Concentration effect of γ‐glycidoxypropyltrimethoxysilane on the mechanical properties of glass fiber–epoxy composites

In this study, glass fibers were modified using γ‐glycidoxypropyltrimethoxysilane of different concentrations to improve the interfacial adhesion at interfaces between fibers and matrix. Effects of γ‐glycidoxypropyltrimethoxysilane on mechanical properties and fracture behavior of glass fiber/epoxy composites were investigated experimentally. Mechanical properties of the composites have been investigated by tensile tests, short beam tests, and flexural tests. The short‐beam method was used to measure the interlaminar shear strength (ILSS) of laminates. The tensile and flexural properties of composites were characterized by tensile and three‐point bending tests, respectively. The fracture surfaces of the composites were observed with a scanning electron microscope. On comparing the results obtained for the different concentrations of silane solution, it was found that the 0.5% GPS silane treatment provided the best mechanical properties. The ILSS value of heat‐cleaned glass fiber reinforced composite is enhanced by ∼59% as a result of the glass fiber treatment with 0.5% γ‐GPS. Also, an improvement of about 37% in tensile strength, about 78% in flexural strength of the composite with the 0.5% γ‐GPS treatment of glass fibers was observed. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Influence of silane coupling agents on the surface energetics of glass fibers and mechanical interfacial properties of glass fiber-reinforced composites

The effect of various silane coupling agents on glass fiber surfaces has been studied in terms of the surface energetics of fibers and the mechanical interfacial properties of composites. γ-Methacryloxypropyltrimethoxysilane (MPS), γ-aminopropyltriethoxysilane (APS), and γ-glycidoxypropyltrimethoxysilane (GPS) were used for the surface treatment of glass fibers. From contact angle measurements based on the wicking rate of a test liquid, it was observed that silane treatment of glass fiber led to an increase in the surface free energy, mainly due to the increase of its specific (or polar) component. Also, for the glass fiber-reinforced unsaturated polyester matrix system, a constant linear relationship was observed in both the interlaminar shear strength (ILSS) and the critical stress intensity factor (K_IC) with the specific component, γ_S ^SP, of the surface free energy. This shows that the hydrogen bonding, which is one of the specific components of the surface free energy, between the glass fibers and coupling agents plays an important role in improving the degree of adhesion at the interfaces of composites.     

Effects of chemical surface pretreatment on tensile properties of a single glass fiber and the glass fiber reinforced epoxy composite

The aim of this article is to determine the effect of surface pretreatments, prior to the silanization, on the structure and tensile properties of the glass fibers and their epoxy composites. Commercial glass fibers were washed with acetone to remove the soluble portion of sizing, calcinated for the removal of organic matter, activated for surface silanol regeneration, and silanizated with glycidoxypropyltrimethoxysilane (GPS). Tensile test was carried out. The morphology of pretreated glass fibers and the fracture surfaces of the epoxy composites were observed with a scanning electron microscope (SEM). The results revealed that both apparent modulus and strength of a single glass fiber and the glass fiber/epoxy resin composites strongly depend on the fiber surface pretreatments. The acetone treatment did not change appreciably the composition and tensile properties of glass fibers, but there was a weak interface between fibers and matrix. In calcinated and acid activated fibers, the two competitive effects was observed: (1) degradation of the fibers themselves and (2) improved interfacial adhesion between the glass fibers and the epoxy matrix, once the samples was silanizated. The ATR‐FTIR results show that the surface content of Si OH increases as reflected by the increasing of the Si O band, resulting in an interaction between silane coupling agent and glass fiber. POLYM. COMPOS., 91–100, 2016. © 2014 Society of Plastics Engineers     

Direct measurement of molten poly(ethylene terephthalate) contact angles on single aminopropylsilane coated glass fibers

The kinetics of spreading of molten poly(ethylene terephthalate) (PET) on aminopropylsilane (APS) treated glass fiber surfaces has been studied. The modified Wilhelmy wetting method was used for contact angle determination with small diameter fibers (10-100 μm) used as vertical wetting probes. It is shown that the small meniscus dimensions accelerates wetting, and viscous relaxation effects can be kept to a minimum, so that purely surface effects can be studied in terms of the equilibrium contact angle at elevated temperatures. Experiments were performed using single fibers coated with a 'reactive' coupling agent (APS) in this laboratory. Although complete spreading of PET at 270°C was not initially observed, zero contact angle was eventually obtained due to interfacial chemical reaction between APS and PET. The suggestion that complete spreading is driven by the interfacial reaction was supported by a study of glass fibers coated with a non-reactive silane. In that case, a large initial contact angle was observed but zero contact angle was never obtained. The equilibration rate to = 0° was much faster on bare glass than APS coated glass for PET at 270°C because complete spreading is thermodynamically favorable on bare glass. Data for commercial silane treated 10 μm fibers in terms of the wetting rate in molten PET at 270°C were comparable to that for the APS coated fibers.     

Surface energy of untreated and surface-modified cellulose fibers

Average advancing and receding contact angles made against cotton and glass fibers by a set of probe liquids are determined using the Wilhelmy technique. The dispersive and polar components of the surface energy are calculated from the measured contact angles using both the geometric and the harmonic mean methods. It is found that these components are similar for untreated cellulose and glass fibers, and that they both have a high polar component, corresponding to a hydrophilic surface. Changes in surface energy caused by treatment of the cellulose fiber surfaces with melamine, polyethyleneimine (PEI), and a silane coupling agent are reported. It is found in particular that polyethyleneimine treatment of cellulose significantly reduces the polar component of its surface energy. While treatment of glass fibers with a silane coupling agent reduces the polar component and increases the dispersive component of the surface energy it shows little effect on the surface energy of cellulose.     

Influences of liquid elastomer additive on the behavior of short glass fiber reinforced epoxy

In this study, improvements in mechanical and thermal behavior of short glass fiber (GF) reinforced diglycidyl ether of bisphenol-A (DGEBA) based epoxy with hydroxyl terminated polybutadiene (HTPB) modification have been studied. A silane coupling agent (SCA) with a rubber reactive group was also used to improve the interfacial adhesion between glass fibers and an epoxy matrix. 10, 20, and 30 wt% GF reinforced composite specimens were prepared with and without silane coupling agent treatment of fibers and also HTPB modification of epoxy mixture. In the ruber modified specimens, hardener and HTPB were premixed and left at room temperature for 1 hr before epoxy addition. In order to observe the effects of short glass fiber reinforcement of epoxy matrix, silane treatment of fiber surfaces, and also rubber modification of epoxy on the mechanical behavior of specimens, tension and impact tests were performed. The fracture surfaces and thermal behavior of all specimens were examined by scanning electron microscope (SEM), and dynamic mechanical analysis (DMA), respectively. It can be concluded that increasing the short GF content increased the tensile and impact strengths of the specimens. Moreover, the surface treatment of GFs with SCA and HTPB modification of epoxy improved the mechanical properties because of the strong interaction between fibers, epoxy, and rubber. SEM studies showed that use of SCA improved interfacial bonding between the glass fibers and the epoxy matrix. Moreover, it was found that HTPB domains having relatively round shapes formed in the matrix. These rubber domains led to improved strength and toughness, due mainly to the “rubber toughening” effect in the brittle epoxy matrix.     

硅烷偶联剂改性芳纶的性能测试

采用硅烷偶联剂对芳纶进行改性,然后用傅里叶红外光谱仪、单一纤维接触角测试仪和X射线衍射仪对改性前后的芳纶进行测试、观察并分析。结果显示:红外光谱分析表明芳纶的改性发生在纤维的表面,并没有对纤维大分子产生明显破坏;接触角测试表明改性后芳纶的接触角变小,说明KH550硅烷偶联剂可改善芳纶的亲水性;X射线衍射测试表明芳纶结晶度有所下降,可以更好地与树脂黏结。     

The influence of silane coupling agent composition on the surface characterization of fiber and on fiber-matrix interfacial shear strength

It is well known that the fiber-matrix interface in many composites has a profound influence on composite performance. The objective of this study is to understand the influence of composition and concentration of coupling agent on interface strength by coating E-glass fibers with solutions containing a mixture of hydrolyzed propyl trimethoxysilane (PTMS) and n -aminopropyl trimethoxysilane (APS). The failure behavior and strength of the fiber-matrix interface were assessed by the single-fiber fragmentation test (SFFT), while the structure of silane coupling agent was studied in terms of its thickness by ellipsometry, its morphology by atomic force microscopy, its chemical composition by diffuse reflectance infrared Fourier transform (DRIFT), and its wettability by contact angle measurement. Deposition of 4.5 ‐ 10 m 3 mol/L solution of coupling agent in water resulted in a heterogeneous surface with irregular morphology. The SFFT results suggest that the amount of adhesion between the glass fiber and epoxy is dependent not only on the type of coupling agent but also on the composition of the coupling agent mixture. As the concentration of APS in the mixture increased, the extent of interfacial bonding between the fiber and matrix increased and the mode of failure changed. For the APS coated glass epoxy system, matrix cracks were formed perpendicular to the fiber axis in addition to a sheath of debonded interface region along the fiber axis.     

Development of lightweight thermoplastic composites based on polycarbonate/acrylonitrile–butadiene–styrene copolymer alloys and recycled carbon fiber: Preparation,morphology, and properties

Thermoplastic composites of polycarbonate (PC)/acrylonitrile–butadiene–styrene copolymer (ABS) alloys reinforced with recycled carbon fiber (RCF) were prepared by melt extrusion through a twin‐screw extruder. The RCF was first cleaned and activated with a concentrated solution of nitric acid and was then surface‐coated with diglycidyl ether of bisphenol A as a macromolecular coupling agent. Such an approach is effective to improve the interfacial bonding between the fibers and the PC/ABS matrix. As was expected, the reinforcing potential of the RCF was enhanced substantially, and furthermore, the mechanical properties, heat distortion temperature, and thermal stability of PC/ABS alloys were significantly improved by incorporating this surface‐treated RCF. The composites also obtained a reduction in electrical resistivity. The morphologies of impact fracture surfaces demonstrated that the RCF achieved a homogeneous dispersion in the PC/ABS matrix due to good interfacial adhesion between the fibers and the matrix. In addition, the introduction of RCF into PC/ABS alloys also resulted in an increase in the storage moduli of the composites but a decrease in the loss factors. It is prospective that, with such good performance in mechanical data, heat resistance, and electrostatic discharge, the RCF‐reinforced PC/ABS composites exhibit a potential application in industrial and civil fields as high‐performance and lightweight materials. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

偶联剂改性UHMWPE纤维表面性能的研究

选用硅烷偶联剂KH-550,KH-560和钛酸酯偶联剂NDZ-201作为表面改性剂,对超高相对分子质量聚乙烯(UHMWPE)冻胶纤维在萃取阶段进行表面处理,经干燥、超拉伸制得表面改性UHMWPE纤维。采用红外光谱仪、接触角测量仪测定了纤维的表面化学结构和表面润湿性能,采用单纤维树脂包埋-拔出法测定了纤维与树脂基体的界面剪切强度,比较了改性前后纤维的力学性能变化。结果表明:改性后纤维表面引入了极性基团,硅烷偶联剂KH-550对UHMWPE纤维的表面改性效果最好。采用质量分数为1%的硅烷偶联剂KH-550溶液处理后,纤维与环氧树脂间的界面剪切强度提高了87.8%,纤维的断裂强度和模量分别提高了6.9%和32.6%。     

Styrene/tetradecyl methyl acrylate/3‐methacryloxylpropyl trimethoxyl silane triblock copolymers: Atom transfer radical polymerization synthesis and effects on the glass‐fiber/polypropylene interphase properties as a macromolecular coupling agent

Styrene/tetradecyl methyl acrylate/3‐methacryloxylpropyl trimethoxyl silane triblock copolymers (PSTKs), with well‐defined structures and narrow molecular weight distributions, were synthesized by atom transfer radical polymerization. They were investigated as macromolecular coupling agents for the surface treatment of glass fibers. The reaction kinetics for the triblock copolymers were studied. The contact angles of the copolymers with water and diiodomethane showed that a modified‐glass‐fiber surface treated with a PSTK solution had strong hydrophobicity and that the impregnation of polypropylene on glass fibers was improved dramatically. In comparison with a film of 3‐methacryloxylpropyl trimethoxyl silane, the polarity of the surface free energy of a PSTK film decreased, whereas the dispersion increased greatly. The critical concentration of the macromolecular coupling agents was obtained, and the monolayer saturated adsorptive capacity was calculated with the Gibbs absorption isotherm equation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1661–1670, 2007     

原位聚合连续纤维增强聚甲基丙烯酸甲酯复合材料的界面及性能研究

通过选用含不同官能团的硅烷偶联剂3-甲基丙烯酰氧丙基三甲氧基硅烷(MPS)、γ-氨丙基三甲氧基硅烷(APS)和γ-氯丙基三甲氧基硅烷(CPS)处理玻璃纤维,然后通过原位聚合的方法制造了连续纤维增强的聚甲基丙烯酸甲酯(PMMA)复合材料。研究结果表明,经过这三种偶联剂处理的玻璃纤维与基体树脂在界面分别形成了化学键、范德华力和氢键。红外、动态力学分析和扫描电镜研究表明,复合材料的界面粘接强度顺序为:MPS>CPS>APS。MPS处理的复合材料具有最高的弯曲强度,而CPS处理的复合材料具有最佳的冲击韧性和断裂伸长率。     

Effects of silica surface treatment on the impregnation process of silica fiber/phenolics composites

Effects of silica surface treatment on the impregnation process of silica fiber/phenolics composites were studied. Micro‐Wilhelmy method was used to evaluate the surface characterization of silanized silica fibers. The interlaminar shear strength (ILSS) measurements and the void contents of the silica fiber/phenolics composites were also performed. The interactions occurring between silica fiber and the components of phenolic resin solution can affect the contact angle between silica fiber and phenolic solution and the dynamic adsorption behavior of phenolic resin onto silica fiber. There are competitive adsorptions to different extent for phenolic resin and solvent onto silica fibers. Silica fibers as reinforcement treated by silane‐coupling agent, such as γ‐aminopropyl‐triethoxysilane, γ‐glycidoxypropyl‐trimethoxysilane, trimethylchlorosilane, and γ‐methacryloxypropyl‐trimethoxysilane, influence the mechanical interfacial properties of silica fiber/phenolics composites and the uniformity of resin distribution. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Controlled interactions in cellulose-polymer composites. 1: Effect on mechanical properties

The surface properties of cellulose fibers have been modified by heat treatment, by silane coupling agents, and by maleated polypropylene grafts. The effectiveness of these methods has been evaluated by electron spectroscopy (ESCA), by contact angle measurements, and by inverse gas chromatography. The latter analyses yielded information on the fibers' acid/base interaction potential. Cellulose was found to be amphoteric, with prevalent acidic properties. Heat and chloro-silane treatments accentuated acidity, while amino-silane treatment produced net basicity in the fiber surface. Modification with maleated polypropylene reduced specific interactions and converted the fiber to a predominantly dispersion-force solid. The modified fibers were used in composites with polypropylene (neutral), polystyrene (base), and chlorinated polyethylene (acid) as matrix. Stress/strain and dynamic mechanical parameters were found to vary with acid/base interactions between polymer and fiber, significant improvements being noted in elastic and storage moduli, in tensile strength and elongation. In polypropylene, properties were unaffected by acid/base considerations. Acid/base forces, not necessarily dominant, merit consideration in the design of surface modification strategies intended to optimize composite mechanical properties.     

THE INFLUENCE OF SILANE COUPLING AGENT COMPOSITION ON THE SURFACE CHARACTERIZATION OF FIBER AND ON FIBER-MATRIX INTERFACIAL SHEAR STRENGTH

It is well known that the fiber-matrix interface in many composites has a profound influence on composite performance. The objective of this study is to understand the influence of composition and concentration of coupling agent on interface strength by coating E-glass fibers with solutions containing a mixture of hydrolyzed propyl trimethoxysilane (PTMS) and γ-aminopropyl trimethoxysilane (APS). The failure behavior and strength of the fiber-matrix interface were assessed by the single-fiber fragmentation test (SFFT), while the structure of silane coupling agent was studied in terms of its thickness by ellipsometry, its morphology by atomic force microscopy, its chemical composition by diffuse reflectance infrared Fourier transform (DRIFT), and its wettability by contact angle measurement. Deposition of 4.5 ×10 -3 mol/L solution of coupling agent in water resulted in a heterogeneous surface with irregular morphology. The SFFT results suggest that the amount of adhesion between the glass fiber and epoxy is dependent not only on the type of coupling agent but also on the composition of the coupling agent mixture. As the concentration of APS in the mixture increased, the extent of interfacial bonding between the fiber and matrix increased and the mode of failure changed. For the APS coated glass epoxy system, matrix cracks were formed perpendicular to the fiber axis in addition to a sheath of debonded interface region along the fiber axis.     

Nanoscale toughening of carbon fiber‐reinforced epoxy composites through different surface treatments

Interests in improving poor interfacial adhesion in carbon fiber‐reinforced polymer (CFRP) composites has always been a hotspot. In this work, four physicochemical surface treatments for enhancing fiber/matrix adhesion are conducted on carbon fibers (CFs) including acid oxidation, sizing coating, silane coupling, and graphene oxide (GO) deposition. The surface characteristics of CFs are investigated by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, atomic force microscopy, scanning electron microscopy, interfacial shear strength, and interlaminar shear strength. The results showed that GO deposition can remarkably promote fiber/matrix bonding due to improved surface reactivity and irregularity. In comparison, epoxy sizing and acid oxidation afford enhancement of IFSS owing to effective molecular chemical contact and interlocking forces between the fiber and the matrix. Besides, limited covalent bonds between silane coupling and epoxy matrix cannot make up for the negative effects of excessive smoothness of modified CFs, endowing them inferior mechanical properties. Based on these results, three micro‐strengthening mechanisms are proposed to broadly categorize the interphase micro‐configuration of CFRP composite, namely, “Etching” “Coating”, and “Grafting” modifications, demonstrating that proper treatments should be chosen for combining optimum interfacial properties in CFRP composites. POLYM. ENG. SCI., 59:625–632, 2019. © 2018 Society of Plastics Engineers     

Flexibility improvement of short glass fiber reinforced epoxy by using a liquid elastomer

In certain applications of fiber reinforced polymer composites flexibility is required. The aim of this study was to improve flexibility of short glass fiber reinforced epoxy composites by using a liquid elastomer. For this purpose, diglycidyl ether of bisphenol-A (DGEBA) based epoxy matrix was modified with hydroxyl terminated polybutadiene (HTPB). A silane coupling agent (SCA) was also used to improve the interfacial adhesion between glass fibers and epoxy matrix. During specimen preparation, hardener and HTPB were premixed and left at room temperature for an hour before mixing with epoxy resin to allow possible reactions to occur. In order to compare flexibility of the specimens flexural tests were conducted and the data were evaluated numerically by using a derived relation. Test data and scanning electron microscope analysis indicated that surface treatment of glass fibers with SCA, and HTPB modification of epoxy matrix improved flexural properties especially due to the strong interaction between fibers, epoxy, and rubber. It was also observed that HTPB modification resulted in formation of relatively round rubber domains in the epoxy matrix leading to increased flexibility of the specimens.     

Flame retardant synergy between interfacial and bulk carbonation in glass fiber reinforced polypropylene

Glass fiber reinforced polypropylene (GF-PP) composites have high flammability on account of wick effect which leads to accelerated flow of the polymer melt along the glass fibers (GF) surface to the flame zone. In this study, dipentaerythritol (DPER), a charring agent, was adsorbed on the GF surface through the hydrogen bond between silane coupling agent and DPER. DPER has a synergistic effect with the intumescent flame retardants (IFR) added in the composites, which can induce interfacial carbonization on the surface of GF, thus transforming the intrinsic smooth GF surface into roughness one. In this way, the negative effect of the wick effect in flame retardancy is weakened. Moreover, the char residues remained on the surface of GF can bring an improved adhesion between GF and char residues formed in the resin so that a more stable barrier char layer is formed. The PP composites with 20 wt% modified glass fiber (M-GF) and 30 wt% IFR can achieve the UL-94V-0, and its limiting oxygen index (LOI) value increased from 16.5% to 29.5%. Simultaneously, the heat release rate (HRR), total heat release (THR) and total smoke release (TSR) decreased significantly, and the peak of heat release rate (PHRR) reduced 60.6% compared with GF-PP.     

硅烷偶联剂改性玻璃纤维增强硅气凝胶的研究

为了达到增强硅气凝胶力学性能的目的,采用硅烷偶联剂KH550与KH560二步改性接枝玻璃纤维,进而制备纤维增强硅气凝胶。利用扫描电子显微镜、红外光谱仪、比表面及孔径分布仪、热重-差热分析仪、导热系数仪、电子动静态疲劳试验机等对其表征。实验结果表明：硅烷偶联剂改性玻璃纤维与硅气凝胶复合后网络结构更加均匀、骨架强度更加稳定、孔径多在30 nm以下、具有良好的热稳定性;同时,改性玻璃纤维的最佳添加量为20%（质量分数）,此时其密度为0.167 g/cm³,导热系数为0.018 5 W/（m·K）,接触角为127°,抗弯强度为1.042 MPa,抗压强度为0.669 MPa,达到预期实验目的。     

Effect of surface treatment of ramie fiber on the interfacial adhesion of ramie/acetylated epoxidized soybean oil (AESO) green composite

Recently, many researchers have attempted to convert soybean oil into useful polymers. One of the ways to make soybean oil into a matrix of green composites is to modify its triglyceride structure to obtain the acrylated epoxidized soybean oil (AESO) through epoxidization and acrylation. In this study, the effects of ramie fiber surface treatments such as acetylation, silane, and peroxide treatments on the chemical, morphological, and interfacial adhesion properties of a ramie/AESO green composite were studied. Surface-treated fibers were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and dynamic contact angle analysis. The crystallinity and thermal stability of chemically treated fibers were investigated by wide angle X-ray diffraction and thermogravimetric analyzer. It was demonstrated that surface treatments lead to several morphological changes, including the formation of micro-cracks and removal of impurities by acetylation and peroxide treatment as well as surface smoothing by silane treatment. Surface energy of acetylated fiber decreased with treatment time and showed the lowest value for silane treated fiber. The interfacial shear strength (IFSS) of a fiber/AESO composite was investigated through the microbond test. The IFSS of silane treated ramie was higher than that of others. The result indicates that silane treated fibers improve the interfacial property, which is the most important characteristic for the end use of green composites.