利用氟硅烷提高溶胶-凝胶SiO2增透膜的疏水性

 以正硅酸乙酯为前驱体，氨水为催化剂，采用溶胶 凝胶法制备了二氧化硅增透膜；通过自组装技术，用氟硅烷对膜层进行表面修饰，制得了疏水增透膜，克服了常规增透膜亲水的缺点。采用红外光谱、分光光度计、扫描探针显微镜和静滴接触角测量仪等测试手段分析了薄膜的特性。结果表明：疏水增透膜的峰值透光率为99.7％，疏水角为110°；氟硅烷自组装改性不影响二氧化硅增透膜的光学性能。     

PDMS改性环氧树脂/Sm2O3复合涂层的近红外光谱及疏水性研究

以聚二甲基硅氧烷（PDMS）改性环氧树脂（HYSZ）为粘合剂,Sm₂O₃为功能颜料,纳米SiO₂为微纳结构改性剂,制备得到了一种同时具有良好疏水性能和附着力的近红外吸收涂层。系统分析了PDMS和HYSZ质量比、邻苯二甲酸二辛酯(DOP)添加量、总填料添加量、Sm₂O₃和纳米SiO₂质量比对涂层性能的影响。结果表明：PDMS改性可明显降低涂层的表面能,从而使涂层的疏水性得到明显增强。利用DOP强化涂层韧性和微观搭桥作用可增强涂层整体性,从而可明显提高涂层的附着力和近红外吸收性能。涂层的表面粗糙度可随总填料添加量的增加而明显升高,进而可使涂层表现出更优的疏水性能。当涂层中PDMS和HYSZ质量比、DOP添加量、总填料添加量、Sm₂O₃和纳米SiO₂质量比分别为1∶9,20%,50%和5.5∶4.5时,涂层同时具有良好的近红外低反射率（59.1%）、疏水性能（水接触角为137°）及附着力（2级）。     

Fabrication of superhydrophobic coating via a facile and versatile method based on nanoparticle aggregates

Herein, we report a facile and low cost method for the fabrication of superhydrophobic surface via spin coating the mixture of polydimethylsiloxane precursor (PDMS) and silicon dioxide (SiO₂) nanoparticles. The surface hydrophobicity can be well tuned by adjusting the weight percent of PDMS and SiO₂. The water contact angle (WCA) can increase from 106.8 ± 1.2° on PDMS film to 165.2 ± 2.3° on PDMS/SiO₂ coating, companying with a change from adhering to rolling which was observed from tilting angle (TA) characterization. Multi-scale physical structures with SiO₂ nanoparticle aggregates and networks of SiO₂ nanoparticle aggregates are characterized by scanning electron microscopy (SEM) and atomic force microscope (AFM), and they can be observed more clearly from the AFM images treated with software (WSxM). Then the relationship between surface hydrophobicity and structures is further discussed based on Wenzel and Cassie models, indicating that the appearance of networks of nanoparticle aggregates is important in the Cassie state. The superhydrophobic coating can keep the superhydrophobicity at least for one month under environment conditions and readily regenerate after mechanical damage. Additionally, the superhydrophobic coating can be fabricated using other methods including dip coating, spray coating and casting. Thus, a large area of superhydrophobic coatings can be easily fabricated. Therefore the range of possible applications for these facile and versatile methods can be expanded to various actual conditions.     

Preparation of durable hydrophobic cellulose fabric from water glass and mixed organosilanes

Durable superhydrophobic cellulose fabric was prepared from water glass and n-octadecyltriethoxysilane (ODTES) with 3-glycidyloxypropyltrimethoxysilane (GPTMS) as crosslinker by sol-gel method. The result showed that the addition of GPTMS could result in a better fixation of silica coating from water glass on cellulose fabric. The silanization of hydrolyzed ODTES at different temperatures and times was studied and optimized. The results showed that silanization time was more important than temperature in forming durable hydrophobic surface. The durability of superhydrophobicity treatment was analyzed by XPS. As a result, the superhydrophobic cotton treated under the optimal condition still remained hydrophobic properties after 50 washing cycles.     

等离子体结合六甲基二硅胺烷处理提升增透膜抗真空污染性能研究

本文采用溶胶-凝胶法制备了SiO₂增透膜,然后对其进行等离子体结合六甲基二硅胺烷（HMDS）表面改性处理。研究了后处理改性对增透膜表面形貌、微观结构、光学性能及激光损伤性能的影响规律,获得了抗真空有机污染的二氧化硅增透膜。结果表明,增透膜在采用等离子体结合HMDS表面改性处理后,膜层收缩、粗糙度下降、极性羟基等有机基团含量减少;两步后处理改善了增透膜膜层结构和光学性能,显著提高了膜层疏水能力和真空条件下的抗污染性能,并且对溶胶-凝胶二氧化硅增透膜的高损伤阈值属性不产生影响。     

Microstructure and morphology of electrodeposited Ni-P alloys treated by high energy surface mechanical attrition

Fully amorphous Ni-P layer electrodeposited onto a Cu plate was subjected to severe plastic deformation using surface mechanical attrition treatment in a high energy SPEX 8000 shaker mill. Two series of experiments using different milling conditions (series I: 20 6.35-mm balls; series II: 100 1.59-mm balls) were carried out to explore the mechanism of the process and to investigate the structure of the developed coatings. The evolution of the microstructure and mechanical properties of the Ni-P layer after the deformation process was studied by x-ray diffraction, scanning electronmicroscopy and hardness measurements. We demonstrate that the different mechanical treatments controllably influence the mechanical behavior of the Ni-P metallic glass coating. When the vial of the mill is loaded with larger balls, deformation-induced Ni₃P compound particles form in the amorphous matrix resulting in a hard (HV = 17 GPa) but non-uniform coating. In the case of milling with many small balls, the increase in the surface hardness is considerably lower (7 GPa) as a consequence of reduced impact energy.     

(Ti,Al,Si,C)N nanocomposite coatings synthesized by plasma-enhanced magnetron sputtering

Materials’ surface service property could be enhanced by transition metal nitride hard coatings due to their high hardness, wear and high temperature oxidation resistance, but the higher friction coefficient (0.4-0.9) of which aroused terrible abrasion. In this work, quinternary (Ti,Al,Si,C)N hard coating 3-4 μm was synthesized at 300 °C using plasma enhanced magnetron sputtering system. It was found that the coating's columnar crystals structure was restrained obviously with the increase of C content and a non-columnar crystals growth mode was indicated at the C content of 33.5 at.%. Both the XRD and TEM showed that the (Ti,Al,Si,C)N hard coatings had unique nanocomposite structures composed of nanocrystalline and amorphous nc-(Ti,Al)(C,N)/nc-AlN/a-Si₃N₄/a-Si/a-C. However, the coatings were still super hard with the highest hardness of 41 GPa in spite of the carbon incorporation. That a-C could facilitate the graphitization process during the friction process which could improve the coating's tribological performance. Therefore, that nanocomposite (Ti,Al,Si,C)N coatings with higher hardness (>36 GPa) and a lower friction coefficient (<0.2) could be synthesized and enhance the tribological performance and surface properties profoundly.     

单甲基原位改性SiO2疏水减反膜的制备与性能研究

 在碱性条件下通过TEOS和MTES的共水解缩聚反应制备了单甲基原位改性的SiO₂溶胶，并使用提拉法在K9玻璃基片上镀制了疏水减反膜。通过透射电镜（TEM）考察了镀膜溶胶的微结构，分别使用红外光谱（FTIR）分析了薄膜的组分，用原子力显微镜（AFM）观察了薄膜的表面形貌和起伏状况，用紫外可见光谱（UV-vis）考察了薄膜的减反射性能，用接触角仪测量了薄膜对水的接触角。并使用“R-on-1”的方式测量了薄膜在Nd:YAG激光（1 064 nm，1 ns）作用下的损伤阈值。结果表明，通过共水解缩聚反应可以把甲基引入镀膜溶胶簇团中，改善了溶胶簇团的网络结构，使薄膜得到相当好的疏水性能和更好的抗激光损伤性能，同时薄膜能保持较好的减反射性能。     

Tuning the hydrophobicity of ZSM-5 zeolites by surface silanization using alkyltrichlorosilane

ZSM-5 zeolites were modified with alkyltrichlorosilanes of various chain lengths (octyltrichlorosilane, decyltrichlorosilane, dodecyltrichlorosilane and hexadecyltrichlorosilane) and characterized by Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), Thermal gravimetric analysis (TGA) and contact angle measurements (CA). The results showed that a closely packed and hydrophobic layer was presented at the particles surface and the surface wetting property varied from hydrophilic to hydrophobic, even to superhydrophobic. It was interesting to notice that the hydrophobic properties of modified ZSM-5 particles could be tuned by varying the chain length of chlorosilane and changing the pretreatment temperature before silanization. With increasing the alkyl chain length of trichlorosilane, the hydrophobicity increased. However, with an increase in the pretreatment temperature, the hydrophobicity decreased. Moreover, the relationship between the wetting properties and thermal stability was also investigated, the results showed that the modified ZSM-5 particles possessed good hydrophobicity at a temperature below 250 °C in air. These modified ZSM-5 particles may be utilized for many potential applications, such as membrane fillers, selective adsorbents, catalysts, chromatographic supports and so on.     

Influence of substrate hardness transition on built-up of nanostructured WC-12Co by cold spraying

The ability of cold spray process to retain the feedstock microstructure into coating makes it possible to deposit nanostructured WC-Co coatings. In the present study, the deposition behavior of nanostructured WC-12Co coating was examined through the surface morphology and cross-sectional structure of the deposited single WC-12Co particle impacting on the substrates with different hardness using a nanostructured WC-12Co powder. Substrates included stainless steel, nickel-based self-fluxing alloy coatings with different hardness. It was observed from the top surface and cross-section of individual WC-12Co particles that the penetration leading to particle deposition depends on substrate hardness. When the substrate surface is covered by WC-12Co particles, the hardness of the newly formed substrate, i.e. the coating, increases greatly. The significant increase of the surface hardness leads to the rebounding off of impacting particles and erosion of the deposited particles, which prohibits effective built-up of coating. However, it was found that with spray jet fixed, a deposit with a thickness up to over 700 μm can be built-up. A model involving in substrate hardness transition during deposition is proposed to explain such phenomenon, which can be employed to optimize the conditions to build up a uniform nanostructured WC-12Co coating.     

Optically transparent, superhydrophobic methyltrimethoxysilane based silica coatings without silylating reagent

The superhydrophobic surfaces have drawn lot of interest, in both academic and industries because of optically transparent, adherent and self-cleaning behavior. Surface chemical composition and morphology plays an important role in determining the superhydrophobic nature of coating surface. Such concert of non-wettability can be achieved, using surface modifying reagents or co-precursor method in sol-gel process. Attempts have been made to increase the hydrophobicity and optical transparency of methyltrimethoxysilane (MTMS) based silica coatings using polymethylmethacrylate (PMMA) instead of formal routes like surface modification using silylating reagents. The optically transparent, superhydrophobic uniform coatings were obtained by simple dip coating method. The molar ratio of MTMS:MeOH:H₂O was kept constant at 1:5.63:1.58, respectively with 0.5 M NH₄F as a catalyst and the weight percent of PMMA varied from 1 to 8. The hydrophobicity of silica coatings was analyzed by FTIR and contact angle measurements. These substrates exhibited 91% optical transmittance as compared to glass and water drop contact angle as high as 171 ± 1°. The effect of humidity on hydrophobic nature of coating has been studied by exposing these films at relative humidity of 90% at constant temperature of 30 °C for a period of 45 days. The micro-structural studies carried out by transmission electron microscopy (TEM).     

Anti-graffiti nanocomposite materials for surface protection of a very porous stone

The preservation of stone substrates from defacement induced by graffiti represents a very challenging task, which can be faced by applying suitable protective agents on the surface. Although different anti-graffiti materials have been developed, it is often found that their effectiveness is unsatisfactory, most of all when applied on very porous stones, e.g. Lecce stone. The aim of this work was to study the anti-graffiti behaviour of new nanocomposite materials obtained by dispersing montmorillonite nanoparticles (layered aluminosilicates with a high-aspect ratio) into a fluorinated polymer matrix (a fluorinated polyurethane based on perfluoropolyether blocks). Polymeric structure was modified by inducing a cross-linking process, in order to produce a durable anti-graffiti coating with enhanced barrier properties. Several composites were prepared using a naturally occurring and an organically modified montmorillonite clay (1, 3, and 5 % w/w concentrations). Materials were applied on Lecce stone specimens, and then their treated surfaces were soiled by a black ink permanent marker or by a black acrylic spray paint. Several repeated staining/cleaning cycles were performed in order to evaluate anti-graffiti effectiveness. Colorimetric measurements were selected to assess the anti-graffiti performance. It was found that the presence of 3 % w/w organically modified montmorillonite in the polymer coating is enough to induce a durable anti-graffiti effect when the stone surface is stained by acrylic paint. Less promising results are obtained when staining by permanent marker is considered as all the investigated treatments afford a reasonable protection from ink only for the first staining/cleaning cycle.     

ZnO micro-nano composite hydrophobic film prepared bythree-step method

<正>The hydrophobicity of the lotus leaf is mainly due to its surface micro—nano composite structure.In order to mimic the lotus structure,ZnO micro-nano composite hydrophobic films were prepared via the three-step method.On thin buffer films of SiO₂,which were first fabricated on glass substrates by the sol—gel dip-coating method,a ZnO seed layer was deposited via RF magnetron sputtering.Then two different ZnO films,micro-nano and micro-only flowerlike structures,were grown by the hydrothermal method.The prepared films have different hydrophobic properties after surface modification.The structures of the obtained ZnO films were characterized using x-ray diffraction and field-emission scanning electron microscopy.A conclusion that a micro-nano composite structure is more beneficial to hydrophobicity than a micro-only structure was obtained through research into the effect of structure on hydrophobic properties.     

Study on the hydrophobic surfaces prepared by two-step sol-gel process

In this study, the two-step sol-gel process was used to prepare hydrophobic coating films on the glass substrates. The first step was to add hydrogen chloride into TEOS (tetraethoxysilane) solution, and then the second step was to add ammonia into the above reacted solution. We adopted different amount of hydrogen chloride and ammonia to control the sol-gel reaction and observed the change of the viscosity, gelatin period of the solution and contact angles of the coating films. By this method, we created a surface with roughness and then the hydroxyl groups were terminated by adding trimethylchlorosilane (TMCS) to produce a hydrophobic coating layer. The amount of the acid, base and water added in the solution influenced the reaction rate and resulted in the aggregation and condensation of the particles to form rough surfaces. Consequently, the rough surfaces made by aggregation and condensation of the large particles, which were modified by TMCS resulted in higher contact angles (>140°). In this study, a surface with contact angle 150° was obtained.     

Mechanical and microwave absorbing properties of carbon-filled polyurethane

Polyurethane (PU) matrix composites were prepared with various carbon fillers at different filler contents in order to investigate their structure, mechanical and microwave absorbing properties. As fillers, flat carbon microparticles, carbon microfibers and multiwalled carbon nanotubes (MWNT) were used. The microstructure of the composite was examined by scanning electron microscopy and transmission electron microscopy. Mechanical properties, namely universal hardness, plastic hardness, elastic modulus and creep were assessed by means of depth sensing indentation test. Mechanical properties of PU composite filled with different fillers were investigated and the composite always exhibited higher hardness, elastic modulus and creep resistance than un-filled PU. Influence of filler shape, content and dispersion was also investigated.     

Different spray processes for different Al2O3 coating properties

Among the different coating technologies, a thermal spray has a leading position because of its versatility: an extremely wide variety of materials can be deposited to protect back materials from wear, corrosion, thermal flux, etc. For example, atmospheric plasma spray is a rather well-established process but some other ones, such as flame technology, can also be used with lower economical impact. After a respective optimization of the processing parameters, both plasma and wire flame thermal processes were tested to form Al₂O₃ coatings. For each process, in-flight particle conditions, coating cross-section micro-structures and coating properties were successively determined. The experimental parameters were correlated to in-flight particle characteristics and to coating micro-structure and compared to resulting coating features. The evolution of particle velocity and temperature showed well-marked trends and the mean values were dependent on the spray process. The results emphasized the difference of spray system in terms of kinetic and thermal transfers to the particles. Then, the differences observed on in-flight particle characteristics can be used to explain the differences observed in coating properties, such as porosity content and hardness.     

Fabrication of high-performance nickel/graphene oxide composite coatings using ultrasonic-assisted electrodeposition

Ultrasonic-assisted electrodeposition was used to fabricate the nickel/graphene oxide composite coatings with high hardness, low friction coefficient, and high wear resistance. In the present study, the effects of ultrasonic power and concentration of graphene oxide on the mechanical and tribological properties of the electrodeposited nickel/graphene oxide composite coatings were systematically studied. X-ray diffraction (XRD) analyses showed that the crystallite size of the nickel decreased with an increase of ultrasonic power (0–50 W, 40 KHz, square wave) and concentration of graphene oxide (0.1–0.4 g/L). Morphologies of the surface and cross-section of the composite coatings observed by Scanning Electron Microscopy (SEM) confirmed the existence of graphene oxide particles in the nickel matrix. The results from microhardness measurement demonstrated that the hardness was increased by 1.8 times using 50 W ultrasonic-assisted electrodeposition with the fixed concentration of graphene oxide (0.1 g/L), compared to the pure nickel coating. The hardness was increased by 4.4 times for the 0.4 g/L graphene oxide with the optimized ultrasonic power of 50 W in comparison to the pure nickel coating. Meanwhile, the friction coefficient decreased gradually with an increase in ultrasonic power and concentration of graphene oxide, respectively, where the effect of the concentration of graphene oxide played a more important role.     

Sol-gel preparation of a silica antireflective coating with enhanced hydrophobicity and optical stability in vacuum

A new silica antireflective coating with improved hydrophobicity and optical stability in a vacuum is obtained by a two-step route. Firstly, silica sols are prepared with a sol-gel process, in which tetraethyl orthosilicate is utilized as a precursor. And by introduction of fluorine containing glycol into the sols,the porosity of silica particles and surface polarity of the coatings are decreased. Afterward, coatings are constructed with low surface roughness by modification of PMBA-PMMA. The coatings retain transmission of up to 99.6%, and laser damage threshold of about 50 J/cm2at a wavelength of 532 nm(1-on-1, 10 ns).     

A sol-gel based surface treatment for preparation of water repellent antistatic textiles

In this paper a surface treatment is described for preparation of hydrophobic sol-gel coatings that simultaneously offer antistatic properties for an appropriate finishing of textiles and refinement of polymer foils. Sol-gel based formulations are modified with both hydrophilic and hydrophobic components simultaneously. Hydrophobic components are, e.g., alkoxysilanes modified with alkyl chains while the hydrophilic ones are amino-functionalized alkoxysilanes. The basic idea is that due to an enrichment of hydrophobic groups at the solid/air interface the surface of the as prepared coatings will be hydrophobic while the deeper region will be more hydrophilic. Textiles finished with these coatings exhibit sufficient water repellence and simultaneously absorb sufficient amounts of humidity in the deeper areas of the coating guaranteeing antistatic properties. This concept offers interesting approaches for the preparation of multifunctional surface coatings not only focussing on combining water repellence with antistatic properties for textile materials.     

Influence of the viscosity and the substrate on the surface hydrophobicity of polyurethane coatings

Tailor-made polyurethane (PU) dispersions were synthesized as coatings for paperboard for dry food packaging. For this purpose a low moisture-vapor transmission rate and a high surface hydrophobicity are desirable characteristics, which are both met by PU. However, it was found that the surface hydrophobicity of water-borne PU dispersions depends strongly on the viscosity of the dispersion. This dependency was studied by static contact angle measurements (SCA) as well as a novel technique using digital pulsed-force mode atomic force microscopy (DPFM-AFM). Comparison of the results validated that DPFM-AFM is a valuable tool to characterize the surface hydrophilicity. Both techniques confirmed that the surface hydrophobicity varies with the viscosity and that an optimum viscosity for the PU coating with a maximum surface hydrophobicity can consequently be determined. It was found that both lower as well as higher viscosities led to a less hydrophobic surface.