纳米SiO2改性紫外光固化有机硅杂化材料研究

合成了光敏性有机硅树脂PSUA,采用超声分散法将纳米SiO2分散在光敏性有机硅体系中,通过紫外光固化方式制备了光固化有机硅杂化材料.研究了纳米SiO2含量对杂化体系稳定性和光固化速率的影响,测定了光固化膜硬度,用扫描电镜观察了光固化膜断面形貌.实验结果表明,表面改性的纳米SiO2在杂化体系中分散比较均匀,稳定性好,能够有效增强光固化膜的硬度,但降低了光固化速率,杂化体系中纳米SiO2的用量以3%～5%为宜.     

铝合金表面新型有机-无机杂化纳米SiO2涂层的制备及其性能

为了提高铝合金的耐腐蚀性能、耐磨损性能及硬度,通过溶胶-凝胶反应,以纳米硅溶胶为主要原料,有机硅烷为偶联剂,制备了新型纳米SiO2防腐蚀涂料.通过浸渍-提拉法在铝合金(LY12)基体表面形成涂层,通过改变硅溶胶的含量,详细研究了此涂层的显微硬度、耐磨性能和耐腐蚀性能与硅溶胶含量的关系.结果显示,新型有机-无机杂化纳米SiO2涂层厚度为20μm时具有良好的耐腐蚀性能和耐磨性能,由此而使此杂化膜替代对环境有害的铬酸盐转化膜成为可能,并为有机-无机杂化纳化材料的应用提供了理论依据.     

铝合金表面新型有机-无机杂化纳米Si02涂层的制备及其性能

为了提高铝合金的耐腐蚀性能、耐磨损性能及硬度,通过溶胶-凝胶反应,以纳米硅溶胶为主要原料,有机硅烷为偶联剂,制备了新型纳米SiO2防腐蚀涂料。通过浸渍-提拉法在铝合金（LY12）基体表面形成涂层,通过改变硅溶胶的含量,详细研究了此涂层的显微硬度、耐磨性能和耐腐蚀性能与硅溶胶含量的关系。结果显示,新型有机-无机杂化纳米SiO2涂层厚度为20μm时具有良好的耐腐蚀性能和耐磨性能,由此而使此杂化膜替代对环境有害的铬酸盐转化膜成为可能,并为有机-无机杂化纳化材料的应用提供了理论依据。     

纯丙类聚氨酯/SiO_2-ZrO_2光固化纳米复合透明耐磨涂料涂层的制备及性能

目前,鲜见在纯丙类光固化聚氨酯中引入SiO_2和ZrO_2纳米粒子的报道。采用溶液聚合法制备了纯丙类聚氨酯丙烯酸酯,采用溶胶凝胶法制备SiO_2及ZrO_2无机溶胶,将无机前驱体与有机相进行杂化,制备了一系列可光固化的有机无机杂化涂料。采用红外光谱(FTIR)和核磁共振氢谱(1H-NMR)对杂化涂料及其涂层进行了结构表征,采用场发射扫描电镜(SEM)研究了杂化涂料涂层的表面形貌,并对涂层进行了物理性能、透明性以及耐磨性能测试。结果表明:杂化涂料涂层中,无机粒子均匀分散在有机相中,且无机粒子半径为20~30 nm;无机粒子的引入显著提升了涂层的物理性能及耐磨性能,涂层的硬度从1 H提升到6 H,磨耗量减少了80%。     

硅系有机-无机杂化气体分离膜研究进展

硅系有机-无机杂化气体分离膜集取了有机相和无机硅相的优异性能,成为当前气体分离膜领域研究的焦点。概述了硅系杂化膜的发展现状,系统阐述了采用溶胶-凝胶法制备硅系有机-无机杂化膜,讨论了影响硅系杂化膜分离性能的主要影响因素,阐述了硅系有机-无机杂化膜的气体传递机理并展望了未来的发展方向。     

PU(U)A/SiO2杂化水分散液及成膜性能研究

用异佛尔酮二异氰酸酯(IPDI)、聚酯二元醇、二羟甲基丙酸(DMPA)、乙二胺、二乙醇胺、甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、甲基丙烯酸羟乙酯(HEMA)通过原位聚合方法合成了聚氨酯(脲)/聚丙烯酸酯水分散液,并且通过溶胶-凝胶方法合成了聚氨酯(脲)/聚丙烯酸酯/硅溶胶(PU(U)A/SiO2)杂化水分散液.杂化水分散液在pH值为7～11时的贮存稳定性大于1年;经高温、冻融试验后,无絮凝或沉淀出现,与PU(U)A水分散液相同.杂化膜的摆杆硬度、粘附力、耐吸水性、耐溶剂性比无硅溶胶的膜性能好.PU(U)A/SiO2杂化水分散稀溶液成膜后的透射电镜(TEM)结果表明,粒径为8～10nm的硅溶胶(SiO2)包覆在粒径 为50～200nm的PU(U)A粒子外围.ART-FTIR分析结果表明,杂化膜表面富含Si-O-Si官能团.AFM结果表明,与PU(U)A膜相比,杂化膜的硬区相畴尺寸变小.     

纳米SiO_2有机杂化膜制备研究

采用共混法和溶胶-凝胶法制备了纳米SiO_2有机杂化膜,考察了制备方法和SiO_2的性质对杂化膜结构和性能的影响.结果表明:采用溶胶-凝胶技术制备的杂化膜同共混法得到的杂化膜及未杂化膜相比,机械性能明显提高,膜微观结构改善,并表现出良好的气体分离性能.此外,杂化膜中无机相的负载量也是一个影响杂化膜结构和性能的重要因素,当正硅酸乙酯的添加量为30%(wt)时,杂化膜的综合性能较为理想.     

有机/无机杂化膜渗透汽化分离ABE研究进展

有机/无机杂化膜兼具传统有机膜和无机膜的优良性能,已成为膜分离领域的研究热点之一。有机/无机杂化膜可以分为三类:无机膜支撑有机膜、无机粒子/聚合物杂化膜和表面筛分膜。研究者开发了大量有机/无机杂化膜并将其应用于渗透汽化分离丙酮-丁醇-乙醇/水(ABE/W)体系。综述了近年来用于渗透汽化分离ABE/W体系的有机/无机杂化膜研究现状,详细介绍了有机/无机杂化膜微结构、分离性能及两者之间的关系,并针对目前有机/无机杂化膜中存在的问题,对今后的发展前景进行了展望。     

有机/无机杂化纳米粒子共混改性聚偏氟乙烯多孔膜及其表面两性离子化的研究

通过表面引发的可逆-加成断裂链转移(RAFT)聚合,制备了聚甲基丙烯酸甲酯-聚甲基丙烯酸二甲氨乙酯嵌段共聚物(PMMA-b-PDMAEMA)接枝改性的有机/无机杂化二氧化硅纳米粒子(BCP-gSiO2NPs),并将其与聚偏氟乙烯(PVDF)溶液共混,通过传统的非溶剂诱导相分离(NIPS)法制备PVDF/BCP-g-SiO2有机-无机杂化分离膜,进一步通过膜表面PDMAEMA链段与1,3-丙磺酸内酯之间的季胺化反应,实现了PVDF/BCP-g-SiO2有机-无机杂化膜的表面两性离子化。研究结果表明,BCP-g-SiO2NPs的引入以及膜表面的进一步两性离子化显著提高了PVDF膜的亲水性和抗污染性能,是PVDF超滤膜等相转化膜材料改性的有效方法。     

疏水型PA6/SiO2有机无机杂化材料的制备及性能

以正硅酸乙酯(TEOS)、甲基三乙氧基硅烷(MTES)和己内酰胺(CPL)为原料,采用原位阴离子开环聚合法,制备了疏水型PA6/SiO2有机无机杂化材料。PA6/SiO2有机无机杂化材料表面外的Si-CH3基团赋予了材料优异的疏水性能。随着硅溶胶含量(SiO2%,质量分数)的提高,接触角θ增大,当SiO2%大于8.5时,接触角θ增大不明显,并最终稳定在130°左右。红外图谱(FT-IR)和X射线光电子能谱(XPS)分析结果显示,硅溶胶的羟基和未完全水解的烷氧基能够与PA6的前驱体发生杂化反应。X射线衍射结果显示,采用本实验方法制备出的PA6和疏水型PA6/SiO2有机无机杂化材均为α晶型,而DSC结果表明,PA6/SiO2有机无机杂化材料的熔点略高于PA6。     

新型可紫外光固化水性聚氨酯的制备与表征

以异佛尔酮二异氰酸酯(IPDI)、聚酯二元醇Pol-1256、二羟甲基丙酸(DMPA)为主要原料,采用预聚体法制备了水性聚氨酯预聚体,然后用自制的扩链剂对该预聚体进行扩链,并用丙烯酸羟乙酯(HEA)对扩链后的预聚体进行封端,最后中和乳化,制备了高紫外光(UV)固化基团含量的可UV固化水性聚氨酯乳液。采用FTIR对产物的结构进行了鉴定,利用旋转流变仪对分散体的流变性能进行了表征,通过TGA分析了UV固化膜的耐热性能,并对其拉伸性能进行了测试。研究结果表明:所制扩链剂符合预期结构特征,所得产物符合可UV固化的水性聚氨酯结构特征;乳液呈现出剪切变稀的特征,属于假塑性流体;UV固化膜具有良好的耐热性能,同时具有较高的断裂伸长率和良好的拉伸强度。     

Synthesis of organic-inorganic hybrid sols using trifunctional organoalkoxysilanes for dispersion agents

We investigated the properties of synthetically produced organic-inorganic hybrid coatings by a sol-gel process. The properties of organic-inorganic hybrid materials arise from the synergism between the properties of the individual components. One of the typical way to synthesize the organic-inorganic hybrid materials is to use silica and silanes. A colloidal silica sol was used as an inorganic material. Methyltrimethoxysilane and phenyltrimethoxysilane were used as the trifunctional organoalkoxysilanes. Hybrid sols of colloidal silica and silanes were synthesized as a function of reaction time and methyltrimethoxysilane/phenyltrimethoxysilane ratio by a sol-gel process. Physical properties of sol solutions such as stability, viscosity, and transmittance were investigated. The surface roughness and surface free energy of the coatings were also measured.     

Funktionelle Schichten durch UV‐ und Elektronenstrahlhärtung

UV (EB) Curable Functional Coatings Composition, curing kinetics and application potential of acrylate based UV(EB) curable coatings are described. To formulate these coatings a manifold of acrylate oligomers exhibiting either ether, ester, epoxy or urethane functionality can be used as binders whereas acrylate monomers are applied as reactive thinners. Coatings with special functional properties such as resistance against chemicals, scratch and abrasion resistance, UV‐protection and flexibility can be applied on substrates such as paper, plastic films, wood and engineered wood, aluminum etc. Additionally, liquid acrylates can be favourably applied to produce microstructured or super smooth surfaces: the acrylate is brought into contact with either a structurized or a polished drum and rapidly cured in contact with the cylinder surface. Scratch and abrasion resistant coatings are obtained from acrylate nanocomposites. These formulations contain up to 30 w% SiO₂ nanoparticles covered by a polysiloxane shell.     

Synthesis of organic-inorganic hybrid sols with nano silica particles and organoalkoxysilanes for transparent and high-thermal-resistance coating films using sol-gel reaction

Organic-inorganic hybrid sols were synthesized from nano silica particles dispersed in water and from organoalkoxysilanes, using the sol-gel reaction. This work focuses on the effects of the three multifunctional organoalkoxysilanes dimethyldimethoxysilane (DMDMS), methyltrimethoxysilane (MTMS), and tetramethoxysilane (TMOS) to form a transparent and high-thermal-resistance coating film. The stability of the hybrid sol was evaluated as a function of the reaction time for 10 d through the variation of the viscosity. The viscosity of the silica/DMDMS and silica/MTMS sol was slightly increased for 10 d. The multifunctional organoalkoxysilanes formed dense silica networks through hydrolysis and condensation reaction, which enhanced the thermal resistance of the coating films. No thermal degradation of the silica/DMDMS sample occurred up to 600 degrees C, and none of the silica/MTMS and silica/TMOS samples occurred either up to 700 degrees C. The organic-inorganic hybrid sols were coated on the glass substrate using a spin-coating procedure. The organic-inorganic hybrid sols formed flat coating films without cracks. The transmittance of the hybrid sol coating films using MTMS and DMDMS was shown to be over 90%. The transmittance of the silica/TMOS sol coating film reacted for 10 d abruptly decreased due to faster gelation. The silica/DMDMS and silica/MTMS hybrid sols formed smooth coating films while the surface roughness of the silica/TMOS coating film markedly increased when the hybrid sol reacted for 10 d. The increase of the surface roughness of the silica/TMOS coating film can be attributed to the degradation of the stability of the hybrid sol and to the loss of transmittance of the coating film. It was confirmed in this study that the use of organic-inorganic hybrid sol can yield transparent and high-thermal-resistance coating films.     

有机／无机杂化体系中聚氧化乙烯的受限结晶

通过sol-gel技术合成了聚氧化乙烯（PEO）和二氧化硅（SiO2)的有机－无机杂化材料,通过DSC和WAXD方法测试了杂化样吕PEO的结晶度,结晶结构和（120）晶面的微晶尺寸,说明了PEO在该杂化体系中的受阻结晶行为。     

有机硅KH-570改性硅溶胶杂化涂层的制备研究

以硅溶胶、γ-甲基丙烯酰氧丙基三甲氧基硅烷(KH-570)为原料,将低钠型碱性硅溶胶经强酸性阳离子交换树脂离子交换后,得到酸性硅溶胶,将其与KH-570按一定比例共混搅拌,通过KH-570在酸性条件下,水解缩聚,制得有机/无机杂化溶胶。以低碳钢Q235为基材,制备出硅烷偶联剂KH-570(MEMO)改性硅溶胶的杂化涂层。以FT-IR测试方法对其结构进行了表征,采用动电位极化曲线测试涂层的耐蚀性能。以光学显微镜、SEM观察涂层与碳钢裸片在腐蚀前后的表面形貌。研究结果表明:酸性硅溶胶与KH-570的水解缩聚产物通过共缩聚反应在碳钢表面形成带有有机基团的无机交联网络,基本骨架由Si-O-Si组成,经过100℃热处理,即可得致密涂层,涂层均匀、透明,无缺陷。电化学分析表明涂层形成物理屏障,为基体提供了优良的腐蚀保护。杂化涂层显现出良好的耐蚀性能。     

Optical and mechanical properties of jet printed and UV cured blue pixels with phosphated epoxy acrylate as the curing agent

Phosphated epoxy acrylate and phosphated imide-epoxy were synthesized and used as compositions of non-volatile (no solvent) UV curable ink for manufacturing the jet-printed LCD color filter (CF). Phosphated epoxy acrylate oligomer showed not only good solubility in UV curable monomers and pigment compatibility as ink compositions, but also good thermal and mechanical properties after curing. No receiver layer or barrier ribs are necessary to prevent the printed ink from overflowing to the neighboring area. The color inks were precisely ejected to the glass substrate and UV-cured immediately to make the stripe pattern. The printed blue stripes exhibited smooth surface, straight edge, high transparency (transmittance > 84%), high nanoindentation hardness (3.94 GPa) and modulus (72.15 GPa). The influences of curable compositions on the optical properties, patterning properties, surface morphology and nanoindentation hardness of the micro-stripes were discussed.     

Multi-functional hybrid coatings containing silica nanoparticles and anti-corrosive acrylate monomer for scratch and corrosion resistance

Multi-functional hybrid coatings having both anti-corrosion and scratch resistance were prepared from modified silica nanoparticles and functional acrylates. To improve the dispersion properties of silica nanoparticles in the organic/inorganic hybrid coatings, the surface of the nanoparticles was modified with γ-methacryloxypropyltrimethoxysilane. The coating solution could be prepared by mixing modified silica nanoparticles, tetrasiloxane acrylate, di-acrylate monomer containing an anti-corrosion functional group, acrylic acid, and an initiator in a solvent. The mixture was then dip-coated on iron substrates and finally polymerized by ultraviolet (UV) irradiation. Corrosion and scratch resistance of the coated iron was evaluated by electrochemical impedance spectroscopy (EIS) and a pencil hardness test, respectively. From the EIS results, the coatings with tetrasiloxane acrylate and di-acrylate did not show any decrease in impedance or phase angle, even after 50 days' exposure to 0.1 M NaCl electrolyte, whereas the conventional acrylate coatings started to fail after only 24 h. A hybrid coating containing the amine-quinone functional group exhibited excellent corrosion protection properties with 4-5H pencil hardness.     

Concave micro-lens arrays fabricated from the photo-patternable GeO2/ormosils hybrid sol–gel films

Photo-patternable GeO₂/γ-glycidoxypropyltrimethoxysilane hybrid thin films were synthesized by a low-temperature sol–gel spin-coating technique. Optical properties and photochemical activities of the as prepared hybrid sol–gel films baked at different temperature were characterized by atomic force microscopy, prism coupling technique, UV–Visible spectroscopy, and Fourier transform infrared spectroscopy. The thermal stability of the gel powder obtained from the hybrid material sol was also examined by a thermal gravimetric analysis. Advantages for fabrication of concave micro-lens arrays based on the as-prepared photo-patternable hybrid films were demonstrated by a UV-cured imprint technique. Results indicate that the as-prepared photo-patternable hybrid materials have great applicability for the fabrication of photonic components. And the UV-cured imprint technique has advantages of simplicity, cost-effective, mass-production, and potential applications in industry production.     

有机-无机杂化复合材料的合成、表征和热学性质

丙烯酸乙酯(EA)、甲基丙烯酸甲酯(MMA)、苯乙烯(St)、及丙烯酸丁酯(BA)分别和含烷氧基硅烷单体甲基丙烯酰氧基三甲氧丙基硅烷以一定比例通过自由基共聚反应制得共聚物前驱体,将TEOS在HCl催化剂作用下水解、缩合形成SiO2,然后由共聚物和SiO2通过溶胶-凝胶法合成杂化复合材料,制得的复合材料膜有较好的光学透明性,其透光率在79%以上.利用傅立红外光谱分析了杂化材料的化学结构.溶胶抽取结果表明,在杂化材料中凝胶的含量较高,对它们的形貌特性和研究结果表明:在聚合物基体中SiO2具有较好的分散性,有机-无机相相互贯穿.