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.     

溶胶-凝胶法制备环保型彩色玻璃

通过溶胶-凝胶法制备了掺杂有生物染色剂的SiO2彩色溶胶,利用提拉法在普通玻璃上镀膜,制得了均匀透明,颜色鲜亮,可回收利用的彩色玻璃.彩色玻璃在可见光部分的透射率可通过改变薄膜的厚度或溶胶中染料的浓度而进行调控.运用光谱分析法研究了彩色玻璃的耐磨损、耐刮擦、耐腐蚀和抗紫外线等实际耐用性能.     

Transparent hydrophobic organic-inorganic nanocomposite films

Hydrophobic, transparent organic-inorganic hybrid coatings were synthesized by the incorporation of SiO₂ nanoparticles in a matrix of 3-glycidoxypropyltrimethoxysilane (GPTS) and tetramethyl orthosilicate (TMOS) followed by overlaying isobutyltrimethoxysilane (IBTMS) film for enhanced hydrophobicity. Scanning probe microscopy, ellipsometry and contact angle measurements were used to study their morphology, thickness and surface properties. GPTS and TMOS sol with SiO₂ nanoparticles resulted in rough but transparent surface of homogeneous monolayer of ∼40 nm. The rough surface mimicking lotus leaf was chemically modified with a layer of IBTMS resulting in the contact angle of nearly 130°. Morphology as well as contact angles were dependent on the thickness of IBTMS hydrophobic coating layer. Process of creating rough but transparent and durable layer loaded with SiO₂ particles demonstrates the feasibility of meeting all three desired characteristics of transparency, durability and superhydrophobicity.     

聚乙烯醇/二氧化硅共混膜的制备及耐温、耐溶剂性能研究

以聚乙烯醇（PVA）和正硅酸乙酯（TEOS）为原料,通过溶胶－凝胶（Sol-Gel)方法,制备出不同二氧化硅含量的聚乙烯醇／二氧化硅（PVA／SiO2)共混均质膜。通过热重分析（TGA）、示差扫描量热法（DSC）和动态力学分析（DMA）研究了共混膜的热性能。结果表明,与PVA膜相比,PVA／SiO2共混膜具有更高的热稳定性,随SiO2含量的增大,共混膜的分解温度升高,玻璃化温度也略有提高。以水为溶剂,测定了共混膜的耐溶剂性能。与PVA膜相比,PVA／SiO2共混膜的耐溶剂性能有显著的提高。     

Novel pathways for the preparation of silica antireflective films: Improvement in mechanical property

Silica antireflective films by the base catalyzed sol-gel process show poor mechanical property. In this study, silica antireflective films with good mechanical property have been prepared by the acid catalyzed templating sol-gel process. The single-layer film was deposited from an acid-catalyzed silica sol solution with polymer F127 incorporation. The silica sol was first dip deposited onto substrate to form films on both sides of the substrate and then subjected to thermal treatment at 500 °C. After thermal treatment, the abrasion resistant antireflective film was achieved due to the formation of porous structure in the resultant film as a result of decomposing F127. Optical spectroscopic measurement shows that the coated glass with maximum transmittance of 99.5% has been obtained. Nanoindenter measurement shows that the elastic modulus and hardness of films are 16 GPa and 1.3, respectively, which are much better than those films derived from base-catalyzed silica sols. The high transmittance and good mechanical property make such films potential in both military and civil applications.     

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。     

Investigation of MgF2 optical thin films with ultralow refractive indices prepared from autoclaved sols

We have successfully developed a process to form high quality MgF(2) thin films with ultralow refractive indices from autoclaved sols prepared from magnesium acetate and hydrofluoric acid. And we have confirmed that our porous MgF(2) coatings have not only high transmittance in the UV region but also high uniformity of film thickness. They can be uniformly formed on phiv 300 mm substrates as a single coating and as a hybrid coating with sublayers formed by physical vapor deposition. They are expected to be applied to various optics that need high transmittance in the UV region.     

Preparation of black-colored thin films from silica sol containing dissolved metal nitrates by the sol-gel method

Black-colored SiO₂-based films, containing colorant inorganic spinel crystals such as Cu₂MnO₄, CuMn₂O₄, CuMnCrO₄, CuMnFeO₄ or CuMnCoO₄, were prepared from a silica sol containing dissolved metal nitrates using the dipping-withdrawing technique. The inorganic colorants were formed in the SiO₂ matrix of the films by heat-treatment at temperatures from 600 to 660°C. The black-colored coating films were uniform and transparent with a low haze value (less than 1.0%) and with a thickness of 100–800 nm in the SiO₂-(Cu-Mn-Cr-O) system, for which the colorant was the spinel crystal of CuMnCrO₄. The visible light transmittance of the colored films was controlled in a relatively wide range of 15–65% by changing the film thickness or the colorant concentration in the coating solution. Optimization of the composition of the coating solution and the preparation conditions gave black-colored films with excellent durability and visible light transmittance of about 25%, which is similar to that of deeply black-colored glasses commonly produced by the melting method. For example, a black-colored film with a visible light transmittance of 24.6% and a film thickness of 160 nm was obtained from a coating solution with a nominal composition of 36SiO₂·64CuMnCrO₄. The durabilities of the glasses with black-colored coatings against scratching, abrasion and chemicals are good enough for the practical applications.     

Structural and optical properties of nitrogen‐iron co‐doped titanium dioxide films prepared via sol‐gel dip‐coating: Effect of urea and iron nitrate concentration in the sol

In this study, nitrogen‐iron co‐doped titanium dioxide films were prepared via sol‐gel dip‐coating method using urea and iron nitrate as nitrogen and iron source, respectively. Nonmetal doping of TiO₂ have some disadvantages such as massive charge carrier recombination and losing the photo‐catalytic capability. Three different nitrogen‐iron co‐doped titanium dioxide sols with different urea and iron nitrate concentration were prepared. The resulting sols were homogeneous and transparent, and no precipitation was observed in any of them. It was observed that the film prepared with middle urea‐iron nitrate concentration sol got opaque in a short time after the dip‐coating process. All prepared films were characterized by X‐ray diffraction, X‐ray photoelectron spectroscopy, scanning electron microscopy, confocal microscopy and ultraviolet–visible (UV‐Vis) spectroscopy. It was found that the concentration of the urea and iron nitrate in the sol had an effect on the crystal structure, microstructure, surface morphology and optical properties of the resulting films. Samples with middle concentrations had amorphous structure and bigger particle size. It was seen that sample with higher iron amount has lower band‐gap. It is concluded that we can prepare transparent anatase, transparent amorphous and opaque amorphous titanium dioxide films by changing the urea and iron nitrate concentration in the sol.     

透明超疏水涂膜的研究进展

透明超疏水涂膜不但具有超疏水表面的独特性能,而且对可见光具有良好的透光性,在生产和生活中有着广泛的应用潜力,已逐步成为超疏水表面领域的一个研究热点。介绍了超疏水涂膜的透明性,并归纳了近年来透明超疏水涂膜制备方法取得的新进展。根据现有的理论和研究,提出利用氟硅烷类低表面能物质,与溶胶-凝胶法、相分离技术、等离子体刻蚀等能提供表面微观结构和粗糙度的技术有机结合,并控制好粗糙度与可见光透过率之间的关系,可制备出适用的透明超疏水涂膜。     

溶胶-凝胶法制备TiO2纳米薄膜的晶粒长大机理研究

通过sol-gel法在普通钠钙玻璃表面制备了均匀透明的锐钛矿型TiO2纳米薄膜.用透射电镜(TEM)、X射线衍射(XRD)和紫外可见吸收光谱(UV-VIS)等对薄膜的晶粒大小和透光率进行了表征.结果表明:随着镀膜次数和热处理时间的增加,薄膜中的平均晶粒大小接近线性增加.仅增加TiO2薄膜的热处理时间,薄膜中晶粒长大不明显,其吸收阀值未发生明显的红移.因此, 薄膜中晶粒长大的机理可能是: 上一次镀的TiO2晶粒成了下一次镀TiO2溶胶的晶核, 并在此基础上逐渐长大.     

Combined Langmuir-Blodgett and sol-gel coatings

Optical properties and in-depth structure of double-layer coatings on glass substrates were investigated. One of the layers was prepared by dip coating either from silica or titania sol, the other layer was made from ca. 130 nm Stöber silica particles by the Langmuir-Blodgett (LB) technique. Two different types of combined coatings were prepared: (1) nanoparticulate LB films coated with sol-gel (SG) films and (2) nanoparticulate LB films drawn onto SG films.Scanning electron microscopy and optical methods, i.e. UV-vis spectroscopy and scanning angle reflectometry were applied for analyzing the structure and thickness of coatings. These measurements revealed that the precursor sols could not penetrate into the particulate LB film completely in case of coating type (1). For coating type (2) very little overlap between the SG and LB layers was found resulting in significant improvement of light transmittance of combined coatings compared to single SG films.To show some possible advantages of the combination of these techniques additional studies were carried out. Surface morphology of combined coatings (1) was studied by atomic force microscopy. Surfaces with different roughness were developed depending on the thickness of the sol-gel film (titania: ca. 70 nm; silica: ca. 210 nm). The adhesive peel off test revealed improved mechanical stability of combined coatings (2), in comparison to LB films which makes them good candidates for further applications.     

Preparation of properties of SWNT/graphene oxide type flexible transparent conductive films

Single walled carbon nanotube (SWNT)/graphene oxide (GO) hybrid films were prepared by a facile bar coating method on a polyethylene terephthalate substrate using a mixed solution of SWCNTs and GO. An acryl type polymer was employed as a dispersion agent to obtain SWCNT and GO suspension in ethyl alcohol. The SWCNT/GO hybrid films were highly transparent and electrically conductive, showing 80% transmittance and 1.8 x 10(3) ohm/sq surface resistance. The surface resistance of the SWCNT/GO film could be further improved to 750 ohm/sq by hydrazine vapor reduction.     

Electrodeposited silicate films: importance of supporting electrolyte

Silica and hybrid organic-inorganic films, ca. 100-200 nm thick, can be grown on glassy carbon electrodes through reactions initiated by electrogenerated hydroxide or hydronium ions in water under reductive and oxidative conditions, respectively. A variety of different alkoxysilanes (tetramethoxysilane and organoalkoxysilanes) and supporting electrolytes were used to evaluate whether film formation takes place on glassy carbon electrodes. The results of the study indicate that the acid-base properties of the supporting electrolyte are an important factor in determining whether film formation will take place. For cathodic electrodeposition, thin films can be formed using supporting electrolytes that are close to neutral, such as KCl, KNO3, and NaClO4. For anodic electrodeposition, thin films can be formed using supporting electrolytes that are acidic, such as, KH2PO4, HNO3, H2SO4, etc. The acidity/basicity effects of the electrolytes arise in part from the strong dependence of the hydrolysis and condensation rates of the silicon alkoxide precursors on pH.     

正硅酸乙酯为无机组分前驱体的聚碳酸酯耐磨涂层

以正硅酸乙酯(TEOS)作为无机组分的前驱体,甲基三甲氧基硅烷(MTMS)水解聚合产物作为有机组分,通过溶胶-凝胶法在聚碳酸酯(PC)表面形成耐磨涂层。红外光谱分析表明该涂层具有Si—O—Si的交联网络结构。研究了MTMS和TEOS的摩尔比对涂层的光学性能、硬度、附着力和耐磨性能的影响。结果表明,当MTMS和TEOS的摩尔比为2∶1时,涂层的综合性能达到最优,该涂层在经历500次耐磨试验后的雾度为12.69%,而纯PC的雾度增至42.38%。采用SEM和TEM分析了MTMS/TEOS具有优异耐磨性能的原因在于该涂层具有纳米SiO2粒子分散于有机基体的微观结构。     

Hydrophobic properties and color effects of hybrid silica spin-coatings on cellulose matrix

A novel sol–gel derived organic–inorganic hybrid silica sol consisting of organic direct red dye 4BS and inorganic silica (SiO₂) is successfully synthesized by adding coupling agent γ-chloropropyltriethoxysilane (CPTS). Hybrid silica coatings are deposited on cellulose matrix surface via spin-coating approach to introduce effective hydrophobic and color properties. Compared to the dye hybrid silica sol (DHSS), the particle size of CPTS/dye hybrid silica sol (CDHSS) increases from 64.51 to 129.70 nm, while the surface tension reduces from 34.27 × 10⁻³ N m⁻¹ to 31.22 × 10⁻³ N m⁻¹. The hydrostatic pressure of the cellulose matrix coating with CDHSS is 4530.5 Pa, the contact angle is 131.48°, and the wetting time is ~150 min, which attributes to the alkyl chloride aliphatic chain and sharp micro-surface roughness of the hybrid coatings validated directly by AFM and SEM images. The K/S value (5.15) of the cellulose matrix coated with CPTS/dye hybrid silica (CMCCDHS) is 12.44% higher than that of the cellulose matrix coated with dye hybrid silica (CMCDHS), and increased by 30.38% relative to the control coated sample. The maximum absorption wavelengths of the matrixes treated with different processes are the same as the maximum absorption wavelength of the silica sols (510 nm).     

Effect of sol concentration on the structural, morphological, optical and photoluminescence properties of zirconia thin films

ZrO₂ thin films were deposited on quartz substrates from 10 wt.%, 20 wt.% and 40 wt.% solutions of Zirconium-n-butoxide in isopropanol by sol-gel dip-coating technique. Higher concentrated sols of 20 wt.% and 40 wt.% exhibited faster gelation, where as 10 wt.% sol remained stable for two months and films synthesized from this sol remained transparent and continuous even for 12 coatings. Ellipsometric study revealed that refractive index of the films increased with increase in sol concentration which is ascribed to the decrease in porosity. X-ray diffraction study showed that a tailoring of grain size from 7.9 to 39.2 nm is possible with increase in sol concentration. Atomic force microscopy studies showed a change in growth mode from vertical to lateral mode with increase in sol concentration. The film surface revealed positive skewness and high kurtosis values which make them favorable for tribological applications. The average optical transmittance in the visible region is highest (greater than 90%) for the film deposited from 10 wt.% sol. The optical band gap decreased from 5.74 to 5.62 eV with increase in the sol concentration. Photoluminescence (PL) spectra of the films exhibit an increase in the emission intensity with increase in sol concentration which substantiates better crystalline quality of the film deposited from 40 wt.% sol and increase in oxygen vacancies. The “Red shift” of the PL spectra with increase in sol concentration originates from the increase in the grain size with sol concentration which makes it suitable for generation of solid state lighting in light emitting diode.     

Superhydrophobic films on glass surface derived from trimethylsilanized silica gel nanoparticles

The paper deals with the fabrication of sol-gel-derived superhydrophobic films on glass based on the macroscopic silica network with surface modification. The fabricated transparent films were composed of a hybrid -Si(CH(3))(3)-functionalized SiO(2) nanospheres exhibiting the desired micro/nanostructure, water repellency, and antireflection (AR) property. The wavelength selective AR property can be tuned by controlling the physical thickness of the films. Small-angle X-ray scattering (SAXS) studies revealed the existence of SiO(2) nanoparticles of average size ～9.4 nm in the sols. TEM studies showed presence of interconnected SiO(2) NPs of ～10 nm in size. The films were formed with uniformly packed SiO(2) aggregates as observed by FESEM of film surface. FTIR of the films confirmed presence of glasslike Si-O-Si bonding and methyl functionalization. The hydrophobicity of the surface was depended on the thickness of the deposited films. A critical film thickness (>115 nm) was necessary to obtain the air push effect for superhydrophobicity. Trimethylsilyl functionalization of SiO(2) and the surface roughness (rms ≈30 nm as observed by AFM) of the films were also contributed toward the high water contact angle (WCA). The coated glass surface showed WCA value of the droplet as high as 168 ± 3° with 6 μL of water. These superhydrophobic films were found to be stable up to about 230-240 °C as confirmed by TG/DTA studies, and WCA measurements of the films with respect to the heat-treatment temperatures. These high water repellant films can be deposited on relatively large glass surfaces to remove water droplets immediately without any mechanical assistance.     

Transparent anti-stain coatings with good thermal and mechanical properties based on polyimide-silica nanohybrids

In this work, we synthesized polyimide/silica hybrid materials via sol-gel method using a fluorinated poly(amic acid) silane precursor and a variety of perfluorosilane contents. We studied the influence of a hybrid coating film with the following characteristics; hydrophobicity, oleophobicity, optical transparency, and surface hardness of the coating films. The hybrid coatings with the fluorosilane contents up to 10 wt% are optically transparent and present good thermal stability with a degradation temperature of > 500 degrees C as well as a glass transition of > 300 degrees C. Both water contact angle and oil contact angle increase rapidly with introducing small amount of the fluorosilane in the hybrids and reaches the maximum of 115 degrees and 61 degrees, respectively. The hardness of the hybrid coatings increases up to 5H with an increase of the FTES content in the hybrids. These colorless, transparent, and thermally stable hybrid materials could be suitable for applications as anti-stain coatings.     

Control of wall thickness in the formation of ordered mesoporous silica films

Ordered mesoporous silica thin films using block copolymer have drawn an attention for low-k application due to its ordered pore structure. From the respect of dielectric and mechanical properties of the film, there is trade-off between pore size and wall thickness. In this work, factors for increase of wall thickness were investigated. It was found that body-centered cubic structure was maintained irrespective of the concentration of catalytic acid. The catalytic acid thickens the framework wall because counterion reduces the repulsion force between silicic acids. The highly ordered mesoporous silica films were obtained although high concentration of acid was added to the silica sol. However, wormlike micelle exists more with high HCl concentration due to fast gellation rate. And excess water, which has the role similar to the humid atmosphere, also increases the thickness of silica wall. However, large amount of excess water at the micelle interface disrupts organic-inorganic electrostatic interaction. As a conclusion, optimization of HCl concentration in the silica sol and control of humidity during spin coating can simultaneously increase the framework thickness while maintaining the pore periodicity.