Effects of Rice Husk Derived Amorphous Silica on the Thermal-Mechanical Properties of Unsaturated Polyester Composites

Rice husk is rich in amorphous silica which has found various applications as a filler in rubbers and plastics. In the research described here silica was extracted from rice husk ash in the form of sodium silicate which was used to produced amorphous precipitated silica (PS) and silica aerogel (SA) using a sol – gel process and supercritical drying. These materials were then physically mixed with unsaturated polyester (UP) resin and cured at room temperature to form polymer composites. The experimental results showed that the UP composites with 30% (volume percent) of SA filler had lower density and better thermal insulation than the composites with the same amount of PS. Thermogravimetric analysis (TGA) results showed that the T_onset of the PS and SA composites were slightly delayed by 15 and 10°C, respectively. The tensile stress-strain curves showed that addition of the fillers reduced the tensile strength, but increased the elastic moduli of the UP matrix. PS filled UP composites exhibit higher moduli (higher stiffness) than that of SA filled UP composites. This was due to agglomeration and poor adhesion of the SA particles to the UP matrix while better dispersion was observed for the PS filled composite.     

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).     

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.     

Dynamic Fatigue Behavior of Natural Rubber Reinforced with Nanoclay and Carbon Black

The dynamic fatigue behaviors of natural rubber (NR) filled with carbon black (CB) and both nanoclay (NC) and CB at same hardness was evaluated using the stepwise increasing strain test (SIST) and long-term testing. Compared with NR/CB composites, NR/CB/NC nanocomposites exhibited higher fatigue-limited strain, stronger dynamic stress relaxation, and longer compression fatigue life. By examining the fracture morphologies, nonlinear viscoelastic behavior, and hysteresis loss of filled NR, it was found that NR, synergisticly reinforced by NC and CB, exhibited improved anti-fatigue ability than NR filled with CB due to stronger filler–filler interactions between NC and CB (a local filler network) and the high aspect ratio and typical lamellar structure of NC.     

Study on the Tribological Properties of Carbon Fabric Reinforced Phenolic Composites Filled with Nano-Al2O3

Carbon fabric reinforced phenolic (CFRP) composites filled with nano-Al₂O₃ were prepared by a dip-coating and heat molding process and the tribological properties of the resulting composites under different sliding conditions were investigated systematically on a block-on-ring test rig. The worn surfaces were observed in a scanning electron microscope (SEM) to understand the mechanism. Nano-Al₂O₃ particles, as the filler, were effective in reducing the friction coefficient and wear rate of the CFRP composites. The steady state friction coefficient of the CFRP composites filled with 4 wt.% nano-Al₂O₃ particles was about 65.5% of that of unfilled CFRP composites, and the wear rate, in this case, was about 74.7% of that of unfilled CFRP composites. Tribological tests under different sliding conditions revealed that the filled CFRP composites seemed to be more suitable than unfilled CFRP composites for tribological applications under higher sliding speed and load. Moreover, the wear resistances of the unfilled and filled CFRP composites were found to be related to the stability of the transfer film on the counterface.     

Effect of the amounts of glycidyl methacrylate on the mechanical and dynamic properties of styrene–butadiene–glycidyl methacrylate terpolymer/silica composites

GMA-SBRs with GMA contents in the range of 0.06–0.71 wt.% were synthesized and used to evaluate the properties of the silica composites for fuel-efficient tires. The chemical structures of the GMA-SBRs were analyzed using Fourier transform infrared spectroscopy, ¹H nuclear magnetic resonance (¹H NMR), size exclusion chromatography (SEC), and differential scanning calorimetry (DSC). GMA-SBRs can enhance filler–rubber interaction through covalent bond formation between the silica filler and rubber molecules. After compounding, the cure characteristics and mechanical and dynamic properties of the GMA-SBR silica-filled composites were analyzed. The mechanical properties, including the Mooney viscosity, bound rubber, swelling ratio, and moduli, exhibited obvious differences with increasing GMA content. However, the optimum content of GMA in the GMA-SBR, in terms of dynamic properties such as the Payne effect which represents the change in dynamic modulus against the strain to determine the extent of filler flocculation and tan δ at 60 °C representing tire rolling resistance, was ~0.6 wt.%. These results are due to improved silica dispersion, resulting from increased covalent bond formation between GMA-SBR and the silica surface. This approach assists in the determination of functional group contents in functionalized emulsion styrene–butadiene rubber for fuel-efficient tires, leading to a decrease in vehicular greenhouse gas emission.     

Mechanical and microwave absorbing properties of carbon-filled polyurethane

Polyurethane (PU) matrix composites were prepared with various carbon fillers at different filler contents in order to investigate their structure, mechanical and microwave absorbing properties. As fillers, flat carbon microparticles, carbon microfibers and multiwalled carbon nanotubes (MWNT) were used. The microstructure of the composite was examined by scanning electron microscopy and transmission electron microscopy. Mechanical properties, namely universal hardness, plastic hardness, elastic modulus and creep were assessed by means of depth sensing indentation test. Mechanical properties of PU composite filled with different fillers were investigated and the composite always exhibited higher hardness, elastic modulus and creep resistance than un-filled PU. Influence of filler shape, content and dispersion was also investigated.     

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.     

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.     

Investigation of Carbon Black Network in Natural Rubber with Different Bound Rubber Contents

A new method was applied to modify the surface activity of virginal carbon black (VCB). LA‐57, one kind of hindered amine light stabilizer, was adsorbed onto the carbon black surface through a strong shear force induced by the screws of a HAAKE internal mixer. The modified carbon black (MCB) was characterized by FT‐IR and thermogravimetric analysis (TGA). The bound rubber content of the natural rubber (NR) compounded with MCB and VCB varied with the fraction of LA‐57 on the MCB surface. The nonlinear effect at small strains, generally referred as the Payne effect, was investigated in the rubber compounds based on the different bound rubber contents. The NR compound containing the lowest bound rubber content had an obvious Payne effect. Based on the bound rubber content, the types of filler network varied from direct contact mode to the joint rubber shell mechanism.     

Reduced filler flocculation in the silica-filled styrene–butadiene–glycidyl methacrylate terpolymer

This study presents a method to improve the dispersion of silica in rubber compounds using a styrene-butadiene-glycidyl methacrylate terpolymer (GMA-SBR) synthesized by cold emulsion polymerization. It has been demonstrated that silica particles in conventional rubbers tend to agglomerate during storage, as well as at the onset of vulcanization, because of their polarity. GMA-SBR can improve the compatibility with silica by the formation of covalent bonds between the epoxy groups of GMA-SBR and silanol groups on the silica surface. SBR 1721 and GMA-SBR silica-filled compounds were prepared without curatives by a kneader and a two-roll mill. After compounding, the reaction of the epoxy group, filler flocculation, and morphology of the compounds were analyzed using infrared spectroscopy, a rubber process analyzer, and transmission electron microscopy, respectively. In addition, the content of bound rubber in the compounds was determined by extracting the unbound rubber material with toluene. The GMA-SBR silica-filled compounds had a higher bound rubber content and exhibited significantly different filler flocculation and silica dispersion behaviors compared with the SBR 1721 silica-filled compounds.     

In situ Grafting onto Silica Surface with Epoxidized Natural Rubber via Solid State Method

An in situ solid state grafting reaction between epoxidized natural rubber (ENR) and silica was performed in a Haake internal mixer. Resulting ENR‐grafted silica was characterized by Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA) measurements. Based on these results, it was concluded the silanol groups (Si‐OH) of silica caused the ring opening of ENR oxirane rings so that ENR was grafted onto the silica surface. Transmission electron microscopy (TEM) photographs showed ENR‐grafted silica had better dispersibility and smaller aggregates compared with the original silica. Dynamical mechanical analysis (DMA) of vulcanized rubber compounds contained ENR‐grafted silica showed the glass transition temperature (T _g) of grafted ENR molecules shifted to higher temperature, from ?3°C to 20°C, indicating the mobility of ENR was greatly restricted. As a result, the compounds containing ENR‐grafted silica have higher hysteresis, and can be applied in a much wider field, such as damping materials, tires of racing cars, and so on.     

Filler effect on formation and properties of reinforced interpenetrating polymer networks

The formation processes of unfilled and filled interpenetrating polymer networks (IPNs) and some of their physico-mechanical properties have been investigated. The formation kinetics and constituent network curing rates determine the rate and degree of microphase separation. This in turn determines the boundary layer composition and structure. Introduction of filler into the IPN during formation affects greatly the crosslinking reaction and the microphase segregation of homopolymers. It has been shown that the degree of phase segregation in filled IPNs differs from that in unfilled ones. All the fillers were found to shorten the time of internal stress appearance and to increase its value for IPNs with predominantly high-modulus component content. Some filled IPNs were shown to have greater thermodynamic stability than unfilled ones.     

Four Non-Gaussian-Type Tube Models of Rubber-Like Elasticity: Analysis of Tensile Data for Lightly and Highly Carbon-Black Filled Styrene-Butadiene Elastomers

Recently, using a new, non-Gaussian, tube-based entropy model for active-filler filled elastic networks with the polymer phase influenced by the filler loading, proposed by the author, a data analysis of literature tensile data for carbon-black filled styrene-butadiene rubber (SBR) networks of different loadings was carried out; the data-fittability and the particular influence of the filler loading were examined in detail. In this report, the data-fitting performances of three other non-filled network models, all tube-based and finite chain extensible, along with a common strain-amplification factor that is necessary to extend them to the analysis of the filled networks, as well as the model which was employed in the above study were compared. As tensile data for this analysis, those observed for the same unfilled SBR, the same lightly loaded SBR and one of the same highly loaded SBR networks, as in our previous study, were chosen.     

Tribological Properties of Surface-Modified Graphene Filled Carbon Fabric/Polyimide Composites

To improve the wear resistance of carbon fabric reinforced polyimide (CF/PI) composite, surface-modified graphene (MG) was synthesized and employed as a filler. The flexural strength, Rockwell hardness and thermal properties of the composites were tested. The composites were also evaluated for their tribological properties in a ring-on-block contact mode under dry sliding conditions. The results showed that the wear rate of MG reinforced CF/PI composites was reduced when compared to unfilled CF/PI composite. It was found that the 1?wt% MG filled CF/PI composites exhibited the optimal tribological properties. The worn surface, wear debris and transfer films were analyzed by scanning electron microscopy (SEM) and optical microscopy (OM) with the results helping to characterize the wear mechanism.     

Influence of filler type on wet skid resistance of SSBR/BR composites: Effects from roughness and micro-hardness of rubber surface

The wet skid resistance (WSR) of SSBR/BR(solution styrene-butadiene rubber/butadiene rubber) composites filled with carbon black, silica, and nano-diamond partly replacing carbon black or silica, respectively, was measured with a portable British Pendulum Skid Tester (BPST). A dynamic mechanical thermal analyzer was used to obtain the viscoelasticity of the composites. A 3D scanning white-light interfering profilometer was used and the scratch test performed to characterize surface roughness and micro-roughness, respectively, of the composites. WSR of the silica-filled composite was better than that of the carbon black-filled one, and further enhancement of WSR was obtained by replacing silica with nano-diamond. Tan δ of the composites at 0 °C, 10 Hz, and tensile strain of 2% did not show good correlation with WSR. The surface roughness of the composites had effects on WSR. The scratch test indicated that the higher the hardness of the filler in the composite, the higher the micro-hardness and the better the WSR. Therefore, the surface micro-hardness of the composites is an important factor affecting WSR, besides viscoelasticity and surface roughness.     

Carbon Black Filled Powdered Natural Rubber

Carbon black (CB) filled powdered natural rubber [P(NR/N234)] was prepared using a patented method of latex/CB coagulation technology. The influence of curing recipes and CB contents on the curing, mechanical, and dynamic properties were studied in depth, and the results were compared with that of NR/N234 compounds based on traditional dry mixing of bale NR and CB. The results showed that, compared with NR/N234, P(NR/N234) showed higher tensile strength, tear strength, rebound elasticity and flexibilities, and the antiabrasion properties were similar, while the dynamic temperature-build-up and dynamic compression permanent set were about 50% of that of NR/N234. The analysis based on scanning electron micrographs (SEM) and the Payne effect showed that the fine dispersion of CB in the rubber and the enhanced interaction between CB and rubber contributed to the excellent properties of P(NR/N234), sufficient that they make P(NR/N234) a potential material for the tread compounds of heavy-duty all-steel cord radial tires.     

Aerosols emitted by the combustion of polymers containing nanoparticles

The fire behavior and the characterization of solid and gaseous fire effluents of polymers [polymethyl methacrylate (PMMA) and polyamide-6 (PA-6)] filled with nanoparticles (silica, alumina, and carbon nanotubes) used to improve their flame retardancy were investigated. To determine the impact of these composites on the emission of airborne particles produced during their combustion in accidental fire scenarios, an experimental setup was developed to measure the mass distribution in the 30 nm–10 μm range, and the concentrations of submicrometric particles in the aerosol. Comparisons were made between unfilled and filled polymers, and the influence of filler surface treatments (silane-based), as well as combinations with a flame retardant [ammonium polyphosphate (APP)], was investigated. The presence of nano-oxides in PMMA shows a significant effect on the rate of particle emission with a decrease in the concentration of the emitted submicrometric particles. APP in PMMA led to a decrease in the mass fraction of ultrafine particles and an increase in the rate of submicrometric particle emission compared to filled compositions with nano-oxides. Atomic force microscopy was used as a complementary tool for the characterization of the particles emitted during combustion, allowing direct observation of nanoparticle morphology, detection of carbon nanotubes in the aerosol, and visualization of the effect of APP on nanoparticle morphology.     

Effect of Wood Flour on the Curing Behavior,Mechanical Properties,and Water Absorption of Natural Rubber/Wood Flour Composites

The preparation of natural rubber/wood flour (NR/WF) composites and the influence of WF content, modification, and particle size on the vulcanizing behavior, mechanical properties, and water absorption of NR/WF composites are described. Results show that the addition of WF into NR delayed the scorching time and vulcanizing time of NR. The appropriate WF contents can improve the mechanical properties of NR. However, the overloading of WF destroys the mechanical properties of NR. The addition of WF increased the water absorption of NR. The silicone couple agents that were used to modify the WF had little effect on the water absorption of NR/WF composites. Decreasing the WF particle size enhanced the water absorption of NR/WF composites because the water-absorbing surface area increased with decreasing WF particle size. The water absorption of sisal-fiber-filled NR-based composites was larger than that of the WF-filled NR-based composites. A useful equation, w=ktⁿ , was inferred from the water absorption results to calculate the water absorption (w) of the NR/WF composites as a function of time (t), where k was a constant concerning the compounds’ character that was primarily determined by the WF's character and n was the power of time that was related to the NR's inherent character, such as cross-linking density, and primarily determined the water absorption rate.     

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.