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。     

Fabrication of superhydrophobic fiber coatings by DC‐biased AC‐electrospinning

Mesh‐like fiber mats of polystyrene (PS) were deposited using DC‐biased AC‐electrospinning. Superhydrophobic surfaces with water contact angles greater than 150° and gas fraction values of up to 97% were obtained. Rheological study was conducted on these fiber surfaces and showed a decrease in shear stress when compared with a noncoated surface (no slip), making them excellent candidates for applications requiring the reduction of skin‐friction drag in submerged surfaces. We have also shown that addition of a second, low‐surface energy polymer to a solution of PS can be used to control the fiber internal porosity depending on the concentration of the second polymer. Contact‐angle measurements on mats consisting of porous and nonporous fibers have been used to evaluate the role of the larger spaces between the fibers and the pores on individual fibers on superhydrophobicity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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。     

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.     

Heat‐resistant hydrophobic–oleophobic coatings

Thermally and chemically durable hydrophobic oleophobic coatings, containing different ceramic particles such as SiO₂, SiC, Al₂O₃, which can be alternative instead of Teflon, have been developed and applied on the aluminum substrates by spin‐coating method. Polyimides, which are high‐thermal resistant heteroaromatic polymers, were synthesized, and fluor oligomers were added to these polymers to obtain hydrophobic–oleophobic properties. After coating, Al surface was subjected to Taber‐abrasion, adhesion, corrosion, and thermal tests. The effects of the particle size of ceramic powders, organic matrix, and heat on the coating material were investigated. Coating material was characterized by FTIR spectrophotometer. Surface properties and thermal resistance of the coating materials were investigated by SEM and TGA analyses. After thermal curing, contact angles of these coatings with H₂O and n‐hexadecane were measured. It was observed that coatings like ceramic particles are more resistant against scratch and abrasion than the other coatings. Also, they are harder than coatings, which do not include ceramic particles. It was seen that coatings, containing Fluorolink D10H, have high‐contact angles with water and n‐hexadecane. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2386–2392, 2006     

水性超疏水涂层的制备、调控与应用的研究进展

基于可持续发展和绿色环保的要求,以水替代有机挥发性溶剂的新型水性超疏水涂层逐渐成为研究热点,但是水性涂料的分散性及涂层的疏水稳定性、涂层性能等相关问题也随之而来。本文介绍了水性超疏水涂层制备方法的发展现状,针对水性超疏水涂层力学耐久性能差的问题提出可行性方案,例如制备内外一致的一体化复合结构,加强涂层内界面相互作用,交联作用或设计自修复水性超疏水涂层等。此外,还对水性超疏水涂层在油水分离、防结冰、自清洁等领域的进展进行阐述,并探讨了水性超疏水涂层的规模化制备、涂层力学性能的强化和耐久性研究将成为主要探索方向,只有夯实水性超疏水涂层的基础研究,工业应用才能突破。     

Mid‐IR transparent TeO2‐TiO2‐La2O3 glass and its crystallization behavior for photonic applications

In this report, effect of enhanced rare earth (La₂O₃) concentration on substitution of TeO₂ within ternary TeO₂‐TiO₂‐La₂O₃ (TTL) glass system has been studied with respect to its thermal, structural, mechanical, optical, and crystallization properties with an aim to achieve glass and glass‐ceramics having rare‐earth‐rich crystalline phase for nonlinear optical and infrared photonic applications. DSC analysis (10°C/min) demonstrates a progressive increase in glass‐transition temperature (T_g) from 359 to 452°C with the increase in La₂O₃ content. Continuous glass network modification with transformation of [TeO₄] to [TeO₃/TeO₃₊₁] units is evidenced from Raman spectra which is corroborated with XPS studies. While mechanical properties demonstrate enhancement of cross‐linking density in the network. These glasses exhibit optical transmission window extended from 0.4 to 6 μm with calculated zero dispersion wavelength (λ_ZDW) varying from 2.41 to 2.28 μm depending upon La₂O₃ content. Crystallization kinetics of TTL10 (80TeO₂‐10TiO₂‐10La₂O₃ in mol%) glass has been studied via established models. Activation energy (E_a) has been evaluated and dimensionality of crystal growth (m) suggests formation of surface crystals. Glass‐ceramic with crystalline phase of La₂Te₆O₁₅ has been realized in heat‐treated TTL10 glass samples (at 450°C). As predicted from DSC analysis, FESEM study unveils the formation of surface crystallized glass‐ceramics.     

Rare‐earth‐doped SiO2‐CaF2 glass ceramic nano‐particle with upconversion properties

Rare‐earth‐doped upconversion nano‐phosphor shows new possibilities in the field of bioimaging because of its unique properties like higher penetration depth, low signal to noise ratio (SNR), good photo stability, and zero auto fluorescence. The oxyfluoride glass system is the combination of both fluoride and oxide where fluoride host offers high optical transparency due to low phonon energy and oxide network offers high physical stability. Thus, in the present work, an attempt has been made to synthesize 1 mol% Er³⁺ doped SiO₂‐CaF₂ glass ceramic nano‐particles through sol‐gel route. The synthesized glass ceramic particles were heat treated at 4 different temperatures starting from 600°C to 900°C.The X‐ray diffraction (XRD) analysis and Transmission electron microscopy (TEM) analysis confirmed the formation of CaF₂ nano‐crystals in the matrix which is 20‐30 nm in size. The vibrational spectroscopic analysis of the glass ceramics sample has been investigated by Fourier transform infrared (FTIR) spectroscopy. The UV‐Visible‐NIR spectroscopy analysis was carried out to analyze the absorption intensity in the near infrared region. Upon 980 nm excitation, the sample shows red emission corresponds to ⁴F_9/2→⁴I_15/2 energy level transition. The prepared nano‐particles showed excellent biocompatibility when tasted on MG‐63 osteoblast cells.     

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.     

Electric Field‐Induced Light Scattering in Eu‐Doped PMN‐PT Transparent Ceramics

Highly transparent Eu‐doped Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃(PMN‐PT) ferroelectric ceramics were obtained by a two‐stage sintering method. Eu doping play a significant role in the domain structures of PMN‐PT ceramics and resulted in different light scattering responses under electric field. The dielectric behaviors, ferroelectric properties, and domain configurations in the ceramics with increasing Eu doping concentration were studied, which were consistent with the electric field‐induced light scattering responses.     

Preparation and characterization of durable superhydrophobic protective coatings on aluminum alloy

The durable superhydrophobic protective coatings on the 7B04 aluminum alloy surface was prepared by using acid etching and boiling water bath to construct micro-nano hierarchical structure, and then spraying suspension containing aluminum phosphate adhesive (AP) and perfluorooctyltrichlorosilane (PFOTS) to increase adhesion and reduce surface energy. The samples were characterized by field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), contact angle measurement (CA), electrochemical impedance spectroscopy(EIS) and a variety of the environmental simulation experiments. The results showed that the static water contact angle (WCA) of the surface is 158.4° and the slide angle (SA) is about 0°, suggesting superhydrophobicity and low adhesion to water. The coating resistance (R_c) was as high as 101.55 kΩ· cm² and the charge transfer resistance (R_t) in NaCl corrosion medium increased by nearly two orders of magnitude, showing excellent protective performance. The sample can withstand a variety of damages, with ideal mechanical durability, chemical durability and environmental durability.     

铝合金表面耐久性超疏水防护膜的制备与表征

通过酸刻蚀-沸水浴处理构筑微纳米分级结构,进而通过喷涂含有磷酸铝胶黏剂(AP)和低表面能物质——全氟辛基三氯硅烷(PFOTS)的悬浮液增强结合力并降低表面能,从而在国产7B04铝合金表面制备了耐久性超疏水防护膜。利用场发射扫描电子显微镜(FESEM)、X射线光电子能谱仪(XPS)、傅里叶变换红外光谱仪(FTIR)、接触角测试仪(CA)、电化学阻抗谱(EIS)等技术以及多种环境模拟实验对样品进行了表征,结果显示,制备的防护膜表面水静态接触角(WCA)高达158.4°,滑动角(SA)为0°,呈现出超疏水和低黏附性;膜层电阻(Rc)约为101.55 kΩ·cm2,在NaCl腐蚀介质中的电荷转移电阻(Rt)增大了近2个数量级,表现出优异的防护性能;样品可以经受多种破坏,具有理想的机械耐久性、化学耐久性和环境耐久性。     

纳米二氧化钛/氟树脂超疏水涂层的制备及性能

以金红石型纳米TiO2及自制的氟树脂制备了氟碳涂料,采用刷涂法于铁片表面构筑了超疏水涂层。考察了纳米TiO2与氟树脂用量、热处理温度等对涂层疏水性的影响,并分别用扫描电镜(SEM)、接触角测量仪观察和测试了涂层表面的微观结构及疏水性。结果表明,涂层表面的水接触角随着氟树脂用量的增加而增大,随纳米TiO2用量的增加呈先增后减的趋势。涂层的吸水率随着氟树脂用量的增加而减少,随纳米TiO2用量的增加呈先减后增的趋势。随着热处理温度的升高,涂层的水接触角先增后减,吸水率先减后增。最佳工艺条件是TiO2及氟树脂的质量分数分别为12%与40%,热处理温度170℃。此条件下得到的涂层表面具有微/纳二元粗糙结构,对水静态接触角达152°,为超疏水涂层,并具有优异的耐水、耐酸碱、耐洗刷、耐沾污及自清洁性能。     

超临界CO2快速膨胀法制备SiO2/聚氨酯超疏水涂层

用超临界CO₂快速膨胀法制备了SiO₂/聚氨酯超疏水涂层。首先用十三氟辛基三乙氧基硅烷（F-硅烷）和γ-(甲基丙烯酰氧基)丙基三甲氧基硅烷（KH-570）改性纳米二氧化硅,制备出含双键的纳米二氧化硅粒子,将其分散在超临界CO₂中,再利用超临界CO₂快速膨胀法将其喷射到双键封端的且已添加了引发剂的聚氨酯涂层表面,通过加热,使纳米二氧化硅粒子接枝在聚氨酯涂层表面,形成稳固粗糙结构,获得了超疏水性质。研究了喷嘴温度、反应釜温度和压力、偶联剂配比、表面粗糙度对涂层疏水性的影响。结果表明：涂层的静态水接触角可达到169.1°±0.6°;在喷嘴和釜内温度都为90℃,釜内压力为16 MPa,F-硅烷和KH-570配比为1∶1,表面粗糙度为7.3 μm时,所制得涂层具有较好的超疏水性,且具有优良的耐刮伤性。该法高效环保,涂层性能优良,适于大面积制备。     

Carbon nanotube/graphene oxide‐added CaO‐B2O3‐SiO2 glass/Al2O3 composite as substrate for chip‐type supercapacitor

A CaO‐B₂O₃‐SiO₂ (CBS) glass/40 wt% Al₂O₃ composite sintered at 900°C exhibited a dense microstructure with a low porosity of 0.21%. This composite contained Al₂O₃ and anorthite phases, but pure glass sintered at 900°C has small quantities of wollastonite and diopside phases. This composite was measured to have a high bending strength of 323 MPa and thermal conductivity of 3.75 W/(mK). The thermal conductivity increased when the composite was annealed at 850°C after sintering at 900°C, because of the increase in the amount of the anorthite phase. 0.25 wt% graphene oxide and 0.75 wt% multi‐wall carbon nanotubes were added to the CBS/40 wt% Al₂O₃ composite to further enhance the thermal conductivity and bending strength. The specimen sintered at 900°C and subsequently annealed at 850°C exhibited a large bending strength of 420 MPa and thermal conductivity of 5.51 W/(mK), indicating that it would be a highly effective substrate for a chip‐type supercapacitor.     

UV固化SiO_2/超支化聚氨酯丙烯酸酯透明涂层制备与性能

以TEOS和MAPTMS改性硅溶胶为无机组分,以超支化聚氨酯丙烯酸酯(HBPUA)为有机组分,制备了可UV固化HBPUA/(MAPTMS-SiO2)杂化涂层材料,nSiO2∶nMAPTMS=1∶2,改性硅溶胶用量为30ω/%,HBPUA/(MAPTMS-SiO2)杂化涂层材料的凝胶时间大于180 d,透光率为92.8%,硬度为4 H,附着力为0级,柔韧性为3 mm,冲击强度为46 kg·cm,磨耗量为17.5 mg,涂层性能较佳。     

聚氯乙烯基超疏水材料的制备及应用研究进展

聚氯乙烯（PVC）是世界上应用最广泛的塑料之一,因其具有化学和机械特性优异、廉价易得等优点而广泛应用于医疗器械制造、建筑、食品和电子等行业。PVC对水的接触角为90°,而在生物医学和金属防腐蚀等领域的应用中,需要PVC达到超疏水性能。因此,PVC基超疏水材料的需求也变得愈加迫切。本文综述了聚氯乙烯基超疏水材料的分类、制备方法和应用领域,对比了不同种类、不同制备方法的聚氯乙烯基超疏水材料的疏水性能优劣,总结出目前该领域的一些问题,主要包括制备工艺仅限于实验室操作、材料的耐磨耐久性及机械强度有待考察等,并指出该领域的发展方向：(1)开发简单、环保、低成本的大规模制备工艺;(2)克服PVC材料热、光稳定性差的弱点,发扬其耐腐蚀性好、机械强度高的优点,进一步扩大材料的应用范围。     

Synthesis of novel phosphorous‐containing biphenol, 2‐(5, 5‐dimethyl‐4‐phenyl‐2‐oxy‐1,3,2‐dioxaphosphorin‐6‐yl)‐1,4‐benzenediol and its application as flame‐retardant in epoxy resin

A novel phosphorous‐containing biphenol, 2‐(5,5‐dimethyl‐4‐phenyl‐2‐oxy‐1,3,2‐dioxaphosphorin‐6‐yl)‐ 1,4‐benzenediol (DPODB), was prepared by the addition reaction between 5,5‐dimethyl‐4‐phenyl‐2‐oxy‐1,3,2‐dioxaphosphorinane phosphonate (DPODP) and p‐benzoquinone (BQ). The compound (DPODB) was used as a reactive flame retardant in o‐cresol formaldehyde novolac epoxy resin (CNE) for electronic application. The structure of DPODB was confirmed by FTIR and NMR spectra. Thermal properties of cured epoxy resin were studied using differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The flame retardancy of cured epoxy resins was tested by UL‐94 vertical test and achieved UL‐94 vertical tests of V‐0 grade (nonflammable). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3842–3847, 2006     

Transparent polycrystalline nanoceramics consisting of triclinic Al2SiO5 kyanite and Al2O3 corundum

Transparent polycrystalline nanoceramics consisting of triclinic Al₂SiO₅ kyanite (91.4 vol%) and Al₂O₃ corundum (8.6 vol%) were fabricated at 10 GPa and 1200‐1400°C. These materials were obtained by direct conversion from Al₂O₃‐SiO₂ glasses fabricated using the aerodynamic levitation technique. The material obtained at 10 GPa and 1200°C shows the highest optical transparency with a real in‐line transmission value of 78% at a wavelength of 645 nm and a sample‐thickness of 0.8 mm. This sample shows equigranular texture with an average grain size of 34 ± 13 nm. The optical transparency increases with decreasing mean grain size of the constituent phases. The relationship between real in‐line transmission and grain size is well explained by a grain‐boundary scattering model based on a classical theory.     

Salinity effects on the degree of hydrophobicity and longevity for superhydrophobic fibrous coatings

Previous studies on submerged superhydrophobic surfaces focused on performance variables such as drag reduction and longevity. However, to use such surfaces for practical applications, environmental factors such as water salinity must be investigated and understood. In this work, experiments were carried out to investigate the impact of salt (sodium chloride, NaCl) concentrations in aqueous solutions on the hydrophobicity and longevity of polystyrene (PS) fibrous coatings. Rheological studies using salt water as a test fluid were performed to determine the effect of salt concentration on drag reduction. Contact‐angle measurements were used to validate the results from the rheometer. In situ noninvasive optical reflection was used to measure the longevity of the coating—time‐dependent loss of entrapped air within the coating—as a function of salinity. The superhydrophobic coating used herein consisted of PS fibers that were deposited using DC‐biased AC‐electrospinning. Electrospinning is scalable and far less expensive than conventional methods (e.g., microfabrication), bringing the technology closer to large‐scale submerged bodies such as submarines and ships. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011