The role of additional silane coupling agent treatment in oxygen plasma-treated UHMPE fiber/vinylester composites

Ultra-high modulus polyethylene (UHMPE) fiber was treated with oxygen plasma and a silane coupling agent in order to improve the interfacial adhesion between the UHMPE fiber and vinylester resin. The oxygen plasma and γ-methylmethacryloxypropyltrimethoxysilane (γ-MPS)-treated UHMPE fiber/vinylester composites showed a slightly higher interlaminar shear strength than the oxygen plasma-treated UHMPE fiber/vinylester composites. The interfacial adhesion of the oxygen plasma-treated UHMPE fiber/vinylester composites in this study is mainly due to mechanical interlocking between the micropits formed by the oxygen plasma treatment and the vinylester resin. The γ-MPS molecules adsorbed onto the UHMPE fiber surface neither affected the morphology of the UHMPE fiber surface, nor reduced the extent of mechanical interlocking. The improved interfacial adhesion by the γ-MPS treatment is due to enhanced wettability and chemical interaction through the chemically adsorbed γ-MPS molecules, as detected by Fourier-transform infrared (FT-IR) spectroscopy. The γ-MPS molecules adsorbed onto the ultra-high molecular weight polyethylene (UHMWPE) plate surface also reduced the aging effect of the oxygen plasma-treated UHMWPE surface.     

Silicone‐Organic Resin Hybrid Matrix Composites

Summary: Glass fabric reinforced hybrid matrix composites of a toughened silicone resin and a vinyl ester resin were fabricated and their properties investigated. The hybrid composites consisted of multi‐layers of fiber reinforced silicone resins and vinyl ester resins. The toughened silicone resin, a crosslinkable phenylsilsesquioxane resin with high thermal and thermal oxidation resistance but relatively low T_g, was chosen to be the outer layers. The vinyl ester resin, with better strength, toughness and a much higher T_g than the toughened silicone resin, was used as the inner layers. A co‐cure process proved to establish a strong interface between the two in a hybrid composite. The hybrid composites had better flammability properties and much lower short term moisture absorption than the vinyl ester composites. The strength and modulus retention of the hybrid composites at elevated temperatures was higher than the composites using any single resin as the matrix. For example, when tested at 150 °C the flexural modulus and strength values of a twelve layer composite, with eight inner vinyl ester resin layers and four silicone outer layers, were almost an order of magnitude higher than the composite using the silicone resin alone, and were significantly higher than the one using vinyl ester resin alone. The room temperature short beam shear strength of the hybrid composites was also higher. DMA revealed that the inter‐diffusion of reactive components between the two resins was probably responsible for this synergistic effect, resulting in an α transition temperature of 182 °C for the hybrid composite, higher than that of either the silicone resin (85 °C) or the vinyl ester resin (162 °C).

     

Impact behavior of carbon fiber/polyethylene fiber hybrid composite: The effect of surface treatment of polyethylene fiber

Hybrid composites were prepared by adding one or two plies of polyethylene (PE) fabric to the bottom side of four-ply carbon fiber/vinylester composites. The effect of the surface treatment of PE fiber on the impact properties of carbon fiber/PE fiber hybrid composites was investigated using oxygen plasma, γ-MPS, and γ-MPS-modified polybutadiene (PB/γ-MPS) as surface modifiers. Carbon fiber/vinylester composite exhibited brittle failure with cross-shaped crack at the back side. The addition of PE fabric on the bottom side resulted in a change of the impact behavior of hybrid composites. After hybridization, the absorption of much impact energy was attributed to a considerable degree of plastic deformation in PE plies and the delamination at the interface between carbon and PE layer. However, the surface treatment of PE fiber reduced the impact energy of composites with restriction of deformation at the interface between the carbon and the PE layer. Moreover, the addition of a treated PE layer decreased the degree of deformation with a dagger-shaped deformation zone at the back side. The extent of the deformation area had a significant effect on the impact energy of the hybrid composites.     

Catalytic grafting: A new technique for polymer/fiber composites. II. Plasma treated UHMPE fibers/polyethylene composites

In this paper, the catalytic grafting technique for preparation of polymer/fiber composites is extended to plasma treated ultra-high modulus polyethylene (UHMPE) fiber/high density polyethylene (HDPE) system. The OH groups introduced on the UHMPE fiber surface by oxygen plasma treatment were used to chemically anchor Ziegler-Natta catalyst which then was followed by ethylene polymerization on the fiber surface. The morphology and interfacial behavior, as well as the mechanical properties, of the HDPE composites reinforced by catalytic grafted or ungrafted UHMPE fibers were investigated by SEM, DSC, polarized light optical microscopy, and tensile testing. The experimental results show that the polyethylene grafted on the fibers acted as a transition layer between the reinforcing UHMPE fibers and a commercial HDPE matrix. The interfacial adhesion was also significantly improved. Compared with the composite reinforced by ungrafted UHMPE fibers, the composite reinforced by catalytic grafted UHMPE fibers exhibits much better mechanical properties.     

Formation of a carbon fiber/polyhedral oligomeric silsesquioxane/carbon nanotube hybrid reinforcement and its effect on the interfacial properties of carbon fiber/epoxy composites

A carbon fiber/polyhedral oligomeric silsesquioxane/carbon nanotube (CF–POSS–CNT) hybrid reinforcement was prepared by grafting CNTs onto the carbon fiber surface using octaglycidyldimethylsilyl POSS as the linkage in an attempt to improve the interfacial properties between carbon fibers and an epoxy matrix. X-ray photoelectron spectroscopy, scanning electron microscopy, dynamic contact angle analysis and single fiber tensile testing were performed to characterize the hybrid reinforcements. Interlaminar shear strength (ILSS), impact toughness, dynamic mechanical analysis and force modulation atomic force microscopy were carried out to investigate the interfacial properties of the composites. Experimental results show that POSS and CNTs are grafted uniformly on the fiber surface and significantly increase the fiber surface roughness. The polar functional groups and surface energy of carbon fibers are obviously increased after the modification. Single fiber tensile testing results demonstrate that the functionalization does not lead to any discernable decrease in the fiber tensile strength. Mechanical property test results indicate the ILSS and impact toughness are enhanced. The storage modulus and service temperature increase by 11 GPa and 17 °C, respectively. POSS and CNTs effectively enhance the interfacial adhesion of the composites by improving resin wettability, increasing chemical bonding and mechanical interlocking.     

Plasma etching and plasma polymerization coating of carbon fibers. Part 2. Characterization of plasma polymer coated carbon fibers

Unsized AS-4 carbon fibers were subjected to RF plasma etching and/or plasma polymerization coating in order to enhance their adhesion to vinyl ester resin. Ar, N₂ and O₂ were utilized for plasma etching, and acetylene, butadiene and acrylonitrile were used for plasma polymerization coating. Etching and coating conditions were optimized in terms of plasma power, treatment time, and gas (or monomer) pressure by measuring the interfacial adhesion strength. Interfacial adhesion was evaluated using micro-droplet specimens prepared with vinyl ester resin and plasma etched and/or plasma polymer coated carbon fibers. Surface modified fibers were characterized by SEM, XPS, FT-IR, α-Step, dynamic contact angle analyzer (DCA) and tensile strength measurements. Interfacial adhesion between plasma etched and/or plasma polymer coated carbon fibers and vinyl ester resin was reported previously (Part 1), and characterization results are discussed is this paper (Part 2). Gas plasma etching resulted in preferential etching of the fiber surface along the draw direction and decreased the tensile strength, while plasma polymer coatings altered neither the surface topography of fibers nor the tensile strength. Water contact angle decreased with plasma etching, as well as with acrylonitrile and acetylene plasma polymer coatings, but did not change with butadiene plasma polymer coating. FT-IR and XPS analyses revealed the presence of functional groups in plasma polymer coatings.     

Plasma etching and plasma polymerization coating of carbon fibers. Part 1. Interfacial adhesion study

Unsized AS-4 carbon fibers were etched by RF plasma and then coated via plasma polymerization in order to enhance their adhesion to vinyl ester resin. Gases utilized for plasma etching were Ar, N₂ and O₂, while monomers used in plasma polymerization coating were acetylene, butadiene and acrylonitrile. Plasma etchings were carried out as a function of plasma power (30–70 W), treatment time (1–10 min) and gas pressure (20–40 mtorr). Plasma polymerizations were performed by varying the treatment time (15–60 s), plasma power (10–30 W) and gas pressure (20-40 mtorr). The conditions for plasma etching and plasma polymerization were optimized by measuring interfacial adhesion with vinyl ester resin via micro-droplet tests. Plasma etched and plasma polymer coated carbon fibers were characterized by SEM, XPS, FT-IR and α-Step, dynamic contact angle analyzer (DCA) and tensile strength measurements. In Part 1, interfacial adhesion of plasma etched and plasma polymer coated carbon fibers to vinyl ester resin is reported, while characterization results including tensile strength of carbon fibers are reported in Part 2. Among the treatment conditions, a combination of Ar plasma etching and acetylene plasma polymer coating provided greatly improved interfacial shear strength (IFSS) of 69 MPa, compared to 43 MPa obtained from as-received carbon fiber. Based on the SEM analysis of failure surfaces and load-displacement curves, the failure was found to occur at the interface between plasma polymer coating and vinyl ester resin.     

Hybrid carbon-glass fiber vinyl ester resin composites

Hybrid carbon-glass fiber composites of novolak epoxy-based vinyl ester resins have been investigated. The chemical resistance, the thermo-oxidative stability and the mechanical properties such as tensile strength and tensile modulus, as well as flexural strength and flexural modulus, interlaminar shear strength (ILSS) and impact strength have also been estimated. The combination of glass and carbon fibers in the hybrid turns out to be an excellent mix. These composites have good tensile and flexural properties as well as the good chemical resistance of the carbon fibers and the high impact strength of the glass fibers and also the thermo-oxidative stability of highly aromatic vinyl ester resins based on novolak epoxy.     

Fabrication of hybrid matrix/silane modified carbon fabric composites and study of their mechanical properties

Carbon fiber reinforced polymer composites are an extremely strong and light fiber-reinforced plastics that contains carbon fiber. In the present study, carbon fabrics were treated with various weight percentages of silane and were confirmed by spectral analysis (Fourier transform infrared). The treated carbon fibers were reinforced in hybrid resin (a combination of vinyl ester and epoxy at a ratio of 80:20) by using vacuum-assisted resin transfer mold technique. The composites were tested to know their tensile strength, modulus, flexural strength, modulus, and interlaminar shear strength. The hybrid matrix specimen was also prepared and tested for the mechanical properties and confirmed the miscibility by differential scanning calorimetry and X-ray diffraction. The mechanical properties of hybrid matrix composites (HMCs) were studied by fracture surface morphology with scanning electron microscope. The mechanical properties of the HMCs increased with silane treatment. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47695.     

Study on interfacial properties of unidirectional flax/vinyl ester composites: Resin manipulation on vinyl ester system

Flax fibers are widely used as reinforcements in bio‐based polymer matrix composites. This study investigated the hydrophilic nature and surface purity of flax fiber that affects fiber/matrix adhesion in combination with hydrophobic structural polymers via matrix modification and the utilization of fiber treatment, specifically in a flax/vinyl ester (VE) composite. A new method to manipulate the vinyl ester system with acrylic resin (AR) was developed to produce flax reinforced. On the other hand, different types of chemical and physical treatments were applied on the flax fiber. FTIR was applied to evaluate the effects of surface treatments. Dynamic mechanical analysis (DMA) was used to analyze the unmodified and modified VE resin system. The surface of untreated and treated flax fibers and their composites were analyzed by scanning electronic microscopy (SEM). Sodium ethoxide‐treated flax/VE with 1% (wt) AR caused the best mechanical performance among all the flax/VE composites evaluated. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Mechanical performance of vinyl ester—polyurethane interpenetrating polymer network composites

In this study, a carbon fiber/vinyl ester-polyurethane interpenetrating polymer network (IPN) laminate composite was fabricated and characterized for the first time. The IPN matrix, consisting of a commercially available vinyl ester and polyurethane, was synthesized via a sequential method with vinyl ester as the rigid phase and polyurethane as the flexible phase. Good compatibility between the two phases in the matrix was achieved and confirmed via differential scanning calorimetry and dynamic mechanical analysis. The thermomechanical response of the IPN matrix was compared with that of an unmodified vinyl ester resin. The presence of the more ductile polyurethane in the IPN matrix depressed the glass transition temperature (from 94 to 84°C), but also served to improve damping response at all frequencies studied. Tensile and flexural tests were performed on the carbon fiber/IPN and carbon fiber/vinyl ester composites to determine their mechanical response. The IPN composite exhibited lower tensile properties than the vinyl ester composite. However, its flexural properties were on par with those of the vinyl ester composite.     

Influence of oxygen plasma treatment parameters on the properties of carbon fiber

This study is focused on the impact of oxygen plasma treatment on properties of carbon fibers and interfacial adhesion behavior between the carbon fibers and epoxy resin. The influences of the main parameters of plasma treatment process, including duration, power, and flow rate of oxygen gas were studied in detail using interlaminar shear strength (ILSS) of carbon fiber composites. The ILSS of composites made of carbon fibers treated by oxygen plasma for 1 min, at power of 125 W, and oxygen flow rate of 100 sccm presented a maximum increase of 28% compared to composites made of untreated carbon fibers. Furthermore, carbon fibers were characterized by scanning electron microscopy (SEM), tensile strength test, attenuated total reflectance Fourier transform infrared (ATR-FTIR), and Raman spectroscopy analyses. It was found that the concentration of reactive functional groups on the fiber surface was increased after the plasma modification, as well the surface roughness, which finally improved the interfacial adhesion between carbon fibers and epoxy resin. However, high power and long exposure times could partly damage the surface of carbon fibers and decrease the tensile strength of filaments and ILSS of treated fiber composites.     

VARTM工艺用乙烯基酯树脂基体配方及性能研究

以溴化改性乙烯基酯树脂、氨基甲酸酯改性乙烯基酯树脂为混合基体,以E-玻璃纤维(GF)为增强材料,通过真空辅助树脂传递模塑(VARTM)工艺制备乙烯基酯树脂/GF复合材料,对其力学性能和阻燃性能进行了研究.结果表明,在两种树脂质量比为1:1时该复合材料的拉伸强度与弯曲强度达到最大值,且综合性能最优.氧指数随溴化改性乙烯基...     

Synthesis of restorative microcapsules having vinyl ester healing medicine for hybrid resin/modified carbon fiber self-healing composites

In this study, we aimed to synthesize restorative microcapsules using aminopropyl triethoxy silane through a combination of both microemulsions with a sol–gel technique and vinyl ester resin used as a healing component. The characteristic features of the microcapsules were analyzed by FTIR, XRD, and SEM and confirmed by the formation of core-shell microspheres with desired properties. The fabricated core-shell microspheres were reinforced into a hybrid resin (vinyl ester (80): epoxy (20)/silane modified carbon fiber composites) using the hand lay-up method. The effect of the microspheres on the mechanical and self-healing properties of composites was investigated. The mechanical test results showed a significant improvement in the flexural and impact strength by approximately 23% and 30%, respectively. The healing property was observed using the flexural test and the results indicated that the recovered strength almost 74% of the composites after initial damage was due to the healing medicine released from the broken portion of the core-shell microspheres that filled and cured the cracked area of the composites.     

界面粘结对GF/VE复合材料在硫酸介质中耐蚀性能的影响

本文采用实验室模拟环境因素加速老化的方法,比较了两种界面粘结性能不同的防腐容器用玻璃纤维增强乙烯基酯树脂复合材料(GF/VEA,GF/VEB)在硫酸介质中的吸湿特性以及动态和静态力学性能的变化。结果表明,在55℃、40wt%的硫酸水溶液中,两种树脂的吸湿性能相差不大,但界面粘结情况的不同使两种复合材料的吸湿特性表现出明显差别;两种复合材料的弹性模量(E′)、剪切强度和弯曲性能均随浸泡时间的延长而下降,且GF/VEB材料因具有较好的界面粘结而呈现较高的性能保留率。     

Effect of fiber chemical treatment of nonwoven coconut fiber/epoxy composites adhesion obtained by RTM process

In this work untreated and alkali treated nonwoven coconut fiber mats/epoxy resin composites were manufactured using the resin transfer molding process. The alkaline solution removes some impurities present on fibers superficial layers and the effect regarding fiber/matrix adhesion were investigated by thermogravimetric analysis, dynamic mechanical analysis (DMA), scanning electron microscopy (SEM), ultrasonic C‐scan, and quasi‐static flexural test. Results show a removing of some amorphous fibers constituents, mainly waxes, extractives, and hemicellulose, revealing the fiber roughness surface but no initial degradation temperature changing. Regarding the composites, a similar interfacial adhesion was observed in both one through the results of SEM, DMA and quasi‐static flexural tests. The conclusion is that chemical treatment conditions applied on the fiber surface was been suitable to improve fiber roughness but did not the adhesion between coconut fibers mat and epoxy resin. POLYM. COMPOS., 38:2518–2527, 2017. © 2015 Society of Plastics Engineers     

Influence of plasma treatment on properties of ramie fiber and the reinforced composites

In this research, 9 series of ramie fibers were treated under low-temperature plasma with diverse output powers and treatment times. By analysis of the surface energy and adhesion power with epoxy resin, 3 groups as well as control group were chosen as reinforced fibers of composites. The influences of these parameters on the ramie fiber and its composites such as topography and mechanical properties were tested by scanning electron microscopy (SEM), atomic force microscopy (AFM), tensile property and fragmentation test of single-fiber composites. Contact angle and surface free energy results indicated that with the increased treatment times and output powers, surface energy and adhesion work with epoxy resin improved. Compared with the untreated fibers, surface energy and adhesion work with epoxy resin grew 124.5 and 59.1% after 3 min-200 w treatment. SEM and AFM showed low temperature plasma treatment etched the surface of ramie fiber to enhance the coherence between fiber and resin, consequently fiber was not easy to pull-out. After 3 min-200 w treatment, tensile strength of ramie fiber was 253.8 MPa, it had about 30.5% more than that of untreated fiber reinforced composite. Interface shear stress was complicated which was affected by properties of fiber, resin and interface. Fragmentation test showed biggest interface shear stress achieved 17.2 MPa, which represented a 54.0% increase over untreated fiber reinforced composites.     

树脂对碳纤维/玻璃纤维层间混杂复合材料湿态弯曲特性影响

为了探究树脂基体对相同铺层方式下碳纤维/玻璃纤维层间混杂复合材料(碳/玻体积混杂比为1.86/1)干态、湿态(100℃水煮2 h)弯曲特性的影响,首先对环氧树脂和乙烯基树脂浇铸体试样分别开展了耐水性加速老化试验,并对两种树脂浇铸体试样在每个老化试验周期下分别开展剩余弯曲特性试验;然后对碳/玻层间混杂复合材料开展干、湿态弯曲试验。结果表明,无论是在常规试验(未经过老化)还是在各个老化试验周期,两种树脂浇铸体试样弯曲应力–位移曲线变化规律基本一致,但总体而言,环氧树脂浇铸体试样常规弯曲强度和各个阶段老化后弯曲强度均优于乙烯基树脂浇铸体试样;相同试验状态下,两种树脂基混杂复合材料试样湿态弯曲强度和弯曲弹性模量均较干态试样产生不同程度的降低,但环氧树脂基混杂复合材料试样在干、湿态环境下的弯曲性能均优于乙烯基树脂基混杂复合材料试样。     

Mechanical behavior of two-dimensional carbon/carbon composites with interfacial carbon layers

Effect of interfacial carbon layers on the mechanical properties and fracture behavior of two-dimensional carbon fiber fabrics reinforced carbon matrix composites were investigated. Phenolic resin reinforced with two-dimensional plain woven carbon fiber fabrics was used as starting materials for carbon/carbon composites and was prepared using vacuum bag hot pressing technique. In order to study the effect of interfacial bonding, a carbon layer was applied to the carbon fabrics in advance. The carbon layers were prepared using petroleum pitch with different concentrations as precursors. The experimental results indicate that the carbon/carbon composites with interfacial carbon layers possess higher fracture energy than that without carbon layers after carbonization at 1000°C. For a pitch concentration of 0.15 g/ml, the carbon/carbon composites have both higher flexural strength and fracture energy than composites without carbon layers. Both flexural strength and fracture energy increased for composites with and without carbon layers after graphitization. The amount of increase in fracture energy was more significant for composites with interfacial carbon layers. Results indicate that a suitable pitch concentration should be used in order to tailor the mechanical behavior of carbon/carbon composites with interfacial carbon layers.     

酚醛环氧乙烯基酯树脂碳纤维复合材料的制备及性能研究

把酚醛环氧乙烯基酯树脂分别与固化剂过氧化氢异丙苯(CHP)、过氧化苯甲酸叔丁酯(TBPB)、过氧化二异丙苯(DCP)进行混溶,模压成型,碳纤维层合板,进行了力学性能和热稳定性的研究。结果表明,研究的碳纤维-酚醛环氧基乙烯基酯树脂复合材料具有非常好的力学性能及热稳定性,弯曲强度达到1 400～1 900 MPa。