原位聚合制备尼龙6/纳米SiO2复合材料研究

对原位聚合制备尼龙6／纳米SiO2进行研究。结果表明，无论是否对纳米SiO2复合材料进行偶联化处理，其表面均将在原位聚合过程中与尼龙6产生接枝；SiO2表面接枝物的生成，可在某种程度上造成体系结晶程度的降低，但复合体系的力学性能主要由SiO2粒子的分散程度、粒子和其体之间的相界面性质等因素决定；采用经偶联剂处理并具有较小粒径和较大比表面积的SiO2对尼龙6进行复合，可使复合体系的力学性能指标达到较高的水平，且硅烷偶联剂的最佳用是为SiO2的3％左右。     

The influence of interphase on nylon‐6/nano‐SiO2 composite materials obtained from in situ polymerization

Three commercially available silane, titanate and aluminate based coupling agents were used to pretreat nano‐SiO₂ for the preparation of nylon‐6/nano–SiO₂ composites via in situ polymerization. The interphases formed in different composite systems and their influence on material properties were investigated. Results indicated that the interfacial interactions differed between composite systems, whereas rigidity and toughness of composites were all improved by addition of pretreated silicas at an optimal content of 4.3 wt%. The presence of pretreated silicas did not have a distinct influence in the non‐isothermal crystallization behaviour of the nylon matrix. The composites containing pretreated silicas had slightly higher dynamic viscosities and superior storage moduli at high frequency, compared with neat nylon‐6. Copyright © 2003 Society of Chemical Industry     

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。     

The effect of the interface structure of different surface‐modified nano‐SiO2 on the mechanical properties of nylon 66 composites

The nylon 66‐based nanocomposites containing two different surface‐modified and unmodified SiO₂ nanoparticles were prepared by melt compounding. The interface structure formed in different composite system and their influences on material mechanical properties were investigated. The results indicated that the interfacial interactions differed between composite systems. The strong interfacial adhesion helped to increase tensile strength and elastic modulus of composites; whereas, the presence of modification layer in silica surface could enhance the toughness of composites, but the improvement of final material toughness was also correlated with the density of the adhered nylon 66 chains around silica nanoparticles. In addition, the results also indicated that the addition of surface‐modified silica nanoparticles has a distinct influence on the nonisothermal crystallization behavior of the nylon 66 matrix when compared with the unmodified silica nanoparticle. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Plasma surface modification of silica and its effect on properties of styrene–butadiene rubber compound

The effects of surface modification of silicas by plasma‐polymerization coating, together with modification using a silane coupling agent for a comparison on the dispersion and physical properties of styrene–butadiene rubber (SBR) are reported. The chemical compositions of the plasma‐polymerization coating were characterized using FTIR and Auger spectrometer and it was found that the plasma coating was composed of C?C and C? H bonds. The surface modification of silica by either plasma polymerization or silane greatly improved the dispersion of silica particles in SBR vulcanizates. The plasma‐polymerization modification of silica improved the tensile modulus of SBR vulcanizates without deterioration of important basic properties such as tensile strength and elongation at break. © 2002 Society of Chemical Industry     

Properties of organic–inorganic composite materials prepared from acrylic resin emulsions and colloidal silicas

To design an organic–inorganic composite material with colloidal silica as the inorganic component, an acrylic resin emulsion and an organic silane hybridized acrylic resin emulsion were prepared by emulsion polymerization. The organic–inorganic composite films were prepared by blending the emulsion and the colloidal silica. The contact angles for water, gloss at 60°, and the transparencies of those films were measured. The dispersion state of colloidal silica in films was observed with a scanning electron microscope (SEM) and a transmission electron microscope (TEM). From these results, the contact angle for water of the organic–inorganic composite film obtained from the silane hybridized acrylic resin emulsion was lower than that of the organic–inorganic composite film obtained from an acrylic resin emulsion. The contact angles for water in organic–inorganic composite films with colloidal silicas were lower than those of the films without the colloidal silicas. The films prepared from silane hybridized acrylic resin emulsion composites with colloidal silicas of less than 100 nm were more hydrophilic. SEM and TEM observations demonstrated that some aggregations of the small colloidal particle silica were densely dispersed on the film surface. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2051–2056, 2006     

Wood fiber surface treatment level effects on selected mechanical properties of wood fiber-cement composites

The objective of this study was to determine the effects of sodium (N) silicate, potassium (K) silicate, and silane (Si) treatment levels on newspaper and unbleached kraft fibers for enhancing selected mechanical properties of wood fiber-cement composites compared to untreated wood fiber-cement composites. Both wood fiber types were treated with selected aqueous solution strengths, air dried, and mixed with water and cement. The bending and compression properties of the specimens were determined after 28 days of hydration. Results of this study indicated that the aqueous chemical treatments of the wood fibers enhanced some of the mechanical properties of wood fiber-cement composites compared to the untreated wood fiber-cement composites. The enhancement depended on chemical treatment and wood fiber type. All three chemical treatments of newspaper fiber enhanced the normalized toughness values compared to the untreated newspaper fiber-cement composites. In addition, higher treatment levels using N silicate with newspaper fiber improved the compressive strength and bending modulus of the composites compared to the untreated newspaper fiber-cement composites. Kraft fiber treated with all three chemicals enhanced the compressive strength, bending modulus and bending strength compared to the untreated kraft fiber-cement composites. However, only silane-treated kraft fiber improved the normalized toughness values compared to the untreated kraft fiber-cement composites. The results of the study indicated that certain chemical treatments react better with different wood fiber types resulting in selected mechanical property enhancements.     

Anionic nylon 6/TiO2 composite materials: Effects of TiO2 filler on the thermal and mechanical behavior of the composites

The nylon 6‐based composite materials containing untreated and surface‐treated TiO₂ particles with 3‐aminopropyltriethoxysilane (APTEOS), as coupling agent were prepared by in situ anionic polymerization of ε‐caprolactam in the presence TiO₂ as a filler using the rotational molding technique. The thermal behavior and mechanical properties of the neat nylon 6 and its composites were investigated using various techniques such as differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), a tensile and flexural test and impact strength. Experimental results revealed that both untreated and surface‐modified TiO₂ had distinct influence on the melting temperature (T_m), crystallization temperature (T_c), and degree of crystallinity (α_DSC), thermal stability, storage modulus (E′), and loss factor (tan δ), and mechanical properties of nylon 6 matrix. Dynamical mechanical analysis indicated that addition of TiO₂ particles into nylon 6 matrix increased both the storage modulus and the glass transition temperature. The corresponding values of nylon 6 composites with modified filler were higher than that of nylon 6 composite with untreated TiO₂ particles. Tensile and flexural characteristics of the nylon 6 composites were found to increase while the elongation at break and impact strength with increase in TiO₂ concentration relative to neat nylon 6. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

An attempt to quantitatively predict the interfacial adhesion of differently surface treated nanosilicas in a polyurethane coating matrix using tensile strength and DMTA analysis

Surface treatment of nanosilicas with silane coupling agents is a common method by which the interfacial interaction of these particles can be enhanced. This is because of interactions taking place between the silane and silica, as well as the interactions between the organic part of the silane with the polymeric matrix. Therefore, interfacial interaction of silane grafted silica plays a key role to ensure a better reinforcing effect. The present work is an attempt to quantitatively predict the interfacial bonding strength between differently amino silane treated nanosilicas and a polyurethane coating matrix. This was based on the data deduced from tensile strength and dynamic mechanical thermal (DMTA) experiments of differently loaded untreated and treated nanosilicas loaded films. Using a predefined linear model taking into account the yield stresses of the particle loaded polyurethane and that of the matrix itself, an interaction bonding strength parameter was obtained. It was shown that this parameter was directly proportional to the amino silane content on nanosilica. However, for higher loadings of silicas the model best fit the data deviated from linearity and obeyed a second order equation, in which the second power term attributing the extent of interfacial strength was systematically increased. These results were in good agreement with the storage modulus and glass transition temperature values revealed by DMTA analysis.     

Effect of sawdust surface treatment and compatibilizer addition on mechanical behavior,morphology, and moisture uptake of polypropylene/sawdust composites

Polypropylene/sawdust composites were investigated to assess the effect of sawdust surface treatment and compatibilizer addition on polymer/fiber adhesion. Two silane coupling agents were used for sawdust surface treatment: vinyl‐tris (2‐methoxyethoxy) silane and (3‐aminopropyl)triethoxysilane. Maleic anhydride grafted polypropylene was used as compatibilizer. Composites were prepared in a corotating twin‐screw extruder coupled to a Haake torque rheometer and submitted to tensile and bending tests as well as scanning electron microscopy (SEM). Moisture uptake tests were also performed. Results showed that incorporation of untreated sawdust to polypropylene (PP) caused reduction in composite tensile strength and increase in stiffness. When the only treatment used was surface modification with silane coupling agents, no significant changes were observed in mechanical properties. However, when compatibilizer was added to the composites, tensile strength was increased, and % elongation at break reduced, indicating improved system compatibility. The composite presenting the highest increase in tensile strength was that containing sawdust treated with amino silane in addition to the compatibilizer. SEM analyses corroborated the mechanical property results. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Effect of silane integrated sol–gel derived in situ silica on the properties of nitrile rubber

Nitrile rubber/silica composites are prepared by a sol–gel process using tetraethoxysilane as precursor in the presence of γ‐mercaptopropyltrimethoxysilane as a silane coupling agent. Here, we follow a novel processing route where the silica particles are generated inside the rubber matrix before compounding with vulcanizing ingredients. The effect of in situ generated silanized silica on the properties of the rubber composite has been evaluated by studying curing characteristics, morphology, mechanical and dynamic mechanical properties. Enhanced rubber–filler interaction of these composites is revealed from stress–strain studies and dynamic mechanical analysis. Excessive use of silane shows an adverse effect on mechanical properties of the composites. Due to finer dispersed state of the in situ silica and enhanced rubber–filler interaction, the mechanical properties and thermal stability of the composites are improved compared to corresponding ex situ processed composite. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40054.     

Flexural and Charpy impact behaviour of epoxy/glass fabric treated by nano-SiO2 and silane blend

A sizing formulation, containing compatible and incompatible silane coupling agents with epoxy resin in conjunction with nanoscale colloidal silica, was used to modify the surface of glass fabric. The modified glass fabric/epoxy resin composite panels were fabricated and characterised by flexural test, Charpy impact test and scanning electron microscope (SEM). By combining nano silica with silane blend in the fabric sizing, more energy was consumed under bending and impacting, which resulted in an improvement of the toughness in composites. The flexural strength, bending stain and Charpy impact strength of the epoxy composite/glass fabric treated with 1?wt-% nano silica and silane blend were ～42, ～22 and 35%, respectively, higher than those of silane blend coated glass fabric-reinforced composites (without nano silica). Furthermore, the change of the brittle fracture of the composite into ductile fracture was investigated by SEM micrographs. A possible toughening mechanism was also proposed.     

MC尼龙6/纳米SiO2复合材料的合成

用原位聚合法制备MC尼龙6／纳米SiO2复合材料。当纳米SiO2的加入量为1％时,力学综合性能最优。与纯MC尼龙相比,拉伸强度提高21％,弯曲模量提高40．3％,简支梁冲击强度提高69．1％,断裂伸长率降低43％。随着纳米SiO2含量的增加,复合材料的力学性能呈现减小趋势。采用SEM、XRD对产物进行了表征,表明采用修饰后的纳米SiO2加入到产物中,粒子分布均匀,粒径分布窄,粒子的粒径在30nm左右。随着纳米SiO2加入量的增加,MC尼龙6／纳米SiO2复合材料的结晶度下降。     

Simultaneous enhancements of mechanical and thermal properties of monomer cast nylon via kaolin modified by poly (ethylene glycol diglycidyl ether)

Monomer cast nylon was incorporated with different contents of kaolin, which is grafted with poly (ethylene glycol diglycidyl ether) via in-situ polymerization. The influence of treated-kaolin and kaolin contents on composites properties was studied. Treated-kaolin has a better effect on the properties of nylon than kaolin. Thermogravimetric analysis and Differential scanning calorimetry analysis show that that the feeding of kaolin improved thermal stability and crystallinity of nylon. The results indicate that using treated-kaolin as reinforcement, the composites displayed remarkable mechanical properties, the tensile strength and notched impact strength are 83.6 MPa and 4.46 MPa, respectively. The water absorption capacity of composites was greatly reduced by 50% with the feeding of kaolin.     

Synthesis of modified silica spheres used for the preparation of dual ultraviolet‐ and thermo‐cured epoxyacrylate/silica composites

To investigate the interfacial effect on properties of epoxyacrylate–silica composites, submicron‐sized silica spheres were synthesized by sol–gel reaction under a basic environment and their surfaces were endowed with vinyl functional groups by further modification with 3‐methacryloxypropyl trimethoxy silane. The pure silica (PS) and the modified silica (MPS) spheres were characterized by Fourier transform infrared, ²⁹Si‐ and ¹³C‐nuclear magnetic resonance (NMR), scanning electron microscope (SEM), and particle size analyzer. The silica spheres were then added to the presynthesized difunctional epoxyacrylate resin with one vinyl group and one epoxide group at each end, in addition to the photo‐ and thermo‐curing agents. After cure, thermal and mechanical properties of the obtained epoxyacrylate–silica composites were measured and compared. Tensile mechanical properties including initial modulus, ultimate tensile strength, and elongation at break, as well as the fracture energy of the epoxyacrylate–silica composite were all increased by increasing the content of silica spheres. Moreover, the composites filled with MPS had stronger interfacial strength between silica sphere and matrix than those with PS and thus exhibited an additional increase of tensile mechanical properties and fracture toughness. The increase of fracture toughness was owing to the crack deflection and particle–matrix debonding as evidenced by SEM pictures on the fracture surface. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

In situ polymerization of polyamide 66 nanocomposites utilizing interfacial polycondensation. III. Co‐synthesis of silica nanocomposites via sol–gel chemistry

In situ co‐synthesis of nylon 66 (PA66)‐silica nanocomposites can be accomplished through sol–gel chemistry conducted simultaneously with the nylon polymerization. Unfunctionalized silica nanocomposites and bonded silica nanocomposites wherein the inorganic silica phase chemically couples to the nylon polymer through a functionalized silane are generated via the simultaneous initiation of synthesis reactions in the inorganic and organic species. The effects of agitation and water‐to‐silane molar ratio on the courses of the inorganic and organic reactions and the generated silica morphology in the resulting nanocomposites are investigated using the tools of Brookfield Viscometer, Fourier transform infrared spectroscopy, and transmission electron microscopy. Dynamic mechanical analysis confirms the mechanical reinforcement of the various nanocomposites in relation to their silica content and network morphology. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

表面改性对聚丙烯/微米氢氧化镁复合材料性能的影响

研究了表面处理剂（钛酸酯和硅烷偶联剂）和原位聚合方法对聚丙烯/微米氢氧化镁（MH）复合材料的力学性能及流变性能的影响。采用DSC、SEM和毛细管流变仪对PP/MH（80/20）复合材料的性能进行了研究。结果表明：原位聚合改性后的微米MH与PP基体间的界面黏结力得到了加强,复合材料的冲击强度较填充未改性MH的复合材料提高了26.4 ％。在PP基体中添加聚合物包覆改性微米MH粒子的复合材料熔体流动速率较纯PP上升了64 ％。在相同剪切速率下,填充聚合物包覆改性MH的复合材料熔体表观黏度明显低于填充未改性微米MH的复合材料,表明聚合物包覆改性后的MH降低了其对PP熔体流动的阻碍作用,改善了PP/MH复合材料的流动性能。     

氧化处理对MC尼龙/C3D复合材料摩擦磨损性能的影响

以己内酰胺单体和经氧化处理的碳纤维三维编织物(C3D)为原料,采用原位聚合方法制备了C3D增强浇铸尼龙(MC尼龙/C3D)复合材料。在磨损试验机上进行了滑动摩擦试验,采用扫描电子显微镜对磨痕和磨屑形貌进行观察和分析,研究了氧化处理对MC尼龙/C3D复合材料摩擦学性能的影响。结果表明,C3D经过氧化处理后所制MC尼龙/C3D复合材料的摩擦系数明显小于C3D未经氧化处理的MC尼龙/C3D复合材料。随着载荷的增加,材料的摩擦系数增大,而磨损率减小;在较高滑动速度下,摩擦系数和磨损率均较小;从磨痕和磨屑形貌观察到,C3D经氧化处理后与基体结合好,而未经氧化处理的C3D与基体剥离,但是C3D经氧化处理的复合材料的磨损率在较高载荷下略有增大。表明,C3D的氧化处理提高了碳纤维与基体间的结合强度,同时在一定程度上提高了复合材料的摩擦学性能。     

Improvement in mechanical,electrical, and shape memory properties of the polystyrene-based carbon fiber-reinforced polymer composites containing carbon nanotubes

Carbon fiber-reinforced polymers based on polystyrene matrix containing elastomer and carbon nanotubes (CNTs) were produced by compression molding. The effects of carbon fabric (CF) concentration and silane treatment on the morphology, mechanical, electrical, and shape memory properties of the multilayer composites were investigated. The SEM analyses showed that fibers of the silane-treated CFs were more homogeneously covered with the polymer layers than the untreated CFs. The tensile strength and modulus of the composites increased by 521% and 125%, respectively, with an increasing number of CF plies from one to five. Upon silane treatment, the tensile strength of the multilayer composite improved by 26%, and the tensile modulus decreased by 18.4%. Electrical conductivities of the composites were in the semiconductor region due to the presence of both CNTs and CFs. 100% shape recovery less than a minute recovery time was obtained for all the composites with electrically triggered bending test.     

The Effect of Particle Matrix Adhesion on the Mechanical Properties of Silica Filled Cyanate Ester Composites

Summary: The effect of silica and its surface treatment on the mechanical properties of composites was studied as part of the evaluation of cyanate ester matrices as potential electronic encapsulants. Three filler surface treatments were used, as a qualitative interfacial adhesion scale, in an attempt to gauge the magnitude of interfacial adhesion between untreated filler and the cyanate ester matrix. There was strong interfacial adhesion between matrix and untreated filler. The level of silica content most affected composite modulus and fracture toughness. Filler surface treatment most affected composite strength and fracture toughness/energy. Composite fracture was found to occur via crack pinning and/or crack blunting depending on the strength of adhesion. The composites evaluated were found to possess suitable mechanical properties for potential use as electronic encapsulants.