Morphology and interphase formation in epoxy/PMMA/glass fiber composites: effect of the molecular weight of the PMMA

In this work ternary composites based on an epoxy thermoset modified with a thermoplastic polymer and reinforced with glass fibers were prepared. The aim of this study is to analyze the influence of the molecular weight of the thermoplastic polymer on the final morphologies. To obtain tailor made interphases four poly(methylmethacrylate), PMMA, which differ in their molecular weight (34,000, 65,000, 76,000 and 360,000 g/mol) were chosen to modify the epoxy resin. The amount of PMMA in the composites was fixed to 5 wt.%. Neat polymer matrices (epoxy-PMMA without fibers) were also prepared for comparison. To study all systems dynamic mechanical analysis (DMA), atomic force microscopy (AFM) and scanning electron microscopy (SEM) were used. Although all the systems showed the typical phase separation in the epoxy/PMMA blend, DMA experiments revealed a new phase with more restricted mobility when the glass fibers are present. The amount of this phase increases as molecular weight of PMMA does. The morphologies as well as the fracture surface in the immediate surroundings of the fibers were found to be different from those observed further away from the surface of the fiber, suggesting therefore that, in this case, different fracture mechanism operates. These observations allow us to conclude that an interphase with specific properties is formed. This interphase is based on a polymer or a polymer blend (epoxy-PMMA) enriched in the component with lower mobility.     

Low velocity impact and pseudo-ductile behaviour of carbon/glass/epoxy and carbon/glass/PMMA hybrid composite laminates for aircraft application at service temperature

Carbon/glass hybrid composite (CGHC) laminates are some of the most promising composites for lightweight applications. Sometimes these laminates are used in warm environment, such as aircraft frame structures, and this may affect their performance. In order to investigate this issue, the present research aims to study the effect of temperatures on the impact behavior and pseudo-ductile behaviour of CGHC in presence of different types of thermosets “epoxy” and thermoplastic “acrylic poly-methyl methacrylate-PMMA”. The experiments were started with making of CGHC laminates from different stacking sequences of unidirectional carbon and woven glass fibre layers, using a vacuum-assisted resin transfer method followed by curing treatment. In addition to CGHC laminates, four other neat batches (Carbon/epoxy, Carbon/PMMA, Glass/epoxy, Glass/PMMA) were prepared for comparison. The low velocity impact behaviour of the fabricated panels was evaluated at high temperatures (60 °C and 80 °C) according to ISO 6603-2 standard, using drop tower, while pseudo-ductile behaviour and ductility index (DI) of the specimens were estimated based on the measured total energy and elastic energy. Also, the low-velocity impact response was modeled mathematically based on a modified energy-balance model to predict the absorbed energies. Finally, the failure mechanisms were examined using optical microscope to determine the influence of these damage growth on DI of the composites under different temperatures. The results showed that the impact energy response of both hybrid composites i.e. epoxy and PMMA was stable even as the temperature rose, however, carbon/glass/PMMA exhibited better performance compared with carbon/glass/epoxy with an increase in impact energy response estimated at 50% (25 °C) and 53% (80 °C). Also, the pseudo-ductile phenomenon was strongly evident, which facilitates the predictablility of failure.     

甲基丙烯酸甲酯在改性介孔分子筛SBA-15孔道中的溶液聚合

水热法合成了介孔分子筛SBA-15,分别用硅烷偶联剂KH-151,KH-560和KH-570对SBA-15进行了改性,将不同类型的改性介孔分子筛(M-SBA-15)作为"微反应器",把含MMA的甲苯溶液载入到"微反应器"中,通过溶液聚合法使得MMA在孔道内部形成聚合物.通过XRD,FTIR,N2吸附/脱附,GPC,1H-NMR,TG和DSC测试手段对M-SBA-15和PMMA/M-SBA-15复合材料以及孔道内PMMA进行了分析测试.研究表明,改性介孔分子筛仍保留了有序介孔材料的基本特性,M-SBA-15和相应的复合材料的比表面积、孔径以及孔容降低,表明PMMA载入到介孔分子筛的孔道中.与传统的溶液聚合所得的PMMA相比,介孔孔道内所得的PMMA的分子链的间规立构度有所提高,其分子量约为传统溶液聚合的十几倍,初始热稳定性明显提高,玻璃化转变温度提高9～11℃.此外,KH-151改性SBA-15载入最多的PMMA,所得的PMMA的分子量和玻璃化转变温度最高.     

Effect of silane coupling agent on mechanical interfacial properties of glass fiber‐reinforced unsaturated polyester composites

A silane coupling agent, γ‐methacryloxypropyltrimethoxysilane, for the surface modification of glass fibers was varied between 0.1 and 0.8 wt %. To understand the role of interfacial adhesion of glass fiber/unsaturated polyester composites, contact angles of the silane‐treated glass fibers were measured by the wicking method on the basis of the modified Washburn equation with deionized water, diiodomethane, and ethylene glycol as testing liquids. As a result, silane‐treated glass fibers led to increased surface free energy, mainly because of their increased specific or polar component. The mechanical interfacial behaviors based on the interlaminar shear strength (ILSS) of the composites determined by short‐beam tests and the critical stress‐intensity factor (K_IC) were also improved in the case of silane‐treated composites. The surface free energy and the mechanical interfacial properties especially showed the maximum value in the presence of 0.4 wt % silane coupling agent. It revealed that the increase of a specific component of the surface free energy or hydrogen bonding between the glass fibers and the coupling agents plays an important role in improving the degree of adhesion at interfaces in a composite system. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 55–62, 2003     

Mechanical Behavior of Unidirectional Curaua Fiber and Glass Fiber Composites

Summary: This work intends to promote the use of natural fibers by comparing the behavior of isophthalic polyester matrix composites reinforced with unidirectional curaua fibers with that of unidirectional glass fiber composites. The composites were produced varying the reinforcement angle (0°, 15°, 30°, 45°, 60°, 75° and 90°) with the aim of studying the fiber orientation effect on composite strength. Composites were also made varying the fiber volume fraction (10%, 20%, 30%, 40% and 50%). The efficiency of an alkaline (5% NaOH) surface treatment of the curaua fiber was also evaluated. The unidirectional composites were characterized using tensile, flexural and short beam tests as per ASTM standards. The properties of a lamina reinforced with either glass or curaua fibers were also studied using theoretical micromechanical approach available in commercial software. The curaua fiber alkaline treatment produced higher tensile strength results compared with untreated fibers. The increase in reinforcement angle significantly decreased strength and modulus of the composites, as expected, and the glass fiber composites showed a more pronounced dependence with fiber orientation. Although the glass fiber laminas showed the best mechanical performance, the results obtained with the curaua fibers were considered similar for angles greater than 45°.     

Plasticizer-assisted bonding of poly(methyl methacrylate) microfluidic chips at low temperature

As an important phthalate plasticizer, dibutyl phthalate (DBP) was employed to decrease the bonding temperature of poly(methyl methacrylate) (PMMA) microfluidic chips in this work based on the fact that it can lower the glass transition temperature of PMMA. The channel plates of the PMMA microchips were fabricated by the UV-initiated polymerization of prepolymerized methyl methacrylate between a silicon template and a PMMA plate. Prior to bonding, DBP solution in isopropanol was coated on PMMA covers. When isopropanol in the coating was allowed to evaporate in air, DBP was left on the PMMA covers. Subsequently, the DBP-coated covers were bonded to the PMMA channel plates at 90 °C for 10 min under pressure. The channels in the complete microchips had been examined by optical microscope and scanning electron microscope. The results indicated that high quality bonding was achieved below the glass transition temperature of PMMA (∼105 °C). The performance of the PMMA microfluidic chips sealed by plasticizer-assisted bonding has been demonstrated by separating and detecting ionic species by capillary electrophoresis in connection with contactless conductivity detection.     

Effect of surface treatment with potassium permanganate on ultra-high molecular weight polyethylene fiber reinforced natural rubber composites

The effects of surface treatment using potassium permanganate on ultra-high molecular weight polyethylene (UHMWPE) fibers reinforced natural rubber (NR) composites were investigated. The results showed the surface roughness and the oxygen-containing groups on the surface of the modified fibers were effectively increased. The NR matrix composites were prepared with as-received and modified UHMWPE fibers added 0–6 wt%. The treated fibers increased the modulus and tensile stress at a given elongation. The tear strength increased with increasing fiber mass fraction, attained maximum values at 4 wt%. The hardness of composites exhibited continuous increase with increasing the fiber content. The dynamic mechanical tests showed that the storage modulus and the tangent of the loss angle were decreased in the modified UHMWPE fibers/NR composites. Several micro-fibrillations between the treated fiber and NR matrix were observed, which meant the interfacial adhesion strength was improved.     

注塑型聚甲基丙烯酸甲酯多通道微流控芯片的研制及其性能考察

微流控芯片技术因具有微量、快速、高效和高通量等特点,已成为分析化学领域中的研究热点之一．在微流控芯片中,最常见的可用作芯片的材料为玻璃、石英和各种塑料．玻璃和石英有很好的电渗性和光学性质,可采用标准的刻蚀工艺加工和用化学方法进行表面改性,但加工成本较高,封接难度较大．     

Nanocarbon-poly(methyl methacrylate) composite materials

Nanocarbon-poly(methyl methacrylate) sols were prepared by pulsed laser ablation at the interface of target submerged in flowing liquid (PLA-IT/SFL) method, and the corresponding composite films were prepared by solution-casting. Spectra results indicated that there existed interactions between nanocarbon and the polymethyl methacrylate (PMMA) matrix, which was consistent with the decrease in glass transition temperature of the composites with increase of carbon content. TEM images revealed that a carbon encapsulated core/shell structure was formed in the composites, which could ensure good dispersion of carbon nanoparticles within the PMMA matrix. The decomposition of the composites was less influenced by the introduction of nanocarbon particles. Translated from Acta Polymerica Sinica 2006, 2(2) (in Chinese)     

Surface grafting of bamboo fibers with 1,2-epoxy-4-vinylcyclohexane for reinforcing unsaturated polyester

The present study focused on the surface treatment of bamboo fibers (BFs) with a bifunctional monomer, 1,2-epoxy-4-vinylcyclohexane (EVC), in the presence of N, N-dimethylbenzylamine as the catalyst, which results in the grafting of the fibers with C=C bonds on the surface. The modified BFs carrying C=C bonds were used to prepare bamboo fibers reinforced unsaturated polyester (UPE) composites by hand lay-up compression molding. Hence, chemical connections between the modified-fibers and UPE resins were formed via the free-radical polymerization of the C=C bonds during the preparation of the BFs–UPE composites. XPS analysis proved that the EVC was covalently bonded onto BFs. XRD analysis revealed that EVC-grafting did not alter the crystal structure of the fibers, but slightly decreased their crystallinity degrees. SEM images indicated an markedly improved interfacial adhesion between BFs and UPE matrices after fiber modification, which significantly increased the tensile strength, flexural strength, flexural modulus, storage modulus, glass transition temperature, and water resistance of the resulting BFs–UPE composites.     

高分散性SiO2/PMMA复合材料的制备与表征——接枝与交联

以硅烷偶联剂3-(甲基丙烯酰氧)丙基三甲氧基硅烷(MPS)改性SiO2/甲基丙烯酸甲酯(MMA)分散液为原料,通过原位本体聚合制得一系列具有不同SiO2含量和PMMA接枝率的高分散性SiO2/PMMA复合材料,索氏抽提分析复合材料的接枝和交联情况.发现抽提后体系中主要存在3部分物质:抽提液中含游离SiO2的PMMA溶液...     

Rapid prototyping of poly(methyl methacrylate) microfluidic systems using solvent imprinting and bonding

We have developed a method for rapid prototyping of hard polymer microfluidic systems using solvent imprinting and bonding. We investigated the applicability of patterned SU-8 photoresist on glass as an easily fabricated template for solvent imprinting. Poly(methyl methacrylate) (PMMA) exposed to acetonitrile for 2 min then had an SU-8 template pressed into the surface for 10 min, which provided appropriately imprinted channels and a suitable surface for bonding. After a PMMA cover plate had also been exposed to acetonitrile for 2 min, the imprinted and top PMMA pieces could be bonded together at room temperature with appropriate pressure. The total fabrication time was less than 15 min. Under the optimized fabrication conditions, nearly 30 PMMA chips could be replicated using a single patterned SU-8 master with high chip-to-chip reproducibility. Relative standard deviations were 2.3% and 5.4% for the widths and depths of the replicated channels, respectively. Fluorescently labeled amino acid and peptide mixtures were baseline separated using these PMMA microchips in <15s. Theoretical plate numbers in excess of 5000 were obtained for a approximately 3 cm separation distance, and the migration time relative standard deviation for an amino acid peak was 1.5% for intra-day and 2.2% for inter-day analysis. This new solvent imprinting and bonding approach significantly simplifies the process for fabricating microfluidic structures in hard polymers such as PMMA.     

PMMA-TiO2有机无机杂化玻璃的制备与表征

有机无机杂化材料是随着对溶胶凝胶方法的广泛研究而发展起来的，有时它们被称为ORMOSILS（OrganicallyModifiedSilicates）[1,2]或ORMOCERS（OrganicallyModifiedCerandcs）[2]．溶胶凝胶过程通过溶液化学（WetChemistry）的途径来形成无机骨架，在过去的几十年里，被广泛应用     

MMA接枝改性PVC/CaCO3纳米复合材料的力学性能

采用熔融共混法制备PMMA接枝改性纳米CaCO3增韧PVC（PVC/CaCO3）复合材料,并研究了复合材料的力学性能.结果表明,通过表面PMMA的接枝改性,可以显著提高纳米CaCO3增韧聚氯乙烯复合材料的拉伸强度和拉伸模量,在纳米CaCO3颗粒表面PMMA包覆层厚度为2nm时,复合材料的拉伸强度和拉伸模量达到极大值.对比于未处理纳米CaCO3和钛酸酯偶联剂处理纳米CaCO3,PMMA接枝改性纳米CaCO3增韧PVC复合材料的拉伸强度得到较大幅度提高.SEM显示,经过PMMA接枝改性后的碳酸钙在PVC基体中分散均匀,与基体界面结合良好.     

纳米碳/聚甲基丙烯酸甲酯复合材料的研究

采用脉冲激光轰击浸于流动液相中固体靶的方法,直接连续制备了纳米碳/PMMA的乙酸乙酯溶液,经浇膜法得到了纳米碳/聚甲基丙烯酸甲酯复合材料.光谱分析表明复合体系中存在某种作用,导致该复合材料的玻璃化转变温度明显下降.透射电镜结果表明纳米碳可与聚甲基丙烯酸甲酯形成核/壳结构,使得纳米碳均匀分散于聚合物基体中.热分析结果表明纳米碳的加入对聚甲基丙烯酸甲酯的热分解性能没有显著影响.     

Study of the gamma irradiation effects on the PMMA/HA and PMMA/SW

The behavior of the poly(methyl methacrylate) (PMMA) under the action of gamma radiation has been sufficiently studied. In this work, we present results from melt flow index (MFI), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and electron paramagnetic resonance (EPR) of PMMA composites with hydroxyapatite (HA) and seaweed residues (SW) irradiated with gamma rays at 1.08 kGy/h. Composites of PMMA/HA and PMMA/SW with 10%, 20% and 30% of the filler were prepared. The results show an increase in the MFI values with the integral dose of radiation, being consistent with chain-scission reactions. No EPR signal was observed in pure PMMA, while in the composites, the typical EPR signal of the PMMA radicals was observed, which increased with the amount of HA or SW. When comparing the relative intensities of the EPR signals for both types of composites, a slight increase in the concentration of free radicals generated in the sample with SW respect to that of PMMA/HA composite was obtained. A decay of the total free radical concentration was observed as time elapsed.     

Influence of surface modified TiO2 nanoparticles by gallates on the properties of PMMA/TiO2 nanocomposites

Nanocomposites based on poly(methyl methacrylate) (PMMA) and TiO₂ nanoparticles were synthesized by in situ radical polymerization of MMA in solution. The surface of TiO₂ nanoparticles was modified with four gallic acid esters (octyl, decyl, lauryl and cetyl gallate). The content of gallates present on the surface of TiO₂ was calculated from the TGA results. The influence of length of hydrophobic tail of amphiphilic alkyl gallates on dispersability of surface modified TiO₂ nanoparticles in PMMA matrix, the molecular weight and glass transition temperature of PMMA, as well as the thermal stability of the prepared PMMA/TiO₂ nanocomposites in nitrogen and air was investigated. The influence of content of TiO₂ nanoparticles on the properties of these nanocomposites was also examined. The formation of a charge transfer complex between the surface Ti atoms and the gallates was confirmed by FTIR and UV spectroscopy. TEM micrographs of the PMMA/TiO₂ nanocomposites revealed that degree of TiO₂ aggregation can be significantly lowered by increasing the length of aliphatic part of the used gallates. The molecular weight of PMMA slightly decreases with the increase of TiO₂ content, indicating that used TiO₂ nanoparticles act as radical scavengers during the polymerization of MMA. The presence of surface modified TiO₂ nanoparticles do not have an influence on the mobility of PMMA chain segments leading to the same values of glass transition temperature for all investigated samples. Thermal and thermo-oxidative stability of the PMMA matrix are improved by introducing TiO₂ nanoparticles modified with gallates.     

聚甲基丙烯酸甲酯微流控分析芯片的简易热压制作法

提出聚甲基丙烯酸甲酯(PMMA)微流控分析芯片的一种简易热压制作法,研究了镍基、单晶硅和玻璃3种阳模制备芯片及芯片的封合条件.采用扫描电镜(SEM)和电荷耦合检测器(CCD)对PMMA芯片的微通道及其横截面形貌进行了表征.SEM图和CCD图表明实现了热压封接.测定了PMMA芯片的伏安曲线和电渗流,其电渗流值与文献报道值基本一致.本法制作的PMMA芯片用于电泳分离Cy5荧光染料,峰高RSD为2.2%(n=11),理论塔板数7.4×10⁴m^-1.     

Low temperature bonding of poly(methylmethacrylate) electrophoresis microchips by in situ polymerisation

A novel method for bonding poly(methyl methacrylate) (PMMA) electrophoresis microchips at the temperature below the glass transition temperature of PMMA based on in situ polymerization has been demonstrated. Methyl methacrylate (MMA) containing initiators was allowed to prepolymerize in an 85 degrees C water bath for 8 min and 15 min to produce a bonding solution and a dense molding solution, respectively. The channel plate of the PMMA microchip was fabricated by the UV-initiated polymerization of the molding solution between a nickel template and a PMMA plate at room temperature. Prior to bonding, the blank cover was coated with a thin layer of the bonding solution and was bonded to the channel plate at 95 degrees C for 20 min under the pressure of binder clips. The attractive performance of the PMMA chips bonded by the new approach has been demonstrated by separating and detecting dopamine, catechol, three cations, and three organic acids in connection with end-column amperometric detection and contactless conductivity detection.     

Effect of Chemical Treatment and Fiber Loading on Mechanical Properties of Borassus (Toddy Palm) Fiber/Epoxy Composites

The aim of the present study was to investigate and compare the mechanical properties of untreated and chemically modified Borassus fiber–reinforced epoxy composites. Composites were prepared by the hand lay-up process by reinforcing Borassus fibers with epoxy matrix. To improve the fiber-matrix adhesion properties, alkali (NaOH) and alkali combined with silane (3-aminopropyltriethoxysilane) treatment of the fiber surface was carried out. Examinations through Fourier transform-infrared spectroscopy and scanning electron microscopy (SEM) were conducted to investigate the structural and physical properties of the Borassus fibers. Tensile properties such as modulus and strength of the composites made with chemically modified and untreated Borassus fibers were studied using a universal testing machine. Based on the experimental results, it was found that the tensile properties of the Borassus-reinforced epoxy composites were significantly improved as compared with the neat epoxy. It was also found that the fiber treated with a combination of alkali and silane exhibited superior mechanical properties to alkali-treated and untreated fiber composites. The nature of the fiber/matrix interface was examined through SEM of cryo-fractured samples. Chemical resistance of composites was also found to be improved with chemically modified fiber composites.