基于纳米二氧化硅的防冰疏水涂层的制备及性能研究

采用HTPS(端羟基聚二甲基硅氧烷)和APTES(氨基丙基三乙氧基硅烷)改性纳米SiO_2,并制备了改性纳米SiO_2/氟硅树脂-环氧树脂(M-SR)复合涂料。采用傅里叶变换红外光谱仪和扫描电镜对改性前后纳米SiO_2颗粒,以及M-SR复合涂料的结构和表面微观形貌进行了表征,并通过水接触角、水滴结冰时间和覆冰层的剪切附着强度评估了M-SR复合涂层的防覆冰效果。结果表明,经过HTPS和APTES改性后,纳米SiO_2颗粒表面的亲水基团被HTPS和APTES中低表面能的甲基取代,纳米SiO_2表面能更小,疏水性能更佳。随着改性纳米SiO_2颗粒含量的增加,M-SR复合涂层的疏水性增强,纳米SiO_2颗粒含量为50%的M-SR复合涂层综合性能最优,水接触角168.1°,水滴结冰时间279 s,覆冰剪切粘附强度小于5 kPa,是较为理想的防覆冰材料。     

聚四氟乙烯-碳酸钙超疏水复合涂层的制备及其性能

采用三甲基甲氧基硅烷对微纳米级CaCO_3进行表面改性。将改性CaCO_3颗粒与聚四氟乙烯(PTFE)颗粒混炼后喷涂在铝基层板上得到PTFE/CaCO_3超疏水复合涂层。采用原子力显微镜、扫描电子显微镜、同步热分析仪等研究了涂层的表面粗糙度、形貌特征以及热稳定性。结果表明:PTFE/CaCO_3涂层的静态接触角为(156±4)°,滚动角为(1.6±0.5)°;涂层的表面具有类似微纳米双层结构,耐热温度高达520℃;改性CaCO_3颗粒能够有效改善PTEF的疏水性能。     

辊式涂布法构建纸基牢固超疏水表面

采用辊式涂布的方法在纸基材料上构建超疏水表面，并对超疏水表面的牢固性、自清洁性和疏水性能进行评价。用γ-氨丙基三乙氧基硅烷和1H,1H,2H,2H-全氟辛基三乙氧基硅烷（POTS）对微米级和纳米级两种尺寸的TiO₂粒子进行疏水改性处理，然后将改性后的微/纳米TiO₂涂布在纸基材料表面。采用红外光谱（FTIR）对改性后的微/纳米TiO₂的化学组成进行了分析，采用扫描电镜（SEM）对涂布纸表面结构进行了表征，通过接触角、耐磨性和自洁净测试评价了涂层表面的超疏水性、牢固性和自清洁性。改性TiO₂的FTIR分析显示在1000～1500cm^-1之间出现多个C—F键的伸缩振动峰，表明POTS通过化学键与TiO₂表面发生了结合。涂布纸表面的SEM分析可以看出，纸基材料表面上均匀分布了微米和纳米尺寸的TiO₂颗粒，具备了类似荷叶表面微-纳结构的粗糙表面。涂层表面的水接触角为153°±1.5°，滚动角为3.5°±0.5°，水滴在涂层表面呈球形，极易滑落，涂层在水中浸泡7天后，接触角没有发生明显变化，表明纸张表面具备了优异的超疏水性能，且疏水稳定性较好。涂层表面经过10次循环磨损试验后，接触角仍能达到150°，滚动角为9°，表明机械摩擦没有对涂布纸表面的化学成分和粗糙结构造成明显的破坏，超疏水表面的牢固性较好。自洁净测试表明，涂布纸表面具有良好的自清洁和防污性能。该工艺过程操作简单，易于实现工业化生产，为在纸基表面构建综合性能优异的超疏水表面提供了一种新的便利途径。     

SiO_2/水性聚氨酯疏水涂层的制备及性能研究

以纳米二氧化硅(SiO_2)和水性聚氨酯(WPU)为原料,以水为分散剂,KH560和KH550为改性剂,采用喷涂工艺制备出SiO_2/WPU纳米复合涂层。研究了SiO_2粒度、SiO_2/WPU质量比、KH560改性SiO_2、及KH550改性WPU等因素对复合涂层疏水性能的影响。结果表明:采用粒度为30 nm的SiO_2、SiO_2/WPU质量比为1∶5、WPU与KH550质量比为10.6∶1时制备的SiO_2/WPU纳米复合涂层疏水效果最好,接触角达138°,从扫描电镜照片可以看出所制备的SiO_2/WPU涂层具有了与荷叶表面相似的微一纳米粗糙结构。     

硫化天然橡胶超疏水表面的微纳结构设计与构筑

以硫化后的天然橡胶(NR)材料为基体,将其在一定的溶剂中溶胀,然后采用溶胶-凝胶技术使纳米SiO_2颗粒在橡胶溶胀层和表面原位生成、生长,在硫化NR表面构筑出类似荷叶的微纳米结构,达到使NR表面超疏水化的目的。通过调控影响溶胶-凝胶反应的溶胀剂和反应剂的种类及浓度,控制硫化NR表面的微纳米结构的尺寸和形态,并对比分析不同的微纳米结构对硫化NR表面疏水性能的影响。结果表明,采用正丁胺作为溶胀剂,在正硅酸乙酯(TEOS)试剂中发生溶胶-凝胶反应,用硬脂酸(SA)对硫化NR表面修饰,成功使硫化NR表面超疏水化,其水接触角达到153.5°。扫描电镜(SEM)测试表明,硫化NR表面形成了"类荷叶"的高粗糙度SiO_2微纳米复合结构。     

透明超疏水SiO2/硅酮胶复合涂层的制备及性能

以疏水纳米SiO_2和中性硅酮结构胶为主要原料,采用喷涂法在玻璃表面制备出透明超疏水SiO_2/硅酮胶复合涂层。采用FTIR、SEM、接触角测量仪和紫外-可见分光光度计对复合涂层的分子结构、微观形貌、润湿性和透光率进行表征。讨论了纳米SiO_2的添加量与涂层表面微结构、水接触角、透明性三者的关系,考察了复合涂层的耐水冲击性能和耐水稳定性能。结果表明:SiO_2/硅酮胶复合涂层表面呈连续的多孔网络状,团聚的SiO_2纳米粒子分散在作为骨架的亚微米级硅酮胶周围,构成了微纳米双尺度的复合粗糙结构。当SiO_2质量分数为2.0%时,复合涂层的水接触角达到最大为169.8°±0.7°,在380～760nm可见光范围内的平均透光率为82.9%;当硅酮胶质量分数为4%时,复合涂层分别经5 h水冲击以及10 d水浸泡后,水接触角仍保持在140°以上。     

纳米二氧化钛/氧化锌超疏水涂层的制备及其性能

将纳米TiO2和微米ZnO机械搅拌,制备了纳米TiO2/ZnO复合粒子。通过硬脂酸对其改性,于200°C下烘烤15min,在钢试片上得到纳米TiO2/ZnO复合超疏水涂层。采用扫描电镜、红外光谱和接触角分析仪对涂层表面的形貌和疏水性进行了表征。结果表明,复合粒子经硬脂酸表面改性后引入了疏水性的甲基,形成微/纳米双重粗糙结构。当硬脂酸含量为9%时,所得涂层表面与水的静态接触角为165.3°,滚动角4°。该涂层具有优异的耐溶解性、耐温性及自清洁性。     

多孔结构耐磨超疏水薄膜的制备及性能

为了获得持久稳定的超疏水材料,将聚偏二氟乙烯共六氟丙烯共聚物〔P(VDF-HFP)〕和十六烷基三甲氧基硅烷(HDTMS)改性的Al2O3纳米粒子进行复合并通过溶剂/非溶剂诱导相分离法制备了一种耐磨超疏水薄膜.采用SEM、能谱分析仪和接触角测量仪分别对薄膜的表面微观结构、化学组成、水接触角和滚动角进行了表征.结果表明,制备的薄膜呈多孔微纳米复合微观结构,具有优异的自清洁性和耐机械摩擦性,即使经过360个周期的砂纸(800目)磨损(100 g载重)后仍保持超疏水性,水接触角为155°±2°,滚动角为5°±2°;此外,薄膜具有优异的耐酸/碱溶液和紫外灯照射稳定性.     

环氧/聚二甲基硅氧烷/MCM-41超疏水涂层的制备与性能研究

针对常规超疏水涂层制备工艺繁琐等问题，以介孔SiO₂纳米颗粒(MCM-41)为填料和载体，聚二甲基硅氧烷(PDMS)为低表面能改性剂，环氧树脂及其固化剂为成膜物，采用喷涂法制备了超疏水涂层。通过场发射扫描电子显微镜、共聚焦显微镜、接触角测量仪、拉伸试验机对其表面形貌、结构、疏水性及附着力进行表征。重点考察了PDMS改性的MCM-41(MCM-41/PDMS)和树脂基体质量比对涂层性能的影响。结果表明：当MCM-41/PDMS质量分数为55%，可以得到涂层疏水性(接触角150°，滚动角9°)和附着力(7.33 MPa)的最佳匹配，涂层经过胶带剥离300次和磨损150周期后，水接触角仍大于150°。     

超疏水SiO2@OTES自清洁涂层的制备及性能

以纳米二氧化硅颗粒、正辛基三乙氧基硅烷(OTES)和硅烷偶联剂KH560为前驱体,采用溶胶凝胶法制备了超疏水SiO₂@OTES自清洁涂层。在酸性催化剂及有机溶剂中,OTES、KH560将纳米颗粒表面由亲水改性为疏水。探究了纳米SiO₂、OTES、KH560三种原材料含量对超疏水涂层润湿性能的影响。结果表明,当掺杂3.5 g纳米SiO₂,8%的OTES与2%的KH560时,涂层达到最佳疏水效果,其接触角为(154±1)°,滚动角为(3.3±0.5)°。采用SEM、FTIR红外光谱仪、X射线光电子能谱(XPS)对超疏水SiO₂@OTES材料的表面形貌与化学成分进行了表征。实验表明制备出的超疏水SiO₂@OTES自清洁涂层具有良好的自清洁防污、耐低温与耐磨性能,且将涂层回收重新制得的表面仍具有超疏水性。     

纳米SiO2复合粒子/有机硅低聚物透明超疏水复合涂层的制备及其性能

本文以Stober法制备的胶体SiO2粒子与粉体SiO2粒子结合的SiO2复合粒子在玻璃基底构建粗糙表面,以三乙氧基甲基硅烷（MTES）与正硅酸乙酯（TEOS）为前聚体制备的酸性有机硅低聚物作为粘接剂,使用偶联剂KH540与氟硅烷PFDT进行改性,通过喷涂法在玻璃基底上制备出SiO2复合粒子/酸性有机硅低聚物复合透明超疏水涂层,然后探究SiO2复合粒子、酸性有机硅低聚物、偶联剂KH540以及氟硅烷PFDT对复合涂层的影响。研究表明：当SiO2复合粒子由粒径为110 nm的胶体SiO2粒子与粒径为50 nm的粉体SiO2粒子两种粒子组成,SiO2复合粒子溶液与酸性有机硅稀释液的混合质量比为4:1,添加偶联剂KH540与氟硅烷PFDT的质量比为混合液的1%时,复合涂层在可见光波长范围内透光率可达88%,静态接触角能达155°,在800目砂纸上磨损60 cm后仍能保持超疏水性能,具有良好的自清洁性,为透明超疏水涂层的制备提供一种简便、低成本方案。     

疏水性SiO2增透膜的制备与表征

以三甲基氯硅烷（TMCS）为有机掺杂剂,采用溶胶-凝胶法制备正硅酸乙酯为前驱体,氨水催化的复合SiO2增透膜。用紫外-可见分光光度仪、接触角测量仪对膜层进行了表征。结果表明：未经TMCS掺杂的SiO2增透膜的峰值透过率为97．5％,而一定浓度TMCS掺杂后的SiO2复合膜的峰值透过率为983％,说明掺杂并没有影响薄膜的增透效果。掺杂前后增透膜对水的接触角从15°增加到123°,显著的提高了薄膜的疏水性能。     

Gradient and weather resistant hybrid super‐hydrophobic coating based on fluorinated epoxy resin

A weather resistant super‐hydrophobic coating that can offer good substrate adhesion and yet to be easily processed at large scale can be of practical use in emerging fields of self‐cleaning and anti‐icing paint, combing all these properties together remains challenging task. Here we describe a composite coating composed of a fluorinated epoxy resin emulsion with embedded in situ surface‐modified dual‐scale nano‐silica, which displayed durable super‐hydrophobicity and excellent adhesive strength. The as‐prepared coating possesses water contact angle of 158.6 ± 1°, sliding angle around 3.8 ± 0.2° which remain stable even under acidic/alkaline, heat/cool, and accelerated aging treatment. The results demonstrate that surface roughness had a micron‐ and nanometer scale distribution with increased particle loading beyond 40 wt %. Through quantitative comparison of surface Attenuated Total Reflection (ATR) with bulk FT‐IR transmission spectra, a gradient coating with surface enrichment of hydrophobic groups was determined. The air‐side fluorinated polysiloxane‐rich layer endows coating with weather‐resistance and ultra‐hydrophobicity while bottom epoxy resin layer enhances substrate adhesion. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40955.     

Hydrophobic and tribological behaviors of a poly(p‐phenylene benzobisoxazole) fabric composite reinforced with nano‐TiO2

1H,1H,2H,2H‐Perfluorooctyl trichlorosilane (PFTS) was used to modify TiO₂ nanoparticles, and hydrophobic PFTS–TiO₂ nanoparticles were obtained by an ultrasonic reaction method. The PFTS–TiO₂ surface morphological and hydrophobic properties were analyzed with scanning electron microscopy (SEM), Fourier transform infrared spectrometry, and contact angle (CA) testing. Then, the poly(p‐phenylene benzobisoxazole) fabric–phenolic composite filled with PFTS–TiO₂ as a lubricant additive was fabricated by a dip‐coating process. The tribological properties of the composite were investigated, and the wear surface morphology was observed by SEM. The experimental results show that the water CA of the composite filled with PFTS–TiO₂ was 158°, and the composite containing 4 wt % PFTS–TiO₂ exhibited excellent antifriction and abrasion resistance. The hydrophobic surface of the composite showed excellent durable performance with a static water CA of 126.7° after abrasion. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45077.     

A durable and environmental friendly superhydrophobic coatings with self-cleaning,anti-fouling performance for liquid-food residue reduction

A durable and environmentally-friendly superhydrophobic coatings for liquid-food residue reduction were prepared by using stearic acid (SA) modified organic montmorillonite (SA@OMMT) and poly(dimethylsiloxane) (PDMS). Due to the natural hydrophobicity of SAs, SA@OMMT provides low surface energy as well as roughness for the coating. PDMS not only provided low surface energy in the coating but also contributed to the bonding of SA@OMMT as a result of its high adhesive properties. In addition, PDMS has good physical properties after curing, which can effectively improve the physical properties and durability of a superhydrophobic coating by the self-assembly method using a PDMS/n-hexane solution. For 1 wt.% SA@OMMT and 5 wt.% PDMS, the resulting SA@OMMT/PDMS (SOP) coating showed the water contact angle (WCA) and water sliding angle (WSA) of 156.3°and 2°, respectively. The prepared coatings have good physical and chemical stability, and they still have superhydrophobicity after physical abrasion tests and exposure to the corrosion solutions. In the meanwhile, the prepared coating also has flexibility and superhydrophobicity after bending and folding. Finally, the coating surface shows highly effective antifouling ability to liquid and solid pollutants. The coating can be applied against different substrates and has potential application in the field of liquid-food residue reduction.     

PE基聚硅氧烷/改性SiO2超疏水薄膜的构筑

使用十八烷基三甲氧基硅烷(OTMS)对纳米SiO2进行表面疏水改性,将得到的改性纳米SiO2(OTMS-SiO2)添加到有机硅树脂(SI)中,然后采用两步法在聚乙烯(PE)薄膜表面固化制备了复合涂层SI/OTMS-SiO2.通过FTIR、1HNMR、29SiNMR、TGA对OTMS-SiO2及复合涂层进行了表征,采用接触角测量仪、SEM、AFM对复合涂层疏水特性和形貌进行了测试和观察,最后对复合涂层的耐磨性和附着力进行了分析.结果表明,SiO2表面成功引入了OTMS,且OTMS-SiO2均匀附着在硅树脂涂层上,增加了表面粗糙度,得到了PE基固化超疏水复合涂层.当OTMS-SiO2添加量为正己烷质量的8％时,制得的复合涂层的水接触角为154°,滚动角为7°,并具有良好的耐磨性,其附着力可达4A等级.     

电化学沉积法制备Cu-纳米SiO_2复合镀层及其性能的研究

利用电化学沉积法制备以纳米SiO_2微粒为增强相的Cu-纳米SiO_2复合镀层。研究发现:Cu-纳米SiO_2复合镀层的形貌特征不同于纯铜镀层的,其性能较好。增强相纳米SiO_2微粒引起形核增殖、结晶细化,同时形成弥散强化,致使Cu-纳米SiO_2复合镀层的形貌特征不同,性能得以改善。随着镀液中纳米SiO_2微粒的质量浓度的增加,Cu-纳米SiO_2复合镀层的显微硬度先升高后降低,体积磨损率先减小后增大。当镀液中纳米SiO_2微粒的质量浓度为35g/L时,Cu-纳米SiO_2复合镀层的显微硬度最高,接近1 500 MPa,约为纯铜镀层的1.46倍;体积磨损率最低,为6.59×10-5 mm3/(N·m),比纯铜镀层的降低约35.4%。     

Hydrophobic composite coatings with photocatalytic self-cleaning properties by micro/nanoparticles mixed with fluorocarbon resin

A newly developed hydrophobic composite coating was fabricated by incorporating modified TiO₂ nanoparticles and hydrophobic material polytetrafluoroethylene (PTFE) micropowders dispersed in fluorocarbon resin. Moreover, the surface characteristics and self-cleaning properties of the newly developed composite material were examined. The material was found to exhibit sufficient hydrophobicity with a water contact angle of 133°. The surface free energy of the composite coating was 4.11 mJ/m². Scanning electron microscopy results revealed a micro/nanocomposite structure composed of PTFE micropowders and TiO₂ nanoparticles, which was verified by X-ray photoelectron spectroscopy results. Through ultraviolet irradiation the modified TiO₂-PTFE/FEVE composite coating successfully removed oleic acid absorbed on its surface. These results showed that the functional composite coating had a sufficiently hydrophobic surface with an efficient self-cleaning effect.     

Preparation of composite‐crosslinked poly(N‐isopropylacrylamide) gel layer and characteristics of reverse hydrophilic–hydrophobic surface

The composite‐crosslinked poly(N‐isopropylacrylamide) (PNIPAAm) gels were prepared by grafting N‐isopropylacrylamide on the surface of glass plates modified by organosilanes. The glass plates as the substrate increase the mechanical strength of composite PNIPAAm gel layers. We investigated the effects of a series of organosilanes and the reaction time of organosilanes on surface characteristics, such as the static contact angle and the layer thickness. We discuss the equilibrium swelling ratio and the water release behavior of the gel layers in terms of the crosslinking density of the composite gels. The composite gels exhibit not only the characteristics of remarkable water release but also the reversed hydrophilic–hydrophobic surface properties. The gel layers are hydrophilic under 25°C and change to hydrophobic above 40°C. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1–11, 1999