Tensile properties of styrene-butadiene rubber/silica composites with mercapto functional silane coupling agents: influences of loading method and alkoxy group number

The influences of alkoxy group number and loading method of silane coupling agents on the mechanical properties of a styrene-butadiene rubber/silica composite were investigated. Mercapto functional silane coupling agents with dialkoxy and trialkoxy structures were used. The pre-treatment method and the integral blend method were compared. Both the fracture stress and modulus at 200% strain were higher in the pre-treatment than in the integral blend for dialkoxy type composites. However, they were higher in the integral blend than in the pre-treatment for trialkoxy-type composites. The interaction between the silane chains on the silica surface and the rubber molecular chains at the interfacial region was estimated by ¹H pulse nuclear magnetic resonance spectroscopy using an unvulcanized silica/rubber mixture. It was found that the binding of rubber molecular chains by the silane chains was higher in the pre-treatment system for dialkoxy-type composites, whereas it was higher in the integral blend for trialkoxy-type composites. The reason is proposed as follows: in the pre-treatment for dialkoxy type, a linear silane chain formed in the case of multi-layer coverage. The silane chain entangled with the rubber chain in the interfacial region and improved the reinforcement effect. For the trialkoxy type, a network structure formed using the pre-treatment method, lowering the amount of entanglement. However, in the integral blend for trialkoxy type, the formation of the silane network and the entanglement progressed simultaneously during the preparation process. A well-entangled interfacial region was formed.     

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.     

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.     

Topographical observation of silane-treated inorganic surface using atomic force microscopy

The topography of the silane-treated layer on an inorganic surface was observed using an atomic force microscope. For this purpose, the cleaved mica plate was treated with some silane coupling agent at varying conditions. The silanes having aminopropyl or methacryloxypropyl group as organofunctional groups with di- or trialkoxyl structures were used. Three different solvents for silane solution — 2-propanol, 2-propanol/water mixture and water — were used. The pH of the aqueous solution was controlled. As a result, the most suitable solvent and pH in order to obtain smooth silane layer was clarified. The solubility of silane molecules in the solution, the wettability of silane molecule onto inorganic surface, and prevention of the mutual condensation of silane molecules in the solution were found to be important parameters for this purpose.     

Fixation of silane coupling agents to glass fiber in silane treatment process

Fixation of silane coupling agents to glass fiber was quantitatively determined using pyrolysis-GC/FT-IR to explore the formation of chemical-bonded and physisorbed silanes. The silane coupling agent used was N-phenyl-1-aminopropyltrimethoxysilane (AnPS). In silane treatment, E-glass fiber was dipped into acetic acid solution containing AnPS and was cured under different temperature and time. The fixation of silane was obtained by determining the amount of AnPS at the glass surface after and before washing the treated fiber with methanol. The silane fixation increased with decrease in the silane concentration, but it fell significantly below a lower silane concentration. The change of fixation in curing temperature gave an optimum temperature for the fixing. The dependence of curing time on the fixing ratio showed that the fixation was depressed below the curing temperature of 100°C. These results suggested that more than a specific amount of AnPS deposit on glass fiber was necessary to form silane networks fixed to glass fiber through siloxane bonds. The networks formation was interpreted in terms of the competitive reaction of the silanol group of silane to hydroxyl of glass fiber and to other silane molecules.     

Investigation on resin interphase produced near silane-treated glass fiber in vinyl ester resin

In order to investigate the reaction of silane-treated glass fiber with thermosetting resin, a set of spectra were measured near the interface between the glass fiber and vinyl ester resin using microscopic FT-IR spectroscopy. A thin-sliced sample was made from glass fiber/vinyl ester resin composite to be subjected to the spectroscopy. The spectra were obtained through a 20 × 40 μm of a mask window at each 20 μm step from the glass strand area to the matrix resin. The intensity at 1450 cm^-1 of the spectra decreased from the glass strand area to the matrix resin. It was noticed, however, that the intensity kept the same value even in the matrix at a distance of 80 μm from the glass strand area. This meant that the resin in such an area was denatured by the reaction of silane to resin at the surface. This mechanism was supported by the significant size of the denatured area, which increased with amounts of silane at the surface of glass fiber.     

Improvement of resin impregnation into glass cloth by silane treatment in resin transfer molding

An evaluation method was proposed for resin impregnation using resin transfer molding of unsaturated polyester matrix composites with silane-treated glass cloth. The determination of whitening of the composite was carried out as a parameter of incompleteness of resin impregnation. The change of whitening with silane concentration was compared with the bending modulus as a parameter of chemical reinforcement. The materials used were unsaturated polyester resin as a matrix and methacryloxypropyltrimethoxysilane as a silane coupling agent for glass cloth. Resin transfer molding was used to produce four plies of glass cloth laminates by impregnating the resin. The silane-treated glass cloth repressed whitening above 0.026 w/w% of silane in aqueous solution, while the chemical reinforcement due to silane gave no appearance below 0.2 w/w% based on the bending test of the laminates. The large difference between the concentrations suggested that silane has a couple of functions, that is, chemical reinforcement and physico-chemical resin wettability.     

Role of curing conditions and silanization of glass fibers on carbon nanotubes (CNTs) reinforced glass fiber epoxy composites

Curing behavior of amino-functionalized carbon nanotubes (ACNT) used as reinforcing agent in epoxy resin has been examined by thermal analysis. Experiments performed as per supplier’s curing conditions showed that modification of the curing schedule influences the thermo-mechanical properties of the nanocomposites. Specifically, the glass transition temperature (T_g) of ACNT-reinforced composites increased likely due to the immobility of polymer molecules, held strongly by amino carbon nanotubes. Further, a set of composites were prepared by implementing the experimentally determined optimal curing schedule to examine its effect on the mechanical properties of different GFRP compositions, while focusing primarily on reinforced ACNT and pristine nanotube (PCNT) matrix with silane-treated glass fibers. From the silane treatment of glass fibers in ACNT matrix composition it has been observed that amino silane is much better amongst all the mechanical (tensile and flexural) properties studied. This is because of strong interface between amino silane-treated glass fibers and modified epoxy resin containing uniformly dispersed amino-CNTs. On the other hand, PCNT GFRP composites with epoxy silanes demonstrated enhanced results for the mechanical properties under investigation which may be attributed to the presence of strong covalent bonding between epoxy silane of glass fiber and epoxy–amine matrix.     

Effect of silane/nano-silica on the mechanical properties of basalt fiber reinforced epoxy composites

The present study explains the role of surface modification of constituent materials on composite material performance. The influence of silane and nano-hybrid coatings on mechanical properties of basalt fibers and composite materials on their base was investigated. Infrared spectroscopy indicated that modification of basalt fiber surface and nano-SiO₂ was successfully applied. The surface modification leads to the significant increase in the tensile strength of basalt fibers compared to the non-coated fibers. The tensile strength of silane-treated fibers was established 23% higher than the non-coated fibers, indicating that silane plays a critical role in the strength retention of basalt fibers. Also it was pointed out that silane coupling agents can be used for the preparation of the nano-hybrid coating. Addition of SiO₂ nanoparticles into the fiber surface was incorporated to enhance the interfacial bonding of basalt fiber reinforced epoxy composite.     

Interfacial Properties of Phosphate Glass Fiber/Poly(caprolactone) System Measured Using the Single Fiber Fragmentation Test

Phosphate glass fiber of the composition 20Na₂O–24MgO–16CaO–40P₂O₅ was produced using an in-house fiber drawing rig. The interfacial properties of the phosphate glass fiber/poly(caprolactone) (PCL) system were measured using the single fiber fragmentation test (SFFT). The system was calibrated using E-glass fibers and polypropylene system. This gave an interfacial shear strength (IFSS) of 4.1 MPa, which agrees well with other published data. The IFSS for the unsized (as drawn) phosphate glass fiber/PCL system was found to be 1.75 MPa. Fibers treated with 3-aminopropyl-triethoxy silane (APS) showed an IFSS of 3.82 MPa. X-ray photoelectron spectroscopic (XPS) analysis of unsized and silane sized fibers established the presence of silane on the fiber surface. Degradation tests of the silane treated fiber/PCL samples were carried out in deionised water at 37°C and it was found that the IFSS values decreased over time. Four others silanes were also investigated but APS gave the highest IFSS values.     

切向气流作用下玻璃纤维复合材料的激光辐照效应

实验研究了样品表面有切向空气气流、切向氮气气流和无气流时,976 nm连续激光对玻璃纤维增强E-51环氧树脂复合材料的辐照效应。结果表明:无气流时,喷出的热分解产物会对入射激光产生屏蔽作用;有气流时,激光对玻璃纤维的破坏方式是其升温熔化后再被切向气流带走;当激光功率密度较低时,切向空气气流以加强样品表面的对流冷却作用为主,不利于激光对玻璃纤维复合材料的破坏;当激光功率密度较高时,切向空气气流以降低屏蔽作用和提供氧气助燃为主,有利于激光对玻璃纤维复合材料的破坏。三种气流状态下,质量损失随功率密度呈现单调增加趋势,当入射激光功率密度在100~600 W/cm2范围内,随着功率密度的增大,激光能量的利用效率逐渐增大并趋于稳定。     

Fiber optic flow and cure sensing for liquid composite molding

The Polymer Composites group at the National Institute of Standards and Technology has efforts in both on-line flow and cure sensing for liquid composite molding. For our flow program, a novel fiber optic real-time sensor system has been developed that can sense resin at various locations on a single fiber using long-period gratings and a polychromatic source. The sensor operation and characterization will be discussed along with sensor performance during mold filling with various types of reinforcement. The cure sensing program focuses on the interface-sensitive fluorescence response of a dye molecule grafted to a high-index glass fiber. The fluorescence emission of the fluorophore undergoes a blue shift as the resin cures. The fluorescence sensor is made by grafting a silane functional fluorophore onto the surface of the glass with close attention to layer thickness. Fluorescence emission of the grafted fluorophore film is shown to be sensitive to epoxy resin cure, co-silane, and layer thickness. The response of the grafted fluorophore to cure on a high-index fiber is demonstrated.     

Tilted smectic layers of a liquid crystal between homeotropically treated plates

We investigated SmC^* films sandwiched between silane coated glass plates and observed formation of textures exhibiting a uniform tilt of the smectic layers with respect to the boundary plates. The layer tilt angle increases from zero to as the sample is cooled from the smectic A phase to room temperature. These films show linear electro-optical effects because the permanent polarization can be aligned so that it has a component parallel to the applied field without changing the layer structure. Our analysis indicates that mainly two effects determine the layer tilt. On the one hand, the surface tension tends to minimise the layer tilt. On the other hand, the surface energy promotes the director to be normal to the boundary plates. Received 17 July 1998     

Interfacial strength in glass fibre-polypropylene composites: influence of chemical bonding and physical entanglement

For glass fibre–polypropylene (PP) composites, the non-polar nature of polypropylene presents a problem. The present investigation shows that it is necessary to introduce a functionalised PP, for example PP-g-MAH, in order to enhance the bond strength between the PP matrix and aminosilane treated glass fibre. To achieve a better bonding between the substances, three different systems (1–3) in addition to a reference system (0), have been investigated in this study. The two first are based on PP-g-MAH coupling agents, with different concentrations of acid anhydride groups, and the third is a directly reacting system. In the first system, the silane treated glass fibre is exposed to molten mixture of 95 wt% PP homopolymer and 5 wt% PP-g-MAH. In the second system, the silane treated glass fibre is covered by a thin layer of PP-g-MAH and thereafter exposed to the molten PP. The interfacial shear strength is highest for the systems with the pre-compounded graft-copolymer. The resulting influence of the selected coupling systems on the interfacial bond strength of single fibre composite is studied by fragmentation testing. The intermolecular shear strength between fibre and matrix increases with the intermolecular entanglement length of the PP-g-MAH and not by the degree of functionalisation. The PP-g-MAH mixed into the PP gave better results than the route of first covering the glass fibre with a thin layer of PP-g-MAH. This is explained in terms of the probability of generating entanglements and in terms of a weak boundary layer at the glass surface. This conclusion is also supported by the results from using the third principle, i.e. direct reaction between the PP matrix and azidosilane treated glass fibres.     

Preparation of graphene-glass fiber-resin composites and its electromagnetic shielding performance

The surface of the glass fiber (GF) was modified by silane coupling agent (KH550) and bovine serum albumin (BSA), and then the graphene oxide (GO) was coated onto the modified surface of the glass fiber. Followed by a reduction reaction, the reduced graphene oxide (RGO) coated on glass fiber was obtained. Finally, the reduced graphene oxide-glass fibers (RGO-GF) were combined with unsaturated resins. The interfacial morphology of reduced graphene oxide-glass fibers was investigated by scanning electron microscopy (SEM). The structure of the materials was analyzed by Fourier transform infrared spectroscopy (FT-IR). The crystal phases of the material were identified by X - ray diffraction (XRD). The mechanical properties and electromagnetic shielding effectiveness of the sample were tested. The results showed that the interface between glass fibers and graphene binds more closely after the glass fibers was treated by KH550. The tensile strength of the RGO-GF composites reached 85.05 MPa. Compared with the GF composites, it increased by 51.4% when the glass fibers content was 30%. The shielding effectiveness of the composites reached 21.3 dB at the frequency range of 8.2–12.4 GHz (x-band). Therefore, by coating the surface with reduced graphene oxide, the glass fibers can make a great shielding effect on the electromagnetic wave.     

Hydrolytically Stable Interphase on Alumina and Glass Fibers via Hydrosilylation

The poor hydrolytic stability of silane interphase greatly limits the use of fiber reinforced composites (FRC) in demanding applications in which the FRC part is permanently exposed to a moist environment such as in prosthetic dentistry and orthodontics. To improve hydrolytic stability of the interphase between the matrix composed of a blend of triethyleneglycol dimethacrylate (TEGMA) and bisphenol A glycidylmethacrylate (Bis–GMA) monomers and glass or alumina oxide fibers, a two-step hydrosilylation procedure was employed. The process consisted of creating hydride intermediate on the fiber surface followed by hydrosilylation reaction attaching the unsaturated organic monomer (Bis–GMA) forming stable –Si–C bonds. Infrared spectroscopy (FTIR) confirmed formation of the hydride intermediate on the surface and then, attachment of the appropriate organic compound in the second step. The amount of deposited interphase and its stability was significantly enhanced compared to standard silanization treatment. Fracture surfaces were observed by scanning electron microscopy (SEM) before and after environmental exposure proving that the most stable interfacial bond was obtained with the two-step treated fibers. It was concluded that hydrosilylation provides a viable alternative to silanization for both glass and ceramic fibers in composites intended for applications requiring enhanced hydrolytic stability of the composite parts.     

流速比对颗粒在液固两相平板混合层中沉降的影响

本文采用流动显示的方法对平板混合层中上下层流体速度比对固体颗粒在混合层中沉降的影响进行了研究。实验中分别采用粒径小于 ４０ ｕｍ,粒径 ９８～１０４ｕｍ,粒径 １５４～１６０ｕｍ的玻璃微珠以及环氧树脂作为固相颗粒,对这些颗粒在速度比分别为１：１．２、１：２和１：２．８的液相混合层中的运动进行了显示。结果表明混合层中大涡结构对固体颗粒的沉降具有迟滞作用,其作用程度取决于混合层中上下层流体速度比。速度比越大,颗粒的沉降越慢。     

Field desorption mass spectroscopic analysis of silane coupling agents hydrolyzed in solution

Aqueous solutions of silane coupling agents used for surface treatment of glass fiber were analyzed using gas chromatography (GC), gel permeation chromatography (GPC), and field desorption mass spectrometry (FD-MS). N-Phenyl-3-aminopropyltrimethoxysilane (AnPS) and 3-aminopropyltriethoxysilane (APS) used were hydrolyzed and condensed in water-ethanol solution. FD-MS analysis was found to be suitable for the evaluation of polymerization of silanes in the process of hydrolysis and condensation in the aqueous solution. FD-MS analysis gave the molecular weight of each silane condensate to evaluate the respective molecular structure.     

Effect of surface treatment of nanoclay on the mechanical properties of epoxy/glass fiber/clay nanocomposites

A new method of silane treatment of nanoclays is reported where in the clay is nanodispersed in hydrolyzed silanes. The surface functionalization of Cloisite^® 15A nanoclay has been carried out using two different silane coupling agents: 3-aminopropyltriethoxy silane and 3-glycidyloxypropyltrimethoxy silane using varied amounts of silane coupling agents, e.g. 10, 50, 200, and 400 wt% of clay. The surface modification of Cloisite^® 15A has been confirmed by Fourier transform infrared spectroscopy. The modified clays were then dispersed in epoxy resin, and glass fiber-reinforced epoxy clay laminates were manufactured using vacuum bagging technique. The fiber-reinforced epoxy clay nanocomposites containing silane modified clays have been characterized using small angle X-ray scattering, transmission electron spectroscopy and differential scanning calorimetry. The results indicate that the silane treatment of nanoclay aided the exfoliation of nanoclay and also led to an increase in mechanical properties. The optimized amount of silane coupling agents was 200 wt%. The nanocomposites containing clay modified in 200 wt% of silanes exhibited an exfoliated morphology, improved tensile strength, flexural modulus, and flexural strength. The improved interfacial bonding between silane modified nanoclays and epoxy matrix was also evident from significant increase in elongation at break.