芳纶纤维/SMPU-SiO2复合材料的界面性能研究

选用形状记忆聚氨酯(SMPU)和正硅酸乙酯(TEOS)为前驱体,固体酸对甲基苯磺酸(PTSA)为催化剂,利用空气中的水分为水解水源,通过溶胶-凝胶法原位制备了形状记忆聚氨酯与二氧化硅( SMPU-SiO2)杂化材料,并将杂化材料应用于芳纶纤维增强的柔性复合材料中,以期改善芳纶纤维与基体的界面性能.同时,针对芳纶纤维表面...     

Poly (ether amide) and silica nanocomposites derived from sol–gel process

The sol–gel derived chemically combined organic–inorganic nanocomposites were synthesized from poly(etheramide) and tetraethoxysilane. Reaction of a mixture of 4-aminophenyl ether and 1,3-phenyldiamine with terephthaloyl chloride (TPC) in dimethylacetamide (DMAc) produced the amide chains. These chains were modified with carbonyl chloride end groups using a slight excess of diacid chloride and were then reacted with aminophenyl trimethoxysilane (APTMOS), where the amine group reacted with carbonyl chloride end groups. Hydrolysis/condensation of tetraethoxysilane (TEOS) and alkoxy groups present in APTMOS developed bonding between the polyamide chains and inorganic silica network generated in situ. By changing the relative proportions of the polymer solution and the amount of TEOS, the composition of hybrid films was varied. Thin hybrid films with various concentrations of silica network obtained after evaporation of the solvent were subjected to mechanical, dynamic mechanical thermal and morphological measurements. The results indicate a gradual increase in the modulus (3.84 GPa) and tensile strength (121 MPa) up to 15-wt.% silica relative to the pure polyamide. The elongation at break point and toughness gradually decrease with addition of silica content. These hybrids were found to be thermally stable up to a temperature of 500 °C. The weight retained above 800 °C was roughly proportional to amount of silica in the matrix. The glass transition temperature and the storage moduli increased with increasing silica concentration. The maximum increase in the T _g value (358 °C) was observed with 15-wt.% silica. Scanning electron micrographs indicated the uniform distribution of silica in the composites with an average particle size ranging from 9 to 47 nm.     

Preparation and characterization of chemically bonded aramid-titania hybrids using isocyanatopropyltrimethoxysilane

Transparent aramid based titania hybrid films have been prepared by the sol–gel process. A mixture of m- and p-phenylenediamines was reacted with terephthaloyl chloride forming aromatic polyamide chains in dimethylacetamide solvent. The titania network was generated insitu in this matrix by the hydrolysis and condensation of the various amounts of tetraethylorthotitanate. Hybrid films with concentrations of titania varying from 2.5 to 12.5 wt% were prepared; the higher percentages of titania in the organic matrix showed a tendency towards phase separation. These films were tested for their thermo-mechanical properties. To achieve a further improvement in properties of the matrix, the aramid chain was functionalized and the inorganic network was chemically bonded using isocyanatopropyltrimethoxysilane. The bonded hybrids showed a narrower distribution of titania particles and these were distributed as a co-continuous phase. The glass transition temperature (Tg) of the hybrid films measured through dynamic mechanical analysis showed a relatively higher increase with inclusion of titania in the covalently bonded hybrids. The maximum value of Tg noted in the chemically bonded composites with 12.5 wt% titania was 361 °C and the storage modulus value was 5.214 GPa at 100 °C, showing an increase of 62 % over the pure polymer. The hybrid films with titania showed an improved UV-stability as compared to the pure polymer.     

Influence of clay modification on the properties of aramid-layered silicate nanocomposites

Nanocomposites from organoclay and aromatic polyamide were prepared using solution intercalation method. Aramid chains were synthesised by reacting 4-aminophenylsulfone with isophthaloyl chloride in dimethylacetamide. Dodecylamine was used as a modifier to change the hydrophilic nature of montmorillonite into organophilic. Suitable quantities of organoclay were mixed in the aramid solution with high-speed stirring for homogeneous dispersion of the clay. Thin films cast from these materials after evaporating the solvent were characterised. The morphology of nanocomposites was determined by X-ray diffraction and TEM. Results revealed the formation of delaminated and disordered intercalated clay platelets in the aramid matrix. Mechanical data indicated improvement in the tensile strength and modulus with clay loading up to 6 wt.%. The glass transition temperature increased up to 20 wt.% organoclay, suggesting better cohesion between the two phases and thermal stability augmented with increasing clay loading. The water uptake reduced gradually as a function of organoclay showing decreased permeability.     

Scratch-Resistant Improvement of Sol-Gel Derived Nano-Porous Silica Films

Scratch-resistance of sol-gel derived nano porous silica films were studied. The thin films were prepared with a dip-coating method from both one-step and two-step catalyzed silica sols, and treated in a mixture gas of ammonia and water vapour afterwards. The thin films were characterized by using Atomic Force Microscope (AFM), ellipsometer, Fourier-transform Infrared Spectroscope (FTIR), respectively. Experimental results have shown that the two-step catalysis remarkably improves strength of the films, and abrasion-resistance and adhesion of the silica films were further increased after the mixture gas treatment. It is attributed to the cross-linking of silica particles in the sols by randomly branched or/and entangled linear chains and more Si–O–Si bonds formed by the mixture gas treatment.     

Effect of surface modification of montmorillonite on the properties of aromatic polyamide/clay nanocomposites

The surface modification of montmorillonite clay was carried out through ion‐ exchange reaction using p‐phenylenediamine as a modifier. This modified clay was employed to prepare aromatic polyamide/organoclay nanocomposite materials. The dispersion behavior of clay was examined in the polyamide matrix. Polyamide chains were synthesized from 4‐aminophenyl sulfone and isophthaloyl chloride (IPC) in dimethylacetamide. These amide chains were suitably end‐capped with carbonyl chloride end groups to interact chemically with modified montmorillonite clay. The resulting nanocomposite films containing 2–20 wt% of organoclay were characterized by TEM, X‐ray diffraction (XRD), thin‐film tensile testing; thermogravimetric analysis (TGA), differential scanning calorimetric (DSC) and water absorption measurements. Mechanical testing revealed that modulus and strength improved up to 6 wt% organoclay loading while elongation and toughness of nanocomposites decreased with the addition of clay content in the matrix. Thermal decomposition temperatures of the nanocomposites were in the range 225–450 °C. These nanocomposites expressed increase in the glass‐transition temperature values relative to pure polyamide describing interfacial interactions among the phases. The percent water uptake of these composites reduced upon the addition of modified layered silicate depicting improved barrier properties. Copyright © 2008 John Wiley & Sons, Ltd.     

Highly improved mechanical strength of aramid paper composite via a bridge of cellulose nanofiber

A novel aramid paper composite based on pretreated meta-aramid fiber via the addition of cellulose nanofiber (CNF) was fabricated, and the mechanical strength and interfacial strength of the aramid paper composite were investigated. The results indicated that modified fibers showed higher roughness and more available hydrophilic groups. Besides, compared with the pristine aramid paper, it turned out that the tensile index, tear index and interlayer bonding strength of the paper composites with CNF increased by 2.04 times, 2.36 times and 3 times, respectively. In addition, tensile energy absorption (TEA) was also improved by an increment of 99.7% with 20 wt% CNF. These apparent evidences can be accounted for the following mechanisms. On the one hand, enhanced mechanical properties of aramid paper composite were derived from the strong hydrogen bonding or dipole–dipole coupling interaction between aramid fiber and CNF. On the other hand, significant reinforcement of interlayer bonding strength can be attributed to the pivotal bonding bridge and filling agent between aramid chopped fibers (ACFs) and fibrid, which could improve interfacial adhesion of paper sheet. The thin film structure like “spider web” or “silk” from SEM images indicated the CNF was used as a bridge actually.     

Mesoporous silica reinforced by silica nanoparticles to enhance mechanical performance

Silica nanoparticle/mesoporous silica composite films were prepared by direct mixing with mechanical stirring and thermal imidization. The structural morphology was elucidated by scanning electron microscopy and the surface of the film was imaged by atomic force microscopy. The functional groups and desorption process of the films were elucidated by Fourier transform infrared spectroscopy and thermal desorption spectroscopy. The mechanical properties were investigated using a nanoindenter system. The gel matrix and the filler are very compatible because they have similar molecular content. The composite films had a higher mechanical strength than pure porous silica film. Their strength is related to the silica nanoparticle content. The interfacial compatibility, dispersion effect, and interfacial strength also affect the mechanical strength of composite films.     

Synthesis of zirconocene-based silica phases and evaluation in lindane and heptachlor epoxide adsorption/desorption

Silica (350 m(2) g(-1)) was chemically modified with Cp2ZrCl2 and (nBuCp)2ZrCl2 by grafting. Hybrid silica bearing surface indene groups was synthesized by the sol-gel method, followed by metallation with ZrCl(4)2THF. The resulting phases were characterized by Rutherford backscattering spectrometry (RBS), 13C and 29Si magic angle spin nuclear magnetic resonance, X-ray photoelectron spectroscopy, and diffuse reflectance infrared Fourier transform spectroscopy. According to RBS measurements, metal content was 0.2- to 0.3-wt% Zr/SiO2 for the grafted systems and 4.5-wt% Zr/SiO2 for the phase prepared by the sol-gel method. The solid phases were evaluated for the adsorption/preconcentration of lindane and heptachlor epoxide from aqueous solution. For comparative reasons, the commercial LC-18 phase was also evaluated. Analyte concentration was monitored by gas chromatography electron capture detection. For the grafted phases, the coordination sphere around the metal center seems not to influence the adsorption/desorption properties of these phases vis-a-vis the studied analytes. In the case of the phases prepared by the sol-gel method, recovery results were comparable to those observed for LC-18. Experiments using ZrO2 and ZrO2/SiO2 phases led to lower recovery results.     

Polymer-silica hybrid materials prepared from some functionalized polybenzoxazoles and polybenzobisthiazoles

Hybrid organic-inorganic composites were prepared by precipitating silica into hydroxypolybenzoxazole (HPBO) and sulfopolybenzobisthiazole (SPBT) polymers, with interfacial bonding between the phases improved by use of isocyanatopropyltriethoxy silane and N, N-diethylaminopropyltrimethoxy silane, respectively. The materials were transparent, and scanning electron micrographs indicated a uniform distribution of silica particles of domain sizes less than 1 m. Values of the tensile modulus and tensile strength of the HPBO-silica composites were found to increase with the silica content. Values of the modulus of the SPBT-silica composites also increased in this manner, but the improvements in tensile strength were nearly independent of the amount of silica. The composites exhibited thermal decomposition temperatures of approximately 400–500°C, and the thermal stability was significantly increased for both HPBO and SPBT materials with increase in silica content. The water absorption amount for both types of composites decreased significantly compared to that of the pure polymers, suggesting excellent weatherability.     

Thermal and mechanical properties of fluoroaramid-silica nanocomposites

Fluoroaramids have been used as an attractive matrix polymer for composites due to their excellent mechanical and surface properties. Properties of these polymers can be improved further by dispersing silica in these matrices at a nano-scale via the sol–gel process. The role of interfacial interaction on the thermal and mechanical properties in such hybrids has been investigated in the present work. Two types of hybrids have been prepared; one using the aramid matrix with pendant alkoxy groups on the chain and other without. Silica network was developed by addition of tetraethoxysilane and its subsequent hydrolysis and condensation in the polymer matrix. Well dispersed inorganic domains of nanometer scale were obtained in case of matrix with pendant alkoxy groups on the chain, which showed larger increase in the α- and β-relaxation temperatures, storage modulus and thermal stability as compared to the matrix without alkoxy groups. The role of interfacial interaction, and its effect on properties on the fluoroaramid-silica hybrid composites has been discussed.     

Synergistic modification by mercapto hyperbranched polysiloxane and functionalized graphene oxide on the surface of aramid fiber

With the purpose of improving the interfacial properties of aramid fibers reinforced rubber composites and enhancing the tensile strength of aramid fibers simultaneously, mercapto hyperbranched polysiloxane (HPSi) and functionalized graphene oxide (GO) were used to modify the surface of aramid fibers. Scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy and other characterization methods were performed to confirm the process of synergistic modification. Judging from the results of mechanical property tests, it could be acquired that the tensile strength of modified aramid fiber was increased by 16.8%, which could be ascribed to the wrapping effect of GO sheets. The interfacial properties were assessed by the pull-out tests of composites, and the results showed that the maximum pull-out force after synergistic surface modification was increased by 99.3%, which could be mainly related to additive reaction between double bonds and mercapto groups and the promotion of surface energy. More critically, during pull-out test, aramid fiber bundles might bring a part of shear stress into the grafted GO sheets, namely, GO sheets could convert fracture energy into interfacial energy, which would improve interfacial properties dramatically.     

连续纤维增强含二氮杂萘酮联苯结构聚芳醚砜酮树脂基复合材料的界面

利用射频感性耦合冷等离子体(ICP)处理技术改性连续纤维表面,分别采用X射线光电子能谱(XPS)、原子力显微镜(AFM)及动态接触角分析(DCA)系统研究了等离子体处理时间、放电气压、放电功率等工艺参数对连续碳纤维、芳纶纤维和对亚苯基苯并二噁唑(PBO)纤维的表面化学成分、表面形貌、表面粗糙度及表面自由能的影响.研究结...     

Structure and infrared emissivity of polyimide/mesoporous silica composite films

Polyimide/mesoporous silica composite films were prepared by direct mixing of polyamic acid solution and silylated mesoporous silica particles, or by condensation polymerization of dianhydride and diamine with silylated mesoporous silica particles in N,N-dimethylacetamide, followed with thermal imidization. Structure and glass transition temperatures of the composite films were measured with FTIR, SEM, EDX, XPS and DMTA. The results show that the silylated mesoporous silica particles in the composites tend to form the aggregation with a strip shape due to phase separation. The composite films exhibit higher glass transition temperature as comparing with that of pure polyimide. It is found that the composite films present lower infrared emissivity value than the pure polyimide and the magnitude of infrared emissivity value is related to the content of silylated mesoporous silica in the composite films. Inhibiting actions of silylated mesoporous silica on infrared emission of the composite films may be owing to presence of nanometer-scale pores in silylated mesoporous silica.     

Organic–inorganic nanocomposites prepared from fluoro-aramid and silica

Fluoro-aramid-based sol/gel-derived nanocomposites were synthesized by condensing a mixture of 4,4′-(hexafluoro-isopropylidene)dianiline and 1,3-phenylenediamine with terephthaloylchloride (TPC) in dimethylacetamide. TPC was added in slight excess to produce amide chains with carbonyl chloride end groups and then replaced with alkoxy groups using aminophenyltrimethoxysilane to develop bonding with the silica network. Mechanical, dynamic mechanical thermal, water absorption and morphological measurements were carried out on the thin hybrid films. Increase in the tensile strength and modulus was observed as compared to pristine polyamide. The thermal decomposition temperature was found in the range of 400–500 °C. The water absorption was found to be reduced with higher silica content. The glass transition temperature and the storage moduli increased with increasing silica concentration. The maximum increase in the T _g value (345 °C) was observed with 20 wt% silica. Scanning electron microscopy revealed the uniform distribution of silica in the matrix with an average particle size ranging from 8 to 50 nm.     

Surface modification of silica nanoparticles by a polyoxyethylene sorbitan and silane coupling agent to prepare high-performance rubber composites

The interfacial interaction between nano-silica and rubber matrix is very important for the preparation of high-performance rubber composites. In this paper, we first proposed the use of TWEEN-20 as a new silica modifier, it has four long arms consisting of three polyether chains with terminal hydroxyl group and a fatty chain. The oxygen on the polyether can form a hydrogen bond with the silanol groups on silica surface, and the terminal hydroxyl groups can chemically react with the silanol groups without any VOCs. Moreover, the long fatty chain can weaken silica polarity to obtain a better compatibility with rubber, so that silica modified by TWEEN-20 with chemical reaction and physical absorption can homogeneously disperses in rubber matrix. Nextly, we prepared high-performance natural rubber (NR) composites by adjusting the ratio of TWEEN-20 to TESPT to adjust the physical and chemical interaction between nano-silica and rubber molecular chains. The results indicated that the performances, including the filler dispersion, static mechanical properties, and dynamic heating (viscoelastic self-heating), were optimal when the ratio of TESPT to TWEEN-20 was 2:1. In addition, one-third of TESPT was replaced by TWEEN-20 to prepare silica/rubber composites, which can reduce one-third of VOCs, improve “scorchy”, and achieve high dispersion of silica.     

Preparation and properties of aramid/layered silicate nanocomposites by solution intercalation technique

Polymer—clay nanocomposites were synthesized from aromatic polyamide and organoclay using the solution intercalation technique. Polyamide chains were produced through the reaction of 4,4′‐oxydianiline (ODA) and isophthaloyl chloride (IPC) in N, N′‐dimethyl acetamide, using stoichiometry yielding chains with carbonyl chloride end groups. The intercalation of sodium montmorillonite (Na‐MMT) was carried out using p‐phenylene diamine as a swelling agent through an ion exchange reaction. Different concentrations of organoclay were blended with the polyamide solution for complete dispersion of clay throughout the matrix. The resulting composite films were characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), mechanical testing, thermogravimetry (TGA), differential scanning calorimetry (DSC) and water absorption measurements. The XRD pattern and morphology of the nanocomposites revealed the formation of exfoliated and intercalated clay platelets in the matrix. The film containing a small amount of clay was semitransparent and had a tensile strength of the order of 70 MPa (relative to the 52 MPa of the pure aramid). Thermal decomposition temperatures were in the range of 300–450°C and the weight of the samples remaining after heating to 900°C was found to be roughly proportional to the clay loading. DSC showed a systematic increase in the glass transition temperature with increase in clay content. Water absorption of the pristine aramid film was rather high (5.7%), which reduced upon loading of organoclay. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis of polyether‐based polyurethane‐silica nanocomposites with high elongation property

The NCO‐terminated prepolymers, prepared by reacting a mixture of poly(tetramethylene glycol) and fumed nanosilica with 4,4′‐diphenylmethane diisocyanate, were chain‐extended with 1,4‐ butanediol to yield polyurethane‐silica nanocomposites. The nanosilica particles were well dispersed in the polyurethane matrix up to 3 wt%. The polyurethane chains in the interfaces were covalently linked to the nanosilica surfaces through urethane bonds. Introduction of the nanosilica into the polyurethane enhanced both tensile strength and elongation of the resulting nanocomposite films. Especially, the elongation at break of the nanocomposite films containing 1 wt% nanosilica was 3.5 times greater than that of the pure polyurethane films. Copyright © 2005 John Wiley & Sons, Ltd.     

表面复合纳米SiO_2和碳纳米管玻璃纤维增强尼龙6的结构与性能

利用静电相互作用在玻璃纤维(GF)表面分别复合纳米二氧化硅(SiO2)和多壁碳纳米管(MWNTs),制备了GF-SiO2、GF-MWNTs复合增强体,并通过转矩流变仪制备了尼龙6(PA6)/GF-SiO2和尼龙6(PA6)/GF-MWNTs复合材料.利用扫描电子显微镜(SEM),示差扫描量热仪(DSC),热机械分析仪(DMA)等手段研究了复合材料的微观结构、热学及力学性能.结果表明,静电复合的方法可以使纳米二氧化硅(nano-SiO2)、多壁碳纳米管(MWNTs)在GF表面达到均匀吸附,复合增强体能加快尼龙6的结晶速度,并使材料的玻璃化温度、动态模量、拉伸强度、结晶温度等明显提高,其中GF-MWNTs对复合材料性能的提高最明显,拉伸强度提升了21%,模量提高了28%.     

Understanding the effect of filler shape induced immobilized rubber on the interfacial and mechanical strength of rubber composites

Styrene butadiene rubber (SBR) composites with silica, halloysite nanotubes (HNTs) and montmorillonite (MMT) were prepared and the interfacial and mechanical properties were compared to understand the reinforcing behaviours of these fillers based on the results of SEM, DSC, DMA, etc. Due to the formation of interparticle domain, HNTs immobilized more rubber approaching their surface than silica and MMT. Interestingly, only tightly immobilized rubber chains made contribution to the enhancement of interfacial and mechanical strength of SBR composites. This was because the tightly immobilized rubber acted as a bridge in the filler-rubber interface and induced the formation of stretched rubber chains linked filler network when the composites were loaded in tension, while loosely immobilized rubber were easy to slip off from filler surface, causing the separation between filler and bulk rubber. Therefore, silica with more tightly immobilized rubber approaching its surface showed better reinforcing effect on rubber than HNTs and MMT.