二氧化硅气凝胶最佳制备工艺的确定

以正硅酸乙酯为原料,先采用溶胶-凝胶法制备湿凝胶,然后浸泡在反应溶液中进行老化,再利用正己烷进行溶剂交换,三甲基氯硅烷进行表面改性,最终获得轻质多孔二氧化硅气凝胶。并通过正交试验,确定了制备凝胶的最佳工艺条件是:pH=5,TEOS∶乙醇∶水(摩尔比)=1∶4∶8;利用FTIR、XRD和SEM等方法对二氧化硅气凝胶改性特征和添加DCCA前后的物理性质进行表征。     

溶胶-凝胶法制备RDX/SiO_2薄膜

为有效阻止RDX/SiO2膜的开裂,基于溶胶-凝胶法制膜原理,通过调节SiO2溶胶的摩尔配比和陈化时间,在其凝胶点处加入一定量RDX的N,N-二甲基酰胺(DMF)溶液,同时添加适量黏结剂,手工旋涂并冷冻干燥成膜。结果表明,适当增加水与正硅酸乙酯(TEOS)的摩尔比(r),缩短溶胶恒温陈化时间,缓慢干燥的同时保证环境湿度,加入质量分数3%~5%的氟橡胶(FPM2602)或聚乙烯醇(PVA),均可以增强凝胶骨架的连接作用,在一定程度上减少RDX/SiO2膜的开裂。     

NIR-shielding films based on PEDOT-PSS/polysiloxane and polysilsesquioxane hybrid

Near-infrared (NIR)-shielding films based on polysiloxane or polysilsesquioxanes and poly(3,4-ethylenedioxythiophene)-poly(4-styrene sulfonate) (PEDOT-PSS) were synthesized via a sol–gel reaction. Phase-separated mixtures of tetraethyl orthosilicate (TEOS) or methyltriethoxysilane (MTES) with an aqueous dispersion of PEDOT-PSS formed deep-blue homogeneously dispersed sols after stirring. Thin films were prepared by depositing the resulting homogeneously dispersed sols on a glass substrate by spin coating and heating. PEDOT-PSS/TEOS films maintained uniform flat surfaces after 10 coatings. MTES-based films exhibited mottled patterns with nonuniform surfaces. The 10-layer TEOS-based film has high NIR-shielding properties with moderately visible transmittance. NIR absorption by the PEDOT-PSS/TEOS hybrid suppresses air temperature elevation. The five-layer TEOS-based film showed similar NIR-shielding ability and slightly lower visible light transmittance compared with tin-doped indium oxide glass. The 10-layer TEOS-based film exhibited a 15.6% lower temperature rise than the uncoated glass substrate. Specifically, this is an environmentally friendly NIR-shielding material. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48367.     

Formation and structure of polyacrylamide–silica nanocomposites by sol–gel process

The formation of nanocomposites by the sol–gel reaction of tetraethoxysilane (TEOS) in polyacrylamide (PAAm) is studied. The nanocomposites are prepared in aqueous solution. Fourier transform IR spectroscopy shows that substantial hydrogen bonding occurs in the nanocomposites. The fracture surfaces of the nanocomposites are observed by atomic force microscopy (AFM) as a function of the TEOS content. The AFM images reveal that the PAAm–silica nanocomposite exhibits particle–matrix morphology. It is also found that aggregate formation is more dominant than the particle growth with the TEOS contents. The solution of composite precursor is also applied to spin coating. Furthermore, during the calcination there is an observable change in the silica networks, and then a microinterconnected structure is generated. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1817–1823, 2002     

ZrO2-SiO2二元系统平面光波导薄膜的制备与性能表征

应用溶胶-凝胶技术,以TEOS与ZrOCl2·8H2O为先驱体,研制了用于有源光波导基质材料的ZrO2-SiO2二元系统薄膜,探明了ZrO2-SiO2二元系统薄膜折射率、厚度与薄膜组分、匀胶速度、陈化时间、热处理温度的内在关系,实现薄膜厚度和薄膜折射率在一定范围内的连续可调,为研制一类新型的光通信窗口有源光波导材料提供了基质材料.     

DTAB表面活性剂在硅气凝胶干燥中的应用

使用十二烷基三甲基溴化铵（DTAB）阳离子表面活性剂溶液对湿凝胶进行处理,可降低凝胶中液体表面张力,从而得到保持较完整孔隙结构的硅气凝胶。结果表明,采用DTAB水溶液浸泡湿凝胶的方法要优于在凝胶形成前加入DTAB的方式。使用浓度为1.48×10-2 mol/L的DTAB水溶液浸泡湿凝胶可得到孔隙率为81.8%、平均孔径为15.749 nm、总孔体积为2.836 cm3/g、比表面积为923 m2/g的二氧化硅气凝胶;其吸脱附曲线明显高于其他添加浓度的吸脱附曲线,表明具有较高的吸附能力;在TEM图中可明显看出其具有孔隙结构。DTAB处理过的气凝胶明显优于未经处理的二氧化硅气凝胶。     

Effective Air‐Spray Deposition of Thin Films Obtained by Sol–Gel Process onto Complex Pieces of Sanitary Ware

A deposition mechanism by air‐spray technique is carried out for depositing silica‐based thin films obtained by the sol–gel process. The air‐spray deposition is very useful to coat large and complex surfaces with different morphologies and roughnesses which favors the technology scale‐up, contrary to the most used deposition methods in the sol–gel process (dip and spin coating). To establish the adequate conditions of these techniques, a complete study of the sol properties (rheology, FT‐IR, roughness, thickness) is attempted, which has allowed determining the parameters for the effective air‐spray deposition of homogeneous thin films. By means of an experimental design, it has been possible to validate the selected parameters. Finally, a scheme of an effective spray deposition model is proposed for a better understanding of the deposition mechanisms.     

Sol–Gel Fabrication of Epitaxial and Oriented TiO2 Thin Films

Thin films of titania have been prepared by spin coating on fused silica, Si(100), and rutile(110), starting with a sol–gel process. The alkoxide solution was chelated with diisopropanolamine, and the resulting precursor solution was hydrolyzed prior to coating. Oriented rutile films were obtained on fused silica and Si(100), while epitaxially oriented film was formed on rutile (110). X-ray diffraction results indicated that the as-deposited films transformed to rutile via anatase with increasing temperature. The phase transformation temperature was found to be dependent on the substrate, and it was in general higher on the substrates than that observed for the gel powder. Microstructural studies revealed that these films consisted of finely dispersed grains of 0.05 to 0.15 μm in size.     

Effects of Solution History on Sol‐Gel Processed Tin‐Oxide Thin‐Film Transistors

Antimony‐doped tin‐oxide (SbTO) thin films deposited by solution processing methods represent a promising avenue toward low‐cost transparent and flexible electronics, but reproducibility and performance homogeneity of devices prepared from these thin films have been seldom investigated. In this study, the role of sol‐gel precursor aging is investigated by comparing SbTO thin‐film transistors (TFT) fabricated from two different sol‐gel solutions: the first one was aged for 4 years, whereas the second was prepared freshly. For each of the solutions, a set of TFT was assembled on the same chip, to investigate the distinct roles of aging and sample inhomogeneity on the electronic and transport properties of SbTO. Higher electron mobility, but lower on/off ratios, was found in TFTs assembled from freshly prepared solution, an effect that may be assigned to larger size of SbTO grains. This study demonstrates the critical role of the solution “history” in determining the properties and reproducibility of SbTO TFTs, over other factors, including local film inhomogeneity and local fluctuations of the annealing temperature.     

New BST–silica suspension coating material for dielectric thin films fabricated at low temperatures

Abstract

A new Ba_0·7Sr_0·3TiO₃ (BST)–silica suspension has been developed as a coating material for dielectric thin films. Using a spin on glass (SOG) wet process, a thin layer consisting of nanoparticles of BST and silica was formed on an Al/SiO₂/Si wafer. The BST–silica suspension was made by mixing a BST nanoparticle dispersion with methyl siloxane oligomer. A silicon wafer was coated with the BST–silica suspension using a spin coater and heat treated. The sample was then coated with methyl siloxane oligomer and heat treated again, and finally, a top electrode was applied. The Al/SiO₂/BST–SiO₂/Al/SiO₂/Si stack thus prepared is a metal insulator metal (MIM) capacitor. The electrical properties of the MIM capacitor were evaluated and its capacitance, dissipation factor and voltage coefficient of capacitance were determined to be 1054 pF mm^?2, <0·1 and <100 ppm V^?1 respectively.     

不同旋涂方式对铜锌锡硫硒薄膜及相应器件性能的影响

晶体质量是决定铜锌锡硫硒(Cu₂ZnSn(S,Se)₄, CZTSSe)吸收层薄膜吸收效率的关键,旋涂是溶液法制备CZTSSe吸收层的第一步,因此旋涂方式的选择至关重要。为了探究不同旋涂方式对CZTSSe吸收层薄膜质量和相应器件性能的影响,分别采用三组不同的旋涂方式制备铜锌锡硫(Cu₂ZnSnS₄, CZTS)前驱体薄膜及CZTSSe吸收层薄膜,并利用X射线衍射仪(XRD)、能谱仪(EDS)、显微拉曼光谱仪(Raman)、场发射扫描电子显微镜(FE-SEM)分析了不同旋涂方式对所制备的CZTSSe吸收层薄膜晶体结构、元素成分、相纯度、表面形貌的影响。同时,采用电流密度-电压(J-V)测试和外量子效率(EQE)测试对CZTSSe吸收层薄膜太阳电池的光电特性进行了表征。结果表明:旋涂7周期,且第一周期烘烤之前旋涂2次的效果最好,所制备的CZTS前驱体薄膜均匀,无裂纹,CZTSSe吸收层薄膜结晶度更高,薄膜表面更平整致密,晶粒大小更均匀,实现了9.63%的光电转换效率。通过对采用不同旋涂方式制备的器件的性能参数进行统计分析,得出新的旋涂方式可以提高CZTSSe薄膜太阳电池的可重复性,为将来可能的大规模商业化应用做铺垫。     

Thermal stability and flame retardancy of polyester,cotton, and relative blend textile fabrics subjected to sol–gel treatments

Polyester (PET), cotton (COT), and two relative blend textile fabrics were treated by sol–gel processes. Tetraethoxysilane (TEOS) was used as inorganic precursor of silica phases; furthermore, different TEOS/H₂O ratios were examined to explore the effect of the presence of SiO₂ on the thermal and fire stability of the textile fabrics investigated. The distribution and dispersion of SiO₂ were observed by means of scanning electronic microscopy (SEM). SEM magnifications showed the formation of a continuous silica film located in the neighboring fibers; furthermore, in the case of PET, such a film incorporated silica particles with an average diameter ranging between 0.2 and 6 μm. The thermal and thermooxidative stabilities of the treated samples were investigated by thermogravimetric analysis: after the sol–gel treatment, the degradation mechanism was modified both in nitrogen and in air, and the improvement in the thermal stability was attributed to the presence of silica, which played a protective role in the degradation of the textile fabrics. Finally, we investigated the combustion behavior of the textile fabrics by cone calorimetry, measuring the time to ignition, the heat release rate, and the relative peak. The former was found to depend on the type of fabric; the latter generally evidenced a remarkable decrease for all of the treated samples, up to 35% compared to the neat counterparts. This indicated that the sol–gel treatments improved the flame retardancy of the PET/COT fabrics. This conclusion was also confirmed by limiting oxygen index tests, which evidenced burning kinetics changes in the presence of the silica coating. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Assembly of methylated hollow silica nanospheres toward humidity-resistant antireflective porous films with ultralow refractive indices

Humidity-resistant antireflective (AR) porous films with ultralow refractive indices were prepared via an one-step sol–gel process by assembly of methylated hollow silica nanospheres (HSNs). The hydrophobicity and refractive indices of silica-based AR porous films could be varied between 66.0° and 115.0°, and between 1.08 and 1.14, respectively, by tuning the MTES/TEOS molar ratios. A possible assembly mechanism was proposed according to the microstructure of methylated HSNs and porous films. The various properties of silica-based AR porous films were investigated and the AR porous film could demonstrate a good AR capability of 97.6% and excellent humidity resistance.     

超低介电常数纳米多孔SiO2薄膜制备技术进展

纳米多孔SiO2薄膜具有超低的介电常数，作为绝缘介质在超大规模集成电路互连系统有着巨大的应用潜力。文中概述了纳米多孔SiO2薄膜的孔隙度与介电常数的关系，指出所有模型均位于串联和并联模型之间，介电常数均随孔隙度的增加而下降。说明了多孔SiO2薄膜按孔隙度不同主要分气凝胶和干凝胶两类。介绍了从溶液前驱物中合成的原理，绘出了制备纳米多孔SiO2薄膜的一般流程。详细总结了用气凝胶／干凝胶法和模板法制备纳米多孔SiO2薄膜的技术进展。探讨了旋转涂覆制备多孔SiO2薄膜的弱点及改进办法，指明了超低介电常数纳米多孔SiO2薄膜制备技术的发展方向。     

Thermal and mechanical behavior of natural rubber latex‐silica aerogel film

A major problem in most natural rubber latex (NRL) commonly encountered like other polymer is susceptibility to mechanical properties and thermal degradation; particularly in thin film due to the presence of double bonds in the main chain. Therefore, it is desirable to seek for ways of improving these properties. Silica aerogel is a material with extraordinary properties was believed to have potential enhance properties in NRL films because of its high specific surface area. Therefore, based on the unique character of silica aerogel, NRL‐silica aerogel film was developed by latex compounding and dry coagulant dipping to form thin film where silica aerogel acts as filler. Silica aerogel, synthesized from rice husk was dispersed in a ball‐mill using distilled water for NRL compounding. Results indicate that increasing silica aerogel loading enhances the mechanical properties of the NRL‐silica aerogel film. Effects of postvulcanization processes were also investigated, whereby the best reinforcing effect was obtained at 4 phr silica aerogel loading with leaching postvulcanization condition. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Sol–gel incorporation of silica nanofillers for tuning the anti-corrosion protection of acrylate-based coatings

The aim of the present work is to synthesize through sol–gel approach new hybrid polymeric nanocomposites to be used as coating materials. An acrylic-based polymer was prepared by free-radical copolymerization of two monomers widely used for coatings, namely 2-ethylhexylacrylate (EHA) and glycidyl methacrylate (GMA) bearing epoxy moieties, in which silica nanoparticles were incorporated by in situ acid hydrolysis and subsequent condensation of tetraethoxysilane (TEOS). Glycidoxypropyl trimethoxysilane (GPTS) was used as coupling agent to fine-tune the compatibility between organic and inorganic phases. The morphology, mechanical properties and corrosion resistance of thin films applied on aluminum alloys were optimized by varying the content of silica nanoparticles whose properties were strongly affected by the TEOS/GPTS ratios. Performances of the obtained hybrid materials were scrutinized by atomic force microscopy (AFM), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), and electrochemical impedance spectroscopy (EIS). Thus it was evidenced that an optimum amount of silica nanoparticles with a precise morphology and composition in term of TEOS/GPTS ratio is needed to maintain good coating barrier properties. Outstanding anti-corrosion protection was reached by using optimized hybrid films.     

Characterization and Investigation of the Tribological Properties of Sol–Gel Zirconia Thin Films

Sol–gel zirconia thin films were prepared by dip coating in an ethanol solution of zirconium oxychloride. The zirconia films consisted of a completely tetragonal phase and exhibited nanoscale uniformity. They displayed excellent antiwear and friction-reduction performance in sliding against steel. The friction coefficient (0.13–0.15) and the wear life over 5000 sliding cycles were recorded for the films at a sliding speed of 90 mm/min and a load of 0.5 N. The film was characterized by slight scuffing and abrasion at low loads and sliding speeds.     

Fabrication of superhydrophobic silica‐based surfaces with high transmittance by using polypropylene and tetraeyhoxysilane precursors

Preparation of superhydrophobic silica‐based surfaces via sol–gel process by adding polyethylene glycol (PEG) polymer into the precursor solution has been developed. Surface roughness of the films was obtained by removing the organic polymer at 500°C and then the hydrophobic groups bonded onto the films were obtained by self‐assembly modification with a monolayer. Characteristic properties of the as‐prepared films were analyzed by contact angle measurements, scanning electron microscopy, atomic force microscopy, UV–vis scanning spectrophotometer, and X‐ray photoelectron spectrophotometer. The experimental parameters were varied by the type of silane species, the R ratio, the hydrolysis time of the precursor solution, the molecular weight of PEG, the pH value of mixing solution, and the different reagents for modification. The results showed that optimum ratio of TEOS/H₂O/ethanol in the sol–gel process for precursor solution was set to 1/10/4. The better contact angles of the films can be obtained by the acid catalyst reaction, especially the pH value of mixing solution was adjusted to 0. When the as‐prepared rough films were modified with (tridecafluoro‐1,1,2,2‐tetrahydrooctyl) dimethylchlorosilane (TFCS), the contact angle of the film can be promoted to 150.4°, and the transmittance of the films in the visible light region was greater than 94.5%. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Characterization of antireflective coatings on poly(methyl methacrylate) substrate by different process parameters

The high/low refractive index organic/inorganic antireflective (AR) hybrid polymers were formed using the sol–gel process, in which TiO₂/2‐hydroxyethyl methacrylate (2‐HEMA) (high refractive index hybrid polymer) and SiO₂/2‐HEMA (low refractive index hybrid polymer) two‐layer thin films were formed on a hard coating deposited poly(methyl methacrylate) (HC‐PMMA) substrate by both spin coating and dip coating. The relationship between the process parameters and the optical properties, thickness, porosity, surface morphology, and adhesion was determined. The results show that the reflectance of the two‐layer thin films on HC‐PMMA substrate is less than 0.21% (λ = 550 nm), with good adhesion (5B) and a hardness of up to 4H. In addition, the thickness, porosity, and roughness of the films affect refractive index and the antireflection properties of the AR two‐layered thin film. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

电导率调控介孔二氧化硅增透膜透过性能的研究

以正硅酸乙酯（TEOS）为前驱体,三嵌段共聚物（F127）为模板剂,利用酸催化的形式通过溶胶-凝胶法制备介孔二氧化硅增透膜液。采用浸渍提拉法在硼硅玻璃基片上进行镀膜,利用马弗炉对膜层进行固化处理。采用紫外可见分光光度计、电导率仪对膜的透过性能及膜液的电学性能进行分析。结果表明,溶剂在6个月的长期挥发下会导致膜液电导率由243 μS/cm增大到266 μS/cm,相同的提拉速度会使得膜层变厚,透过率峰值出现“红移”现象,300~2 500 nm的平均透光率由96.7%降为96.0%。通过对实验所得数据进行拟合可知,膜液电导率与二氧化硅浓度成简单的线性关系,与最优提拉速度成单指数函数关系,使用膜液电导率对标稀释的方法可使所镀膜层透过率得到恢复,能在不影响生产效率的前提下保证膜层产品的一致性。