超支化聚氨酯阻尼涂层的制备及性能

以甲苯-2,4-二异氰酸酯(TDI)和二乙醇胺(DEOA)为原料, 采用一步法合成了超支化聚氨酯, 并对其改性制备了光固化超支化聚氨酯(UV-HPU)和超支化杂化聚氨酯(HHPU)两种树脂. 用傅里叶红外光谱(FTIR)和核磁共振氢谱(1H NMR)表征了预期产物. 以其为预聚物制备阻尼涂层, 动态力学分析(DMA)研究表明, 这两种涂层都具有高阻尼因子(tanδ≥1.0)、宽阻尼温度范围(tanδ≥0.5, 大于50 ℃)和宽阻尼频率范围(20～160 Hz); 通过基本性能测试和热重分析(TGA)发现杂化涂层聚氨酯较光固化聚氨酯具有更好的机械性能和热稳定性能; 杂化涂层聚氨酯的FTIR分析可知杂化涂层中硅氧烷水解缩合, 提高了交联密度; 杂化材料的断面扫描电镜(SEM)分析表明, 硅氧烷的水解缩合并未形成大颗粒纳米粒子而是形成均相体系.     

绿色合成法制备聚氨酯/纳米二氧化钛杂化复合材料及其荧光性能初探

采用无毒、无害的绿色方法合成聚氨酯,通过原位复合法制备出一种新型的聚氨酯/纳米二氧化钛杂化复合材料。利用傅里叶变换红外光谱分析(FTIR)、差示扫描量热分析方法(DSC)分别对聚氨酯/纳米二氧化钛杂化前后的结构进行表征。通过循环伏安法检测表明此杂化复合材料有良好的电化学稳定性及可逆性。采用荧光技术对聚氨酯/纳米二氧化钛杂化复合材料的性能进行研究。试验结果表明:当纳米二氧化钛与聚氨酯的质量比为100:7,超声时间为5 min时,得到的聚氨酯/纳米二氧化钛杂化复合材料的性能最好。     

溶胶-凝胶法制备光固化聚氨酯丙烯酸酯杂化材料的研究

以溶胶-凝肢法制备的硅溶胶为无机相,聚氨酯丙烯酸酯为有机相,以γ-甲基丙烽酰氧丙基三甲氧基硅烷(TMSPM)为两相间的偶联剂,制得了光固化杂化材料。研究了未固化的杂化体系的稳定性问题,并对其进行了结构表征和性能研究。无机相与有机相通过共价键相连。使得杂化体系光固化膜高硬度的获得并没有以柔韧性的损失为代价。在无机物含量较低时,聚氨酯丙烯酸酯／二氧化硅杂化体系先固化膜的耐磨性略有提高。     

“滑轮环”拓扑结构增韧聚乳酸及其形状记忆性能和机理探究

通过羟丙基化改性聚轮烷(HPPR)引发L-丙交酯(LLA)开环聚合,将具有机械互锁特性的"滑轮环"拓扑结构引入到聚乳酸体系中,制备了高韧度的"滑轮环"聚乳酸基聚氨酯高分子体系(SR-PLAU),并将其与化学交联的聚乳酸基聚氨酯体系(CC-PLAU),以及聚乳酸/HPPR原位化学共混体系(PLA/HPPR)进行对比研究.结果表明"滑轮环"拓扑结构的引入有效地提高了聚乳酸基材料的拉伸性能,杨氏模量大幅度下降,当"滑轮环"拓扑结构含量为1%(摩尔分数)时,材料的断裂伸长率提高了10倍;"滑轮环"拓扑结构的引入赋予材料优异的形状记忆性能,形状固定率和形状回复率都达到了90%以上.提出了可能的形状记忆机理,并利用材料的应力松弛特性对形状记忆机理进行了分析验证.为材料的增韧改性和新性能研究提供新的理论和思路.     

聚乳酸基可降解形状记忆聚合物的制备、结构与性能

以三枝化低不饱和度聚环氧丙烷/聚乳酸两嵌段共聚物(POLA)为原料, 甲苯二异氰酸酯(TDI)交联制备可降解聚环氧丙烷/聚乳酸基聚氨酯(POLA-PU). 通过对POLA共聚物序列结构的调控, 制备了由高模量低断裂伸长率的脆性到低模量高断裂伸长率的韧性POLA-PU可降解形状记忆材料. 由TMA测得POLA-PU的形变温度为96～153 ℃. POLA-PU试样在140 ℃的形状记忆恢复时间不超过20 s. 在200%拉伸形变条件下, POLA-PU的形变固定率在65%～100%之间, 形变回复率均可达100%. 实验表明, 形状记忆行为取决于链的交联密度, 记忆效应归属于不同温度下柔性链的构象熵变化. 降解实验结果表明, 聚乳酸链段的引入赋予了该形状记忆材料良好的降解性能, 且随着聚乳酸含量的降低而下降.     

聚丙烯酸/SiO2杂化纤维的制备与表征

采用溶胶凝胶-原位聚合法以正硅酸乙酯(TEOS)为硅源、乙烯基三乙氧基硅烷(VTEOS)为偶联剂制备了活性SiO2溶胶,经水解、缩合,再于引发剂AIBN作用下与丙烯酸进行原位聚合杂化,制得聚丙烯酸/SiO2杂化溶胶,陈化后用拉丝法制得聚丙烯酸/SiO2杂化纤维。研究了溶胶的杂化机理、成纤性能;采用红外光谱、扫描电子显微镜分析了杂化纤维的结构和微观形态;进行了杂化纤维的TGA和耐水性能测试。结果表明,该聚丙烯酸/SiO2杂化溶胶拉丝性能好,可拉丝时间达1h,杂化溶胶在粘度为1400～3000mPa.s时成纤性能好,可通过拉丝法制得形态良好的杂化纤维;聚丙烯酸与SiO2之间通过化学键作用,在纤维内部有机无机两相间形成均一的连续相;聚丙烯酸/SiO2杂化纤维的耐热和耐水性能均优于纯PAA。     

聚氨酯/苯丙杂化乳液的合成、表征和特性及其在复膜胶中的应用

由聚氨酯(PU)预聚物、丙烯酸丁酯和苯乙烯单体的乳液聚合制备了聚氨酯-苯乙烯-丙烯酸酯(PUSA)杂化乳液,1H NMR显示所得的PU预聚物由烯烃基团封端。 TEM表明,其粒径约为150 nm,且为颜色深浅不同的两部分所组成。 随着PU含量的降低,杂化乳液的热稳定性增加。 DSC分析表明,所得杂化乳液有单一的Tg值,且处于聚氨酯和聚苯丙(PSA)乳液Tg值的中间。 当将得到的杂化乳液用于纸塑和塑塑复合时,其剥离强度分别为14.1 N/2.5 cm和12.2 N/2.5 cm。     

二硫化钼纳米片/碳纳米纤维杂化材料的制备及其析氢性能

以碳纳米纤维(CNFs)作为负载基体和反应器采用静电纺丝技术和碳化工艺生长和调控二硫化钼(MoS_2)纳米片。通过改变前驱体溶液浓度来调控纳米片的形貌和结构,利用MoS_2纳米片的高催化活性和CNFs高比表面积、良好的稳定性以及高电导率的协同作用,研究不同形貌和结构的杂化纳米材料在电催化析氢方面的应用,探索杂化材料形貌与性能之间的潜在规律。运用多种分析测试技术对制备得到的纳米杂化材料进行表征,并对所制备的MoS_2/CNFs杂化材料的电催化析氢性能(HER)进行研究,研究表明近似皮芯结构的MoS_2/CNFs-10杂化材料的电催化析氢性能最好,初始析氢过电位在220 mV,Tafel斜率为110m V·dec~(-1)。     

PVA/SiO2-TiO2杂化电纺纤维膜的形态与性能

以正硅酸乙酯(TEOS)、钛酸四丁酯(TBT)和聚乙烯醇(PVA)为原料, 用溶胶凝胶法制备了PVA/(SiO2-TiO2)杂化纺丝液, 将其电纺成纤维膜. 红外光谱结果证实, PVA的羟基与TEOS和TBT水解后的羟基发生了缩合反应, 杂化电纺纤维膜以网络结构形式相结合; X射线衍射分析表明, 杂化电纺纤维膜的结晶度比纯PVA电纺纤维膜小; 扫描电镜表明, 随杂化纤维膜中无机相含量的增加, 纤维的直径不断增加, 纤维出现一定的弯曲和扭曲, 并伴有少量带状结构的纤维; 紫外-可见光谱结果表明, TiO2的引入增加了纤维膜的抗紫外性; TGA热分析结果表明, 杂化纤维膜的耐热性能优于纯PVA电纺纤维膜的; 耐水性和稳定性测试表明, 杂化纤维膜的耐水性和稳定性优于纯PVA和PVA/SiO2电纺纤维膜的.     

基于聚丙交酯的多嵌段聚氨酯的形状记忆性能和生物相容性

制备了以聚丙交酯(PLA)为软段, 2,4-甲苯二异氰酸酯(TDI)与乙二醇(EG)反应产物为硬段的多嵌段聚氨酯(PLA-PU), 并对其形状记忆效应和生物相容性进行了研究. 形状压缩50%的样品从起始恢复温度(22~37 ℃)开始, 在10 ℃范围内可以恢复到起始形状, 形变恢复率接近100%, 形变恢复力最大值达到1.5~4 MPa. 细胞培养实验结果初步证明PLA-PU的细胞相容性与PLA相当, 因而有可能用作植入形状记忆医疗器械材料.     

表面改性对VGCF分散性质的影响

针对气相生长碳纤维极易团聚及与树脂基体界面结合能力较差的难题,采用双氧水-浓硝酸二步法对VGCF进行表面改性处理。利用X射线衍射仪、热重分析仪、傅立叶红外光谱仪、紫外可见分光光度计等测试分析了改性前后VGCF的表面结构和在溶剂中的分散性,并以形状记忆聚氨酯为基体,采用溶液混合法制备了气相生长碳纤维/形状记忆聚氨酯的复合材料,测试了复合材料的力学性能。经过改性后,VGCF的石墨晶型结构几乎没有改变,VGCF表面的含氧官能团浓度得到较大提高,且其在有机溶剂中的分散性及分散稳定性也得到很大提高;在气相生长碳纤维/形状记忆聚氨酯的复合材料截面中,扫描电镜观察表明表面改性使得VGCF在基体中的分散性及与基体的界面结合能力都得到一定程度的提高;经二步法改性处理后的气相生长碳纤维比未处理气相生长碳纤维对复合材料的力学性能的增强效果更为明显。     

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.     

The interfacial feature of thermoplastic polystyrene composite filled with nitric acid oxidized carbon fiber

The quality of interfacial interaction is dictated by the surface chemistry of the carbon fibers and the composition of the matrix. The composition of polystyrene was modified by the addition of maleic anhydride (MAH) grafted polystyrene. The surface properties of the various matrix formulations were characterized by contact angle. Carbon fibers were modified by oxidation in nitric acid. The surface composition of the carbon fibers was characterized. The interaction between modified polystyrene and the carbon fibers was studied by single fiber pull‐out tests. The best adhesion behavior was achieved between polystyrene containing grafted MAH and nitric acid oxidation carbon fibers. The addition of MAH‐grafted polystyrene to the unmodified polystyrene caused the interfacial shear strength (IFSS) to increase. The IFSS of this fiber‐matrix combination allowed for the full utilization of the tensile strength of polystyrene. Copyright © 2009 John Wiley & Sons, Ltd.     

Interfacial studies on the ozone and air‐oxidation‐modified carbon fiber reinforced PEEK composites

In this work, ozone modification method and air‐oxidationwere used for the surface treatment of polyacrylonitrile(PAN)‐based carbon fiber. The surface characteristics of carbon fibers were characterized by XPS. The interfacial properties of carbon fiber‐reinforced (polyetheretherketone) PEEK (CF/PEEK) composites were investigated by means of the single fiber pull‐out tests. As a result, it was found that IFSS (interfacial shear strength) values of the composites with ozone‐treated carbon fiber are increased by 60% compared to that without treatment. XPS results show that ozone treatment increases the amount of carboxyl groups on carbon fiber surface, thus the interfacial adhesion between carbon fiber and PEEK matrix is effectively promoted. The effect of surface treatment of carbon fibers on the tribological properties of CF/PEEKcomposites was comparativelyinvestigated. Experimental results revealed that surface treatment can effectively improve the interfacial adhesion between carbon fiber and PEEK matrix. Thus the wear resistance was significantly improved. Copyright © 2009 John Wiley & Sons, Ltd.     

Interfacial adhesion and shear behaviors of aramid fiber/polyamide 6 composites under different thermal treatments

Aramid fiber (AF) reinforced by polyamide (PA) composites are excepted to have good interfacial matching due to their similar chemical interactions of hydrogen bonding. Thus, polarizing optical microscope (POM), transverse fiber bundle (TFB) test, and droplet micro-debonding technique were respectively performed to characterize interfacial crystallization, adhesion and shear behaviors of AF/PA6 composites with different thermal treatments. Both interface adhesion and AF fibrillation are enhanced with decreasing cooling rate or increasing annealing temperature due to the increased interfacial transcrystallization interaction. However, fast cooled interface also presents a high interfacial shear strength (IFSS) due to favorable normal residual stress. The apparent IFSS is believed to be a result of competition between crystallization enhancing interfacial interaction, interfacial mismatching aggravating debonding, and an uncertain residual stress positive or negative for load transfer. TFB failure mechanism including AF fibrillation and kinking are schematically presented. Fibrillation strength of AF is found to follow Weibull distribution evaluated by droplet micro-debonding technique.     

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.     

Preparation of Low-dielectric Permittivity Polyimide Resins with High Surface Activity from Chemically Bonded Hyperbranched Polysiloxane

Thermosetting resin matrix is the key component of advanced wave-transparent composites,where low dielectric constant,excellent processability,high thermal stability,as well as good bonding ability are required for resins.Herein,we prepared a series of phenylethynyl terminated polyimide(PI)resins by grafting amine-functionalized hyperbranched polysiloxane(HBPSi)to PI chains during the in situ polymerization.The effects of HBPSi on the processability of oligomers,molecular packing,thermal stability,dielectric property and bonding ability to reinforce Kevlar fibers of the cured PI/HBPSi composite resins have been examined in detail.The dielectric constants of the cured composite resins were greatly reduced from 3.29 to 2.19 without compromising its processability and thermal stability.Meanwhile,the 10 wt％HBPSi-containing PI resin demonstrated better bonding ability to reinforce fibers with the interfacial shear strength(IFSS)of 37.64 MPa,compared with that of neat PI-6 matrix(27.34 MPa),and better adhesion to metal with the lap shear strength of 10.48 MPa,50％higher than that of neat resin PI-6(6.98 MPa).These resultant PI/HBPSi composite resins exhibit excellent comprehensive properties,indicating their great potential as low-dielectric constant resin matrix in radar radome.     

Interfacial Properties of Two-Carbon Fiber Reinforced Polycarbonate Composites Using Two-Synthesized Graft Copolymers as Coupling Agents

Two model coupling agents, water-dispersible (WDGP) and tetrahydrofuran (THF)-soluble graft copolymers (TSGP), were synthesized for carbon fiber/polycarbonate (PC) composites. WDGP contains a long polyacrylamide (PAAm) chain grafted on a PC backbone, whereas TSGP contains a short grafted PAAm chain. Measurements of the interfacial shear strength (IFSS) and other interfacial properties were evaluated using a fragmentation test for two-fiber composites (TFC) to provide the same loading state. Optimal conditions for the treatment was established as a function of treatment time, temperature, initial concentration, and melting procedure. The amount adsorbed on the carbon fiber was higher for TSGP then for WDGP; the maximum improvements in IFSS for WDGP and TSGP were 54% and 74%, respectively. Mechanisms of energy adsorption for WDGP and intermolecular interaction for TSGP can be considered to contribute differently to IFSS improvement. The improvement in IFSS for both coupling agents may be due to chemical and hydrogen bonding in the interface between functional groups in the carbon fiber and PAAm in the coupling agents and to interdiffusion in the interface between PC in coupling agents and matrix PC. Copyright 2000 Academic Press.     

Interfacial Aspects of Electrodeposited Carbon Fiber-Reinforced Epoxy Composites Using Monomeric and Polymeric Coupling Agents

Using a monomeric and two polymeric coupling agents, interfacial aspects of electrodeposited (ED) carbon fiber/epoxy composites were investigated by means of fragmentation techniques and acoustic emission (AE). ED results for dipped and untreated fibers under dry and wet conditions were compared. Multifiber-embedded composites (MFC) were prepared for direct comparison. Various treating conditions such as treating time, concentration of coupling agent, and treating temperature were optimized, respectively. The adsorption mechanisms of the coupling agents onto the carbon fiber were analyzed in terms of the electrolyte molecular interactions during ED process, due to chain mobility in the aqueous solution. The microfailure mechanisms occurring from fiber breaks, and matrix and interlayer cracks were examined by AE parameters. The interfacial shear strength (IFSS) of ED-treated carbon fibers was much higher than that of the other two cases under dry and wet conditions. Well-separated AE groups were found for the untreated, the dipped, and the ED-treated cases, and significantly more AE events occurred from the ED interlayer failure between fiber and matrix than from the untreated and even than from the dipping cases. AE events from different-type interlayers may be correlated with IFSS based on the differing mechanical and chemical roles of the interlayers. Copyright 2000 Academic Press.     

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...