rubber process analyzer; the results showed that the CSDPF-filled compound presented the lowest Payne effect, which is mainly related to the weakened filler network structure in polymer matrix. The temperature sweep measurement, tested by dynamic mechanical thermal analysis, indicated that the glass transition temperature did not change when SBR was filled with different fillers, whereas the storage modulus in rubbery state and the tanδ peak height were greatly affected by the filler network structure of composites.     

Effects of Carbon Black on Chain Mobility and Dynamic Mechanical Properties of Solution Polymerized Styrene-Butadiene Rubber

The structure of the bound rubber, the ¹H NMR (nuclear magnetic resonance) relaxation time, and the crosslink density of the physical network and the glass transition, were studied for solution polymerized styrene-butadiene rubber (SSBR) filled by carbon black, to investigate the effects of carbon black on the chain mobility and dynamic mechanical properties. It was found by ¹H NMR analysis that the rubber chains were adsorbed on the surface of carbon black to form physical crosslinks and restrict the mobility of the chains, especially for some high-mobility units such as chain ends. It was calculated, according to the molecular weight between adjacent crosslinks, that the main motion units of the tightly adsorbed chains appeared to be similar in size to the chain segments. The glass transition temperature (T _g) obtained by differential scanning calorimetry (DSC) could not be used to judge the effect of carbon black on chain mobility, while the appearance and change of the loss-tangent (tan δ) peak at high temperature in dynamic mechanical thermal spectrometry (DMTS) test showed that there were three chain states: free chains, loosely adsorbed chains, and tightly adsorbed chains. The dynamic rheology test showed that the unfilled SSBR compound had the rheological characteristics of entangled chain networks; however the nonlinear viscoelasticities of the filled SSBR were related to the gradual disentanglement of adsorbed chains and free chains. The peaks in tan δ vs. temperature curves implied that the motion unit size decreased with the increase of bound rubber content, and the modulus vs. temperature curve showed an apparently lower mobility of adsorbed chains than that of free chains through the very low dependence of modulus on temperature for the highly filled compounds. The extremely high tensile modulus of the vulcanizate with 63.6% carbon black at room temperature also implied that the adsorbed chains were in the glass state due to their restriction by the carbon black.     

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.     

Comparative Properties of Styrene-Butadiene Rubbers (SBR) Containing Pyrolytic Carbon Black,Conventional Carbon Black,and Organoclay

To evaluate the reinforcing potential of pyrolytic carbon black, styrene-butadiene rubber (SBR) was filled with pelletized pyrolytic carbon black (pCB_p), N660 industrial CB, their blend in a 1/1 ratio, and the latter also in the absence and presence of additional organoclay (OC). The Shore A hardness of the filled SBR gums was 65 ± 2°. Effects of the compositions on the filler dispersion, cure behavior, dynamic mechanical thermal parameters (including the Payne effect), tensile mechanical (including the Mullins effect), and fracture mechanical (making use of the J-integral concept) properties were studied and discussed. Though pCB_p had a higher specific surface weight than CB, the latter proved to be a more active filler with respect to the tensile strength. The opposite tendency was found for the tear strength and fracture mechanics characteristics (J-integral at crack tip opening, tearing modulus, and trouser tear strength). This was traced to an enlargement in the crack tip damage zone supported by the dispersion characteristics of the pCB_p. The performance of pCB_p was similar to that of CB with respect to some other properties. OC supported the filler networking which positively affected the resistance to crack initiation.     

Synthesis of nanoparticles and its effect on properties of elastomeric nanocomposites

Calcium carbonate (CaCO₃) nanoparticles (9, 15, and 21 nm) were synthesized by solution spray of CaCl₂ and NH₄HCO₃ with sodium lauryl sulfate (SLS) as a stabilizing agent, and their effect was studied on polybutadiene rubber (PBR) with variations in wt% loading (4, 8, and 12%). The results of PBR nanocomposites were compared with commercial CaCO₃ (40 μm) and fly ash (75 μm) filled PBR microcomposites. Properties such as tensile strength, young modulus, elongation at break, glass transition temperature, decomposition temperature, and abrasion resistances were determined. Profound effect in properties was observed, because nanometric size of CaCO₃ particles synthesized using solution spray technique. Maximum improvement in mechanical and flame retarding properties was observed at 8 wt% of filler loading. This increment in properties was more pronounced in 9-nm size CaCO₃. The results were not appreciable above 8 wt% of nanofillers because of agglomeration of nanoparticles. In addition, an attempt was made to consider modeling Young’s modulus of PBR–nano CaCO₃ which was predicted by modified Halpin–Tsai equation. It was observed that the predication by the Guth equation and modified Halpin–Tsai equation agreed very well with experimental, whereas the Halpin–Tsai equation can only applied to predict the modulus of rubber nanocomposites in the range of low addition of nanofiller, which agrees the Nielsen equation.     

Ultrasonic degradation of butadiene, styrene and their copolymers

Ultrasonic degradation of commercially important polymers, styrene-butadiene (SBR) rubber, acrylonitrile-butadiene (NBR) rubber, styrene-acrylonitrile (SAN), polybutadiene rubber and polystyrene were investigated. The molecular weight distributions were measured using gel permeation chromatography (GPC). A model based on continuous distribution kinetics approach was used to study the time evolution of molecular weight distribution for these polymers during degradation. The effect of solvent properties and ultrasound intensity on the degradation of SBR rubber was investigated using different pure solvents and mixed solvents of varying volatility and different ultrasonic intensities.     

Effect of Injection Parameters and Addition of Nanoscale Materials on the Shrinkage of Polypropylene Copolymer

The effect of variation of injection conditions and addition of nano-calcium carbonate (CaCO₃), nano-silicon dioxide (SiO₂) and full-vulcanized nano-powdered styrene butadiene rubber (PSBR) on the shrinkage of injection-molded polypropylene-ethylene copolymer (90/10, co-PP) were investigated. The results showed that the shrinkage was different for different locations along the flow path. The shrinkage in the length direction of the injection-molded sample varied with the adjustment of the processing parameters, while the shrinkage in the width and thickness direction was almost unchanged. The addition of nano-CaCO₃ and PSBR decreased the shrinkage of co-PP, while the shrinkage of co-PP/ SiO₂ composite was almost unchanged.     

A neutron spin-echo study of the dynamics of star-shaped polymers (with polystyrene arms grafted to C60) in solutions and in the bulk

Methods of small-angle and inelastic neutron scattering were used to study star-shaped polymers obtained by grafting polystyrene to fullerene C₆₀ (six arms with an elementary mass M=5×10³). The behavior of stars in the solution and bulk was compared with the dynamics of free molecules of polystyrene with a mass equal to the mass of an arm. The slow dynamics of arms in the ranges of times t=0.01–20 ns, momentum transfers q=0.2–0.6 nm^?1, and temperatures T=20–60°C does not obey the simple models of Rouse and Zimm. The interaction of the rays with the C₆₀ fullerene under the conditions of the specific geometry of the macromolecule leads to unusual oscillations of time correlations in the arms of stars.     

Toughening poly(lactic acid) (PLA) through in situ reactive blending with liquid polybutadiene rubber (LPB)

Abstract

Liquid polybutadiene rubber (LPB) was blended with poly(lactic acid) (PLA) through reactive and non-reactive routes to enhance the toughness of the PLA. The reactively blended PLA (PBR10) was prepared by melt blending the PLA with the LPB in the presence of dicumyl peroxide (DCP), a radical initiator, while the PB10 was just melt blended without the DCP. Fourier transform infrared (FTIR) spectra and wide-angle X-ray diffraction (WAXD) patterns were used to study the molecular structure of the blends. Properties were investigated through universal testing machine (UTM), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), scanning electron microscope (SEM) analysis, and rheological measurements. The results indicated that the radical crosslinking by the DCP could increase the compatibility between the PLA and LPB and disperse the rubber particles at the nanoscale in the PLA matrix. As a result, the toughness and melt viscosity of the PLA was significantly enhanced through the reactive blending, which is promising for the practical application of the modified PLA in the area of packaging.     

Spherulite Growth of cis-1,4-Polyisoprene Isolated from Natural Rubber

The crystallization behavior of cis-1,4-polyisoprene, isolated from natural rubber, was investigated by polarized light microscopy. Natural rubber was purified by deproteinization followed by transesterification to remove protein, phospholipid, and fatty acids present in the rubber. The purified rubber was fractionated into seven fractions. For the fractionated rubbers, spherulite growth was observed during the course of crystallization. The size of the spherulites increased linearly with crystallization time, and thus, growth rate was estimated. The growth rate was proportional to TΔT, where ΔT is supercooling. Because the slope of the line was independent of the molecular weight, the growth rate was confirmed to be a function of diffusion of the rubber.     

Dynamically Vulcanized Styrene-Butadiene Rubber/Ethylene-Vinyl Acetate Copolymer/High Impact Polystyrene Blends Compatibilized by Styrene-Butadiene-Styrene Block Copolymer

Thermoplastic vulcanizates (TPVs) based on styrene-butadiene rubber (SBR)/ethylene-vinyl acetate copolymer (EVA)/high-impact polystyrene (HIPS) blends were prepared by dynamic vulcanization, and the TPVs was compatibilized by styrene-butadiene-styrene block copolymer (SBS). The effects of SBS compatibilizer on mechanical, dynamic mechanical, and morphological properties of the TPVs were investigated systemically. Experimental results indicate that SBS had a good compatibilization effect on the SBR/EVA/HIPS TPVs. The tensile strength went through a maximum value at a compatibilizer resin content of 6 phr, and the elongation at break and tear strength increased with increasing SBS content. Morphology study shows that the vulcanized SBR particles were dispersed in the HIPS matrices. A rubber process analyzer reveals that the elastic modulus increased with increasing frequency and the incorporation of EVA in the TPVs led to the obvious decrease of elastic modulus; however, the further addition of compatibilizer SBS affected the elastic modulus less. The tan δ decreased continuously with increasing frequency. The addition of SBS in the TPVs led to enhanced hysteresis behavior and relatively high tan δ.     

Structures and stabilities of CBHz (z ≤ 8) and CxB3-xHz (x = 1, 2, z ≤ 14): prediction of novel organo-boron radicals

Hydrogenated boron-carbon clusters, i.e. organo-borons, have received considerable attention both theoretically and experimentally. Herein, using a topology searching strategy, we systematically explore the structures and stabilities of small organo-borons with CBH_z (z ≤ 8) and C_xB_3-xH_z (x = 1, 2,z≤ 14) stoichiometry, with particular interests in the intrinsic stabilities of the organo-boron radicals. At the CCSD(T)/aug-cc-pVQZ//B3LYP/aug-cc-pVTZ and CCSD(T)/aug-cc-pVQZ//MP2/aug-cc-pVTZ levels, the stabilities of these global minimum organo-boron species were evaluated by considering dissociation pathways and the binding energy per atom. Aside from the five already studied radicals (CBH₂, CBH₄, C₂BH₂, C₂BH₄ and CB₂H₃), we predict six novel radicals, i.e. CBH₆, C₂BH₆, C₂BH₈, CB₂H, CB₂H₅ and CB₂H₇, which could be detected under suitable circumstances. However, observation of the highly hydrogenated CB₂H₉ radical is much less likely due to its minute stability towards H-extrusion. The computationally determined stable/meta-stable maximum hydrogenation numbers for CB, C₂B and CB₂ (6, 8 and 8, respectively) are in excellent agreement with a simple electron-counting model for C_xB_y chains. The newly predicted organo-boron radicals await future laboratory verification.     

Characteristic Frequency of Carbon Black Filled Rubber

Due to the high electrical conductivity of carbon black (CB) particles, the presence of CB improves the conductivity of filled rubbers. The impedance spectra of CB filled rubber were simulated using an infinite resistor‐capacitor (RC) circuit by considering the tunneling conduction mechanism for the CB contact regions. The calculated results had a similar appearance to the experimental results, i.e., the Cole‐Cole plot was a semi‐circle and a peak appeared in a plot of the imaginary component of complex impedance with respect to the frequency from which the characteristic frequency was obtained. For a simple RC circuit in parallel connection, the logarithm of the characteristic frequency should be a linear function of the 1/3 power of the average number of primary particles per aggregate. A slight deviation from the line found in the simulations was attributed to the network contribution. Additionally, low CB loading had little effect on the characteristic frequency, in accordance with the experimental data, while high loading had a marked effect. Furthermore, the calculations showed that the characteristic frequency was affected not only by the distribution of individual CB aggregates, but also by the percentage of agglomerates at high CB loading.     

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.