织物涂层用含氟硅油改性聚氨酯水分散体的合成与表征

为合成高性能织物涂层剂,以聚四氢呋喃醚、聚乙二醇、端氨基含氟硅油为混合软段,合成了有机硅改性的水性聚氨酯(WFSPU)。用红外光谱、核磁共振谱表征了改性聚氨酯的化学组成;通过纳米粒度测定及Zeta电位分析考察了乳液的稳定性;通过差热扫描量热、正电子湮灭谱及静态拉伸试验分别研究了WFSPU膜的热性能、自由体积空洞及力学性能。研究结果表明,当含氟硅油用量(质量分数)<10%时,可以制得稳定的乳液,聚氨酯膜的软段玻璃化转变温度约为-78℃。当含氟硅油质量分数为6%时,WFSPU膜的拉伸模量最高,达到47.33 MPa,断裂伸长率为663.49%。     

采用聚硅氧烷(HPSO VPSO)和Al-Si粉连接无压烧结SiC陶瓷

采用含氢聚硅氧烷(HPSO)和含乙烯基聚硅氧烷(VPSO)2种陶瓷先驱体作为连接剂的主要组分, 以Al-Si粉为填料, 通过反应成形连接工艺连接无压烧结碳化硅。采用热重法、 差示扫描量热法和X射线衍射法研究了Al-Si粉对HPSO和VPSO的混合物(HPSO-VPSO)的裂解过程和陶瓷产率的影响, 同时也研究了Al-Si粉含量、 升温速率及连接温度对连接强度的影响。并采用扫描电镜和能谱仪对连接件界面区域的微观结构和成分进行了分析。Al-Si粉的加入促进了HPSO-VPSO的裂解, 提高了陶瓷产率。当HPSO-VPSO与Al-Si粉质量比为1∶1, 连接压力为50kPa, 连接温度为900℃, 高温保温时间为30min, 升温速率为4℃/min时, 所得连接件的连接强度(剪切强度)达到最大值93MPa。连接层厚度约为75μm, 结构均匀致密, 连接层与母材结合良好, 在界面处没有明显的裂纹、 孔洞等缺陷。Al、 Si元素在连接层与无压烧结碳化硅的界面处发生了扩散, 促进了界面结合, 从而提高了连接强度。      

有机硅改性丙烯酸酯细乳液的合成及其涂料印花性能研究

以侧链乙烯基聚硅氧烷、丙烯酸丁酯、甲基丙烯酸甲酯、苯乙烯、丙烯酸为单体,正十六烷为助乳化剂,过硫酸铵为引发剂,合成了兼具疏水性和柔软性的涂料印花粘合剂。通过测定反应过程中的粒径、反应转化率、乳液电位等对细乳液反应进行研究。结果表明:随着反应时间的延长,有机硅改性丙烯酸酯细乳液粒径逐渐减小,反应的转化率逐渐提高。反应3 h后基本保持稳定。有机硅改性丙烯酸酯细乳液与未改性乳液相比,其电位绝对值较高,更加稳定。将合成的细乳液成膜,研究了焙烘温度和时间对胶膜表面水接触角的影响,最后用于涂料印花。结果表明:随着焙烘温度的提高,胶膜表面接触角变大,最终稳定在95°左右。焙烘时间为10 min,胶膜表面的接触角基本稳定。粘合剂用量为20%时,棉织物涂料印花湿摩擦牢度达到4级,K/S值较大,织物表面疏水性较强,硬挺度较低,透湿量为8 807 g/(m ²·d),效果较好。     

有机氟硅共改性水性聚氨酯乳液的合成及其性能

将异佛尔酮二胺(IPDA)和甲基丙烯酸十二氟庚酯(DFMA)进行Micheal加成反应,合成端仲胺基的有机氟化合物(DFMA-IPDA)。以该化合物为扩链剂、聚醚改性聚二甲基硅氧烷(PDMS)为二元醇,与异佛尔酮二异氰酸酯(IPDI)、聚氧化丙烯二醇(PPG)、二羟甲基丙酸(DMPA)聚合制备了有机氟和硅改性的水性聚氨酯(WPU),研究了有机氟和/或硅用量对WPU乳液性能和胶膜性能的影响。结果表明:用该方法合成的DFMA-IPDA纯度达99.2%,和一定量的PDMS共改性可合成稳定的WPU乳液。随两者用量的增加,WPU乳液的平均粒径增大,胶膜的热稳定性、耐水性提高,表面水接触角增大。PDMS可提高WPU胶膜的柔性,而DFMA-IPDA可提高胶膜的韧性。用PDMS和DFMA-IPDA共改性能获得综合性能优异的WPU,当扩链剂完全采用DFMA-IPDA,PDMS用量为4%时,WPU胶膜的吸水率为4.5%,水接触角达到102.3°。     

聚苯胺/磷酸锌/聚硅氧烷复合涂层自修复和耐蚀性能初探

目的初步探索由聚苯胺/磷酸锌有机-无机复合钝化填料和环氧-聚硅氧烷树脂制备的自修复涂层的修复和防腐性能。方法采用微区交流阻抗技术(LEIS)、扫描电子显微技术(SEM)和电化学阻抗技术(EIS),研究了聚苯胺/磷酸锌/聚硅氧烷复合涂层的防腐性能和在人工损伤部位的修复功能。结果由微区电化学阻抗和电化学阻抗测试可知,环氧-聚硅氧烷清漆具有自修复和优异的耐蚀性能;偶联剂处理的聚苯胺/磷酸锌有机-无机复合钝化填料(HCE),可显著提升环氧-聚硅氧烷涂层的自修复和耐蚀性能。当HCE的添加量为0.3%(以占环氧-聚硅氧烷涂料质量的百分比计)时,涂层的自修复和耐蚀性能最佳,缺陷部位修复后的阻抗值最大达到70 k?,是环氧-聚硅氧烷清漆的9倍。涂层阻抗值随浸泡时间的延长而增加,浸泡3750 h时,涂层阻抗值增至10~(11)?·cm~2。结论当涂层产生缺陷时,一方面聚苯胺/磷酸锌有机-无机复合填料发生氧化还原反应,生成新的氧化膜;另一方面,聚苯胺与环氧-聚硅氧烷树脂发生交联固化反应,在基体缺陷处成膜,提高了涂层的致密性;二者协同作用使HCE3涂层试样具有最佳的耐蚀性能和自修复功能。     

Corrosion resistance of biodegradable polymeric layer-by-layer coatings on magnesium alloy AZ31

Biocompatible polyelectrolyte multilayers (PEMs) and polysiloxane hybrid coatings were prepared to improve the corrosion resistance of biodegradable Mg alloy AZ31. The PEMs, which contained alternating poly(sodium 4-styrenesulfonate) (PSS) and poly(allylamine hydrochloride) (PAH), were first self-assembled on the surface of the AZ31 alloy substrate via electrostatic interactions, designated as (PAH/PSS)₅/AZ31. Then, the (PAH/PSS)₅/AZ31 samples were dipped into a methyltrimethoxysilane (MTMS) solution to fabricate the PMTMS films, designated as PMTMS/(PAH/PSS)₅/AZ31. The surface morphologies, microstructures and chemical compositions of the films were investigated by FE-SEM, FTIR, XRD and XPS. Potentiodynamic polarization, electrochemical impedance spectroscopy and hydrogen evolution measurements demonstrated that the PMTMS/(PAH/PSS)₅/AZ31 composite film significantly enhanced the corrosion resistance of the AZ31 alloy in Hank’s balanced salt solution (HBSS). The PAH and PSS films effectively improved the deposition of Ca-P compounds including Ca₃(PO₄)₂ and hydroxyapatite (HA). Moreover, the corrosion mechanism of the composite coating was discussed. These coatings could be an alternative candidate coating for biodegradable Mg alloys.     

Processing of polysiloxane-derived porous ceramics: a review

Abstract

Because of the unique combination of their attractive properties, porous ceramics are considered as candidate materials for several engineering applications. The production of porous ceramics from polysiloxane precursors offers advantages in terms of simple processing methodology, low processing cost, and easy control over porosity and other properties of the resultant ceramics. Therefore, considerable research has been conducted to produce various Si(O)C-based ceramics from polysiloxane precursors by employing different processing strategies. The complete potential of these materials can only be achieved when properties are tailored for a specific application, whereas the control over these properties is highly dependent on the processing route. This review deals with processing strategies of polysiloxane-derived porous ceramics. The essential features of processing strategies—replica, sacrificial template, direct foaming and reaction techniques—are explained and the available literature reports are thoroughly reviewed with particular regard to the critical issues that affect pore characteristics. A short note on the cross-linking methods of polysiloxanes is also provided. The potential of each processing strategy on porosity and strength of the resultant SiC or SiOC ceramics is outlined.     

高通量超支化聚硅氧烷复合膜渗透汽化分离水中正丁醇

为得到高通量的水中脱除丁醇渗透汽化膜HPSiO-c-PDMS,采用AB₂型单体缩合法合成了超支化聚硅氧烷（HPSiO）并将其与端羟基聚二甲基硅氧烷（PDMS）交联制备渗透汽化复合膜.对超支化聚硅氧烷和HPSiO-c-PDMS膜进行了化学结构和形态表征,并系统研究了PDMS分子量大小对膜结构及其渗透汽化性能的影响.结果表明:超支化聚合物支化度（DB）达到0.73;HPSiO-c-PDMS膜具有较大的通量和分离因子,随着PDMS分子量的增加,其渗透通量减小而分离因子增加.     

石墨烯/聚硅氧烷复合材料的研究进展

介绍了改善石墨烯在聚硅氧烷基质中的分散性的方法,并分别从溶液共混和直接共混两个方面阐述了石墨烯/聚硅氧烷复合材料的制备工艺.重点总结、分析了石墨烯对不同聚硅氧烷材料性能的影响,包括力学强度、导电性、导热性、介电性和热稳定性;并讨论了不同制备工艺对石墨烯增强效果的影响.     

Curing behavior study of polydimethylsiloxane‐modified allylated novolac/4,4′‐bismaleimidodiphenylmethane resin

The curing behavior of polydimethylsiloxane‐modified allylated novolac/4,4′‐bismaleimidodiphenylmethane resin (PDMS‐modified AN/BDM) was investigated by using Fourier transform infrared spectrometry (FTIR) and differential scanning calorimetry. The results of FTIR confirmed that the curing reactions of the PDMS‐modified AN/BDM resins, including “Ene” reaction and Diels–Alder reaction between allyl groups and maleimide groups, should be similar to those of the parent allylated novolac/4,4′‐bismaleimidodiphenylmethane (AN/BDM) resin. The results of dynamic DSC showed that the total curing enthalpy of the PDMS‐modified AN/BDM resins was lower than that of the parent resin. Incorporation of polydimethylsiloxane (PDMS) into the backbone of the allylated novolac (AN) resin favored the Claisen rearrangement reaction of allyl groups. The isothermal DSC method was used to study the kinetics of the curing process. The experimental data for the parent AN/BDM resin and the PDMS‐modified AN/BDM resins exhibited an nth‐order behavior. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008