1H pulse NMR analysis of silane-treated layers on glass fiber surfaces

The surface treatment of a glass fiber using mercapto-functional silane coupling agent having a di- or trialkoxy group has been studied. The surface of silane-treated fiber is observed by scanning electron microscopy. The treated layer looks hard like glass for the trialkoxy silane-treated, whereas it looks soft for the dialkoxy silane-treated. Molecular mobility of the treated layer is analyzed by ¹H pulse nuclear magnetic resonance spectroscopy. The amount of silane loading increases with increased silane concentration in the treatment solution. The relaxation time for the surface layer is longer for the dialkoxy structure than for the trialkoxy structure. The silane chain is flexible in the dialkoxy structure, but is rigid for the trialkoxy structure, independent of the loading amount of silane. The relaxation behavior for the mixture of the di- and trialkoxy structures is between those of the pure dialkoxy and trialkoxy structures and depends on the mixing ratio. The network density of silane chains on the glass fiber can be controlled by varying the mixing ratio of the di- and trialkoxy compounds.     

Surface treatment of CaCO3 with a mixture of amino- and mercapto-functional silane coupling agents and tensile properties of the rubber composites

In order to reinforce the composite consisting of isoprene rubber (IR) and calcium carbonate (CaCO₃) particles, the surface treatment of CaCO₃ particles with a mixture of amino- and mercapto-functional silane coupling agents was investigated. The quantity of chemisorbed silanes in treated CaCO₃ measured using thermogravimetry was greater for amino- than for mercapto-silane and for the tri- than for the dialkoxy structure. Second, the molecular mobility of polycondensate of the mixtures with the trialkoxy structure measured using ¹H pulse nuclear magnetic resonance had the least molecular mobility, i.e., formed the highest density network. The greater values of stress at 500% strain, fracture stress, and elongation at break were determined for the treatment with amino- and mercapto-functional silanes having a trialkoxy structure from the stress-strain curves of composite. The mixture treatment with dialkoxy structure and with amino- or mercapto-functional silane only did not improve the mechanical properties sufficiently. Interactions between the amino group and the CaCO₃ surface, covalent bonding between the mercapto group and the IR, and high density network formation of trialkoxy silane were important for improving the mechanical properties of the composite.     

Mechanical properties of poly(vinyl chloride)/silane-treated glass beads composite: effects of organofunctional group and alkoxy group numbers of silane coupling agent

The surface treatment of glass beads, chosen as model filler, is carried out using four kinds of silane coupling agents with multilayer coverage. For this purpose, the silanes having aminopropyl or methacryloxypropyl group as an organofunctional group with two or three alkoxy group numbers are used. The amount of silane detected on the bead surface is 4–6 times that required for monolayer coverage. Using these treated beads, the effects of the organofunctional group and the alkoxy group numbers of silanes on the mechanical properties of the bead-filled poly(vinyl chloride), chosen as a typical ductile polymer, were investigated. Higher yield stress was observed in the silane with aminopropyl group than with methacryloxypropyl group. The effect of alkoxy group numbers was more effective in the dialkoxy than trialkoxy silanes. Scanning electron microscopy shows improvement in the interfacial adhesion by the silane treatment in the above order. The interfacial debonding at the yield point is depressed.     

Influence of coupling agent chain lengths on interfacial performances of polyarylacetylene resin and silica glass composites

The influence of chain lengths on interfacial performances of polyarylacetylene (PAA)/silica glass composites was studied. In order to obtain different chain lengths on substrates, methyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane and dodecyltrimethoxysilane were grafted onto silica glass surface. Topographies of silica glass surface and the wetting ability of PAA resin on silica glass surface were characterized by atomic force microscopy (AFM) and surface free energy along with contact angles, respectively. At the same time, the interfacial adhesion was evaluated by shear strength testing. The failure mechanisms of composites were also analyzed by fracture morphologies. The results of the study indicate that with chain lengths of coupling agents on silica glass surface increasing, interfacial shear strengths of PAA/silica glass composites increase, while the wetting ability of PAA resin on silica glass surface decreases. The main mechanism for the improvement of the interfacial adhesion is physical entanglement interaction between the chain of coupling agent and the chain of PAA resin.     

The relaxational behavior of heterogeneous polymers

Stress-relaxation data are presented for two commercial grades of ABS and an ABS-polycarbonate blend over a temperature range which includes the glassy, transition, and entanglement regions. Reduced master curves and the shift factor, a_T, are obtained and compared to data for fractionated polystyrene and polycarbonate; the principle of time-temperature superposition is shown to be as applicable to the relaxation data for these heterogeneous polymers as to similar data for homogeneous polymers. Compared with homogeneous polymers, the reduced curves for the composites are different in several ways: A slightly larger negative slope in the glassy region, a more diffuse transition region, a higher and broader entanglement plateau, and a smaller negative slope in the flow region are noted. For the two ABS polymers, the temperature dependences of a_T are about that of a homogeneous polymer with an equivalent Tg, indicating that the discrete rubber particles do not alter the relative relaxational behavior of this heterogeneous system. For the ABS-polycarbonate blend (both phases continuous), the temperature dependence of a_T is close to that of the polycarbonate component. suggesting that in this case the continuous phase with the longest relaxation times dominates the relaxational behavior of the composite.     

In situ near infrared evanescent wave examination of surfactant adsorption on silica optical fibers

The use of composite materials has increased considerably in the past 30 years. However, many of the molecular level processes occurring in the interfacial region have yet to be investigated. In this regard, an in situ Fourier transform near infrared technique has been demonstrated herein. This technique utilizes a seven-fiber bundle to examine monolayer and sub-monolayer level surfactant adsorption at the silica optical fiber/solution interface. It is felt that this technique will greatly increase the knowledge of the processes involved in the improvement of mechanical properties of silane treated composites.     

Interfacial effects in short sisal fiber/maleated castor oil foam composites

In this study, bio-foam composites are produced using short sisal fiber as the reinforcement and modified castor oil as the matrix, respectively. The foam composites with an average cell size of 200 μm possess properties similar to those of commercial polyurethane foams. The effects of fiber loading, fiber length and foam density on the compressive properties of the foam composites are reported in relation to the interfacial interaction. It is found that the addition of chopped sisal alters cell structure of the foam. Surface pre-treatment of sisal by alkali or silane coupling agent helps to improve the mechanical properties and interfacial adhesion. The exposure of the fibers to the gas cells of the foam reduces the effectiveness of interfacial effect, which is different from the case of conventional bulk composites. As a result, the reinforcing ability of sisal fibers becomes a function of fiber length and so on.     

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).     

Effect of silica type and concentrations on the physical properties of EPDM cured by γ -irradiation

This paper reports the results of studies on the thermal and electrical properties of gamma radiation cured composites based on ethylene propylene dieyne rubber (EPDM) reinforced with different concentrations of micro- and nano-silica. The effect of gamma irradiation in the presence of ethylene glycol dimethacrylate (EGDM) as radiation sensitizer on melt flow properties of EPDM was also studied. Thermogravimetric studies of the composites show that the degradation of vulcanizates is controlled mainly by the silica type and its concentration. Increasing the amount of micro- or nano-silica in the vulcanizate decreases the maximum rate of decomposition of the major degradation step compared with that of the unfilled-cured one. The micro- and nano-composites exhibited remarkable heat resistance properties compared with that of the pure EPDM as the filler dispersion of silica inhibited the thermal degradation of the polymeric matrix, which led to the micro and nano-composites showing great improvement in thermal stability. A considerable change in decomposition rate is observed by increasing filler loading from 10 to 39 phr. The dielectric properties of such composites are affected by the silica type and concentration. The dielectric constant and ac-conductivity for all composites were found to increase with increasing silica loading, which is mainly due to the interfacial polarization. The ac-conductivity values of silica/EPDM composites exhibit a strong frequency dependence with both fillers used. The conductance and dielectric constant values have been fitted using a conduction model for all samples.     

Comparison of Structure,Morphology, and Properties of Miktoarms Star Styrene-Butadiene Rubber and Star-Shaped Styrene-Butadiene Rubbe/Polybutadiene Rubber Blends

Four miktoarms star-shaped polybutadiene-Sn-poly(styrene-butadiene) rubber (MSS-PB-PSBR) with 1,1-diphenylhexyl at the ends of the arms were prepared by two different coupling techniques. One technique was a one-step technology, from which two miktoarms star styrene-butadiene rubbers, called AMSS-PB-PSBR, were obtained in which the four arm stars had varying ratios of PB:PSBR arms; another was a two-step technology, from which another two miktoarms star styrene-butadiene rubbers, called BMSS-PB-PSBR, were obtained in which all consisted of PB-Sn-(PSBR)₃ stars. The molecular structure parameters and morphology-properties of the four MSS-PB-PSBR were determined and studied, and compared with that of a star-shaped styrene-butadiene rubber (S-SSBR)/poly butadiene rubber (PBR) blend. The results showed that the total coupling efficiency (the ratio of the total number of polymer chains (arms) coupled by SnCl₄ to that of the total number of polymer chains) of the MSS-PB-PSBR was higher than 60%. However, the coupling efficiency of the polybutadiene arms of BMSS-PB-PSBR was obviously higher than that of the AMSS-PB-PSBR. Compared with the S-SSBR/PBR blend, MSS-PB-PSBR had a more uniform distribution of the PB phase and a smaller phase size of PB. It was found that MSS-PB-PSBR composites filled with carbon black (CB) had a lower Payne effect than the S-SSBR/PBR/CB composite, with the BMSS-PB-PSBR/CB composites being especially lower. The BMSS-PB-PSBR/CB composites had higher mechanical properties and lower rolling resistance than the AMSS-PB-PSBR/CB composites due to the high coupling efficiency of the polybutadiene arms; the results indicated that the two-step technology was better than the one-step technology for preparing the tread material of “green” tires.     

Effect of Fiber Surface Modification on the Interfacial and Mechanical Properties of Kenaf Fiber-Reinforced Thermoplastic and Thermosetting Polymer Composites

The surfaces of kenaf fibers were treated with three different silane coupling agents. 3-glycidoxypropyltrimethoxy silane (GPS), 3-aminopropyltriethoxy silane (APS), and 3-methacryloxypropyltrimethoxy silane (MPS). Among them, the most effective one for the property improvement was GPS when it was applied to the kenaf fiber surfaces at 0.5 wt%. Thermoplastic polypropylene (PP) and thermosetting unsaturated polyester (UPE) matrix composites with chopped kenaf fibers untreated and treated at different GPS concentrations from 0.1 wt% to 5 wt% were fabricated using compression molding technique. The present study demonstrates that the interfacial, flexural, tensile, and dynamic mechanical properties of both kenaf/PP and kenaf/UPE composites importantly depend on the GPS treatments done at different concentrations. The greatest property improvement of both thermoplastic and thermosetting polymer composites was obtained with the silane treatment at 0.5 wt% and the mechanical properties were comparable with E-glass composites prepared the same polymer matrix under the corresponding fiber length and fiber loading. The results also agreed with each other with regard to their interfacial shear strength, flexural properties, tensile properties, storage modulus, with support of fracture surfaces of the composites.     

Oxygen Barrier Properties of Waterborne Polyurethane/Silica Hybrids

The oxygen barrier properties of films obtained from waterborne polyurethane/silica hybrid dispersions were analyzed. Two different types of polyurethanes were used, based on poly(propylene glycol) and poly(1,4-butylene adipate). Three different strategies were followed in the preparation of the hybrid dispersions. In the first type of materials (series 1), the inorganic part came exclusively from the covalent incorporation of trifunctional silane groups into the polymeric chains. The other two series contained, in addition to the trifunctional silane groups, tetrafunctional silane groups either physically blended (series 2) or “in situ” generated (series 3). Materials of series 1 showed an increase of the oxygen permeability coefficient with the silane content. However, the other two types of materials presented just the opposite dependence. In this latter case, the systems containing “in situ” generated silica (series 3) presented higher permeability coefficient values, probably because of the steric hindrance imposed by the polyurethane that gave rise to silica networks containing silanol groups and free volume holes. Moreover, lower permeability coefficient values were obtained when larger size particles were added. This fact could mean that the polyurethane/silica interface effects were not totally hindered even when the organic/inorganic phases were covalently bonded.     

AFM Observation of a Mica Surface Treated with Silane Coupling Agent Having a Mercapto Group

The topography of mica surface after treatment with silane coupling agent having a mercapto group was studied using an atomic force microscope. The cleaved mica plate was used as a model inorganic surface. The effect of treatment condition on the topography of the mica surface was investigated. Agglomerates consisting of self-condensed silane molecules were observed on the surface. However, their amount and size were smaller than those for silanes having other organo-functional groups such as amino, methacryloxy and vinyl groups. Aqueous and water/2-propanol mixture solutions gave a smoother surface as compared with a 2-propanol solution. There was no significant influence discernable from di- and trialkoxy structures. The aqueous solution of silane coupling agent having a mercapto group showed an acidic pH. This was the reason why the smoother silane-treated layer was formed by the silane with the mercapto group than by those with other organic functional groups, because the silanol group generated by hydrolysis is stable in an acidic pH.     

Synthesis of spin labelled silica and EPR molecular dynamics study at silica–polymer interfaces

Information concerning the interface structure in filler/polymer composites is of key importance for the rationalization of reaction mechanisms in mechano‐chemical (extrusion, blending, etc.), thermal or radiation induced free radical processes and for elucidating the factors underlying the reinforcing mechanism. The analysis of the chain dynamics is a suitable tool for undertaking such investigations because any reactivity parameter (rate constants, collisional frequencies, activation energies) and bonding interactions are strictly related to the mobility of the interacting centres. EPR spectroscopy coupled with specific spin labelling at the filler/polymer interface is a tool for making such novel perspective available. In this work, a spin labelling study of the molecular motion at the filler–rubber interface in a silica–SBR blend is reported. Spin labels of different length, spanning a 9–11 Å depth and linked to the surface of silica particles, were prepared and used for determining the rotational diffusion tensors, the T₅₀ and order parameter in silica/SBR interfaces. The measurements carried out as a function of the temperature in comparison with unbound spin probes dispersed in the rubber matrix have afforded information consistent with the structure of the interfaces predicted by molecular–level theoretical models. Copyright © 2010 John Wiley & Sons, Ltd.     

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.     

Structure of polymer solutions at interfaces: a Monte Carlo simulation study

The canonical ensemble Monte Carlo method is applied to study the structure of polymer solutions confined between surfaces. The polymer molecules are modeled as fused-sphere freely rotating chains with fixed bond length and bond angles and the solvent as hard spheres. The simulation results for the configurational and conformational properties of the chains are presented with varying interfacial distances, chain concentrations, and chain lengths. The chains are depleted at the wall at lower density, which, however, becomes less at higher density. With an increase in the interfacial distance, the enhancement/depletion of the chains at the wall becomes more marked. At all interfacial distances and chain lengths, increasing the concentration of the solvent makes the oscillation in the density profile of the chains more pronounced. Conformational properties provide important indications regarding the behaviour of chains as they approach surfaces.     

Effects of three-body interactions on the dynamics of entanglement in spin chains

With the consideration of three-body interaction, dynamics of pairwise entanglement in spin chains is studied. The dependence of pairwise entanglement dynamics on the type of coupling, and distance between the spins is analyzed in a finite chain for different initial states. It is found that, for an Ising chain, three-body interactions are not in favor of preparing entanglement between the nearest neighbor spins, while three-body interactions are favorable for creating entanglement between remote spins from a separable initial state. For an isotropic Heisenberg chain, the pairwise concurrence will decrease when three-body interactions are considered both for a separable initial state and for a maximally entangled initial state, however, three-body interactions will retard the decay of the concurrence in an Ising chain when the initial state takes the maximally entangled state.     

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.     

Determination of interfacial material constants in plain glass woven fabric composites using finite element analysis

Numerical analysis with the finite element method (FEM) was used in order to identify interfacial material constants of plain glass woven fabric composites under mode I loading. Relations between strength, stress intensity factor, and modulus in the interphase which were correlated with the onset of unstable fracture were determined. As a result, it was reasonable that the interfacial moduli were between 2.8 and 8.4 GPa which corresponds to one to three times the resin modulus. It was suggested that the increase of concentration of silane coupling agent has led to an increase of the interfacial strength. Changing of fracture mechanisms from unstable to stable crack propagations was explained through the interfacial material constants.     

Effect of Modified Nano-Silica on the Reinforcement of Styrene Butadiene Rubber Composites

The performance of styrene butadiene rubber (SBR) composites filled with nano-silica has been improved by surface modification of the nano-silica using silane coupling agents. The dispersion of nano-silica in SBR rubber and the bonding force of nano-silica with SBR were significantly improved, and the physical and mechanical properties of the vulcanized rubber were greatly improved. The results showed Si69 (bis-(γ- triethoxysilylpropyl)-tetrasulfide) was the best modifier among the six silane coupling agents used in the experiments, and its optimum amount was 12% (wt) of nano-silica.