纳米SiO_2/改性丙烯酸树脂低表面能防污涂料

低表面能防污涂料是船舶涂料的一个重要分支。利用有机硅改性的丙烯酸树脂作为成膜物质,纳米SiO2为填料,制备了低表面能纳米复合防污涂料。考察了有机硅单体对改性丙烯酸树脂性能的影响,发现随着有机硅含量的增加,改性后的树脂粘度减小,水接触角增加。研究了氟硅烷改性纳米SiO2含量对涂层形貌和水接触角的影响。结果表明,添加少量的氟硅烷处理的纳米SiO2(1%和3%)可显著增大涂层的水接触角,提高涂层的防污性能。添加纳米SiO2浆的涂层的水接触角要高于添加接枝氟硅烷纳米SiO2的涂层,而后者要高于添加未接枝氟硅烷纳米SiO2的涂层。当纳米SiO2的添加量在1%和3%时,涂层的水接触角分别达到101.8°和103°。采用纳米浓缩浆工艺分散后的纳米SiO2可以使涂层的表面形成微米-纳米的特征形貌,从而实现防污的目的。     

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.     

Highly transparent, flexible, and thermally stable superhydrophobic ORMOSIL aerogel thin films

We report preparation of highly transparent, flexible, and thermally stable superhydrophobic organically modified silica (ORMOSIL) aerogel thin films from colloidal dispersions at ambient conditions. The prepared dispersions are suitable for large area processing with ease of coating and being directly applicable without requiring any pre- or post-treatment on a variety of surfaces including glass, wood, and plastics. ORMOSIL films exhibit and retain superhydrophobic behavior up to 500 °C and even on bent flexible substrates. The surface of the films can be converted from superhydrophobic (contact angle of 179.9°) to superhydrophilic (contact angle of <5°) by calcination at high temperatures. The wettability of the coatings can be changed by tuning the calcination temperature and duration. The prepared films also exhibit low refractive index and high porosity making them suitable as multifunctional coatings for many application fields including solar cells, flexible electronics, and lab on papers.     

Slip‐rolling resistance of ta‐C and a‐C coatings up to 3,000 MPa of maximum Hertzian contact pressure

The slip‐rolling resistances of hard and stiff thin films under high Hertzian contact pressures can be improved by optimizing the “coating/substrate systems”. It is known from former investigations that the so‐called “egg‐shell” effect is no general hindrance for high slip‐rolling resistance of thin hard coatings. The coating stability depends more on specific deposition process and coating/substrate interface design. In this article it is experimentally shown, that pure amorphous carbon thin films with hardness between 15 and 63 GPa can be slip‐rolling resistant several million load cycles under a maximum Hertzian contact pressures of up to 3.0 GPa. Whereas all coatings were stable up to 10 million load cycles in paraffin oil at room temperature, reduced coating lifetime was found in SAE 0W‐30 engine oil at 120°C. It was shown how the coating hardness and the initial coating surface roughness influence the running‐in process and coating lifetime. No clear correlation between coating hardness and coating lifetime could be observed, but friction coefficients seem to be reduced with higher coating hardness. Very low friction down to ?0.03 in unmodified engine oils was found for the hardest ta‐C film.     

轮胎模具DLC涂层的制备及性能

为探究高性能轮胎模具类金刚石(DLC)涂层的应用前景,提高模具花纹块内表面的疏水性及耐磨减摩性,采用等离子体增强化学气相沉积法在35钢基体上制备DLC涂层,并对所制备的DLC涂层的表面形貌、粗糙度、疏水性、表面元素组成、纳米硬度、摩擦系数等关键指标进行了测定.结果表明:DLC涂层具有优良的表面完整性,水接触角可达19.62°,乙醇接触角达20.37°,纳米硬度可达19.62 GPa,摩擦系数低至0.405 8,DLC涂层有望替代Teflon涂层,用于高性能轮胎模具.     

C/ Ti 原子比对反应火焰喷涂TiC/ Fe 复合涂层组织结构和硬度的影响

以TiFe 粉和碳的前驱体(石油沥青) 为原料, 用前驱体碳化复合技术制备了Ti-Fe-C 反应喷涂复合粉末, 并采用普通火焰喷涂技术成功制备了TiC/ Fe 陶瓷金属复合涂层。研究了不同C/ Ti 原子比对反应火焰喷涂TiC/ Fe 复合涂层相组成、显微结构和硬度的影响。结果表明, 前驱体碳化复合技术制备的Ti-Fe-C 系反应喷涂复合粉末中C/ Ti 原子比是影响涂层相组成、显微结构和硬度的关键因素。C/ Ti 原子比不同, 涂层的相组成和硬度不同; 随着C/ Ti 原子比增大, 涂层中TiC 团聚富集区增大, 涂层的孔隙率也随之增大。      

Fabrication of nano-structured HA/CNT coatings on Ti6Al4V by electrophoretic deposition for biomedical applications

In order to improve the bone bioactivity and osteointegration of metallic implants, hydroxyapatite (HA) is often coated on their surface so that a real bond with the surrounding bone tissue can be formed. In the present study, cathodic electrophoretic deposition (EPD) has been attempted for depositing nanostructured HA coatings on titanium alloy Ti6Al4V followed by sintering at 800 degrees C. Nano-sized HA powder was used in the EPD process to produce dense coatings. Moreover, multiwalled carbon nanotubes (CNTs) were also used to reinforce the HA coating for enhancing its mechanical strength. The surface morphology, compositions and microstructure of the monolithic coating of HA and nanocomposite coatings of HA with different CNT contents (4 to 25%) on Ti6Al4V were investigated by scanning-electron microscopy, energy-dispersive X-ray spectroscopy and Xray diffractometry, respectively. Electrochemical corrosion behavior of the various coatings in Hanks' solution at 37 degrees C was investigated by means of open-circuit potential measurement and cyclic potentiodynamic polarization tests. Surface hardness, adhesion strength and bone bioactivity of the coatings were also studied. The HA and HA/CNT coatings had a thickness of about 10 microm, with corrosion resistance higher than that of the substrate and adhesion strength higher than that of plasma sprayed HA coating. The properties of the composite coatings were optimized by varying the CNT contents. The enhanced properties could be attributed to the use of nano-sized HA particles and CNTs. Compared with the monolithic HA coating, the CNT-reinforced HA coating markedly increased the coating hardness without deteriorating the corrosion resistance or adhesion strength.     

Investigations into sol-gel silica and silica hybrid coatings for dielectromagnetic soft magnetic composite applications

A series of inorganic and organic–inorganic hybrid silica coatings were synthesised by a sol-gel process from tetraethoxysilane (TEOS) and methyltrimethoxysilane (MTMS) precursors, and used to investigate their effectiveness as insulation materials in dielectromagnetic soft magnetic composites. The coating materials and coated iron powders were analysed by FTIR, electron and atomic force microscopy. Results showed that introduction of the organic phase imparted desirable hydrophobicity and flexibility to the coating, whilst still providing effective electrical insulation at temperatures up to 500 °C. The hybrid coatings covered the iron particle surface very effectively and formed continuous coatings that could remain intact even after compaction at pressures up to 900 MPa, depending on the coating amount. Initial magnetic characterisations are also encouraging. As a result, such hybrid-coated iron powders can be considered suitable candidates as heat-treatable high-performance dielectromagnetics.     

Amorphous alumina coatings: processing, structure and remarkable barrier properties

Amorphous aluminium oxide coatings were processed by metalorganic chemical vapour deposition (MOCVD); their structural characteristics were determined as a function of the processing conditions, the process was modelled considering appropriate chemical kinetic schemes, and the properties of the obtained material were investigated and were correlated with the nanostructure of the coatings. With increasing processing temperature in the range 350 degrees C-700 degrees C, subatmospheric MOCVD of alumina from aluminium tri-isopropoxide (ATI) sequentially yields partially hydroxylated amorphous aluminium oxides, amorphous Al2O3 (415 degrees C-650 degrees C) and nanostructured gamma-Al2O3 films. A numerical model for the process allowed reproducing the non uniformity of deposition rate along the substrate zone due to the depletion of ATI. The hardness of the coatings prepared at 350 degrees C, 480 degrees C and 700 degrees C is 6 GPa, 11 GPa and 1 GPa, respectively. Scratch tests on films grown on TA6V titanium alloy reveal adhesive and cohesive failures for the amorphous and nanocrystalline ones, respectively. Alumina coating processed at 480 degrees C on TA6V yielded zero weight gain after oxidation at 600 degrees C in lab air. The surface of such low temperature processed amorphous films is hydrophobic (water contact angle 106 degrees), while the high temperature processed nanocrystalline films are hydrophilic (48 degrees at a deposition temperature of 700 degrees C). It is concluded that amorphous Al2O3 coatings can be used as oxidation and corrosion barriers at ambient or moderate temperature. Nanostructured with Pt or Ag nanoparticles, they can also provide anti-fouling or catalytic surfaces.     

B_4C加入量对氩弧熔覆Ni-Cr-W合金涂层组织及耐蚀性能的影响

为改善Ni基合金涂层的组织及耐蚀性,采用氩弧熔覆技术在40Cr钢基体表面制备Ni-Cr-W基/B_4C复合涂层,主要研究了B_4C加入量对涂层显微组织、显微硬度以及耐蚀性能的影响。结果表明:合金涂层显微组织由平面晶、柱状晶和树枝状晶等组成;当B_4C含量为5%时,涂层熔覆层的组织明显发生细化;当B_4C含量超过5%时,熔覆涂层表面出现气孔和裂纹等缺陷,内部夹杂增多,涂层质量下降;B_4C的加入提高了合金涂层的硬度,当B_4C含量达到5%时表面硬度较高,达到1 027.4 HV_(0.5N),B_4C含量继续升高,硬度变化不大;B_4C的加入降低了熔覆层耐蚀性,当B_4C含量为5%时耐蚀性相比未加B_4C时的下降不多,耐蚀性较好。     

Characterization and bioactive properties of zirconia based polymeric hybrid for orthopedic applications

Zirconia is a transition metal oxide with current applications to orthopedic implants. It has been shown to up-regulate specific genes involved in bio-integration and injury repair. This study examines the effects of zirconia and polydimethylsiloxane (PDMS) hybrids on the proliferation and viability of human primary osteoblast and fibroblast cells. In this study, zirconia–PDMS hybrid coatings were synthesized using a modified sol gel process. The hybrid material was characterized using optical microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, and contact angle analysis. This study demonstrates that Zr–PMDS surface materials display hydrophobic surface properties coupled with a preferential deposition of polymer near the surface. Primary osteoblast and fibroblast proliferation and viability on hybrid coated surfaces were evaluated via a rapid screening methodology using WST-1 and calcein AM assays. The cells were seed at 5,000 cells per well in 96-well plates coated with various composition of Zr–PDMS hybrids. The results showed increasing cell proliferation with increasing zirconia concentration, which peaked at 90 % v/v zirconia. Proliferation of osteoblasts and fibroblasts displayed similar trends on the hybrid material, although osteoblasts displayed a bi-phasic dose response by the calcein AM assay. The results of this current study show that Zr–PDMS may be used to influence tissue–implant integration, supporting the use of the hybrid as a promising coating for orthopedic trauma implants.     

Effect of amino-modified silica nanoparticles on the corrosion protection properties of epoxy resin-silica hybrid materials

In this paper, a series of organic-inorganic hybrid materials consisting of epoxy resin frameworks and dispersed nanoparticles of amino-modified silica (AMS) were successfully prepared. First of all, the AMS nanoparticles were synthesized by carrying out the conventional acid-catalyzed sol-gel reactions of tetraethyl orthosilicate (TEOS) in the presence of (3-aminopropyl)-trimethoxysilane (APTES) molecules. The as-prepared AMS nanoparticles were then characterized by FTIR, 13C-NMR and 29Si-NMR spectroscopy. Subsequently, a series of hybrid materials were prepared by performing in-situ thermal ring-opening polymerization reactions of epoxy resin in the presence of as-prepared AMS nanoparticles and raw silica (RS) particles. The as-prepared epoxy-silica hybrid materials with AMS nanoparticles were found to show better dispersion capability than that of RS particles existed in hybrid materials based on the morphological observation of transmission electron microscopy (TEM). The hybrid materials containing AMS nanoparticles in the form of coating on cold-rolled steel (CRS) were found to be much superior in corrosion protection over those of hybrid materials with RS particles when tested by a series of electrochemical measurements of potentiodynamic and impedance spectroscopy in 5 wt% aqueous NaCI electrolyte. The increase of corrosion protection effect of hybrid coatings may have probably resulted from the enhancement of the adhesion strength of the hybrid coatings on CRS coupons, which may be attributed to the formation of Fe-O-Si covalent bond at the interface of coating/CRS system based on the FTIR-RAS (reflection absorption spectroscopy) studies. The better dispersion capability of AMS nanoparticles in hybrid materials were found to lead more effectively enhanced molecular barrier property, mechanical strength, surface hydrophobicity and optical clarity as compared to that of RS particles, in the form of coating and membrane, based on the measurements of molecular permeability analysis, dynamic mechanical analysis, contact angle measurements and ultraviolet-visible transmission spectra, respectively.     

Effect of surface fluorination of TiO2 particles on photocatalitytic activity of a hybrid multilayer coating obtained by sol-gel method

A multilayer photoactive coating containing surface fluorinated TiO(2) nanoparticles and hybrid matrices by sol gel approach based on renewable chitosan was applied on poly(lactic acid) (PLA) film by a step wise spin-coating method. The upper photoactive layer contains nano-sized functionalized TiO(2) particles dispersed in a siloxane based matrix. For the purpose of improving TiO(2) dispersion at the air interface coating surface, TiO(2) nanoparticles were modified by silane coupling agent 1H,1H,2H,2H-perfluorooctyltriethoxysilane (FTS) with fluoro-organic side chains. An additional hybrid material consisting of chitosan (CS) cross-linked with 3-glycidyloxypropyl trimethoxy silane (GOTMS) was applied as interlayer between the PLA substrate and the upper photoactive coating to increase the adhesion and reciprocal affinity. The multilayer TiO(2)/CS-GOTMS coatings on PLA films showed a thickness of ~4-6 μm and resulted highly transparent. Their structure was exhaustively characterized by SEM, optical microscope, UV-vis spectroscopy and contact angle measurements. The photocatalytic activity of the multilayer coatings were investigated using methyl orange (MeO) as a target pollutant; the results showed that PLA films coated with surface fluorinated particles exhibit higher activity than films with neat particles, because of a better dispersion of TiO(2) particles. The mechanical properties of PLA and films coated with fluorinated particles, irradiated by UV light were also investigated; the results showed that the degradation of PLA substrate was markedly suppressed because of the UV adsorptive action of the multilayer coating.     

SiC/Al复合材料超疏水表面的制备

采用化学刻蚀法在SiC/Al复合材料表面构筑微纳结构,通过SEM和表面接触角测量仪分析刻蚀表面的微观形貌特征及润湿特性,并探讨了其与刻蚀时间之间的关系;借助热震试验评价SiC/Al复合材料超疏水表面的温度骤变耐受特性。结果表明:弥散分布的微米级SiC颗粒的存在使得刻蚀后的SiC/Al复合材料表面易形成由微米级粒状结构和纳米级凹坑结构复合而成的微观结构;氟硅烷修饰后的蚀刻表面的接触角最高达到166.8°,滚动角最低为3°,具有很好的超疏水特性;SiC/Al基超疏水表面具有较好的耐受温度骤变特性。     

Graphene-based nanostructured hybrid materials for conductive and superhydrophobic functional coatings

A bi-functional, conductive and superhydrophobic, graphene-based nanostructured hybrid material was fabricated. In order to construct the bi-functional hybrid material, carbon nanotubes (CNT) and polyhedral oligomeric silsesquioxane (POSS) were introduced. The water contact angle (WCA) of the graphene/POSS/CNT coating reached about 155 degrees and its conductivity was about 1-10 S/cm. Such graphene-based nanostructured hybrid materials could have great potential as an antistatic and self-cleaning coating in various applications.     

Multi-functional hybrid coatings containing silica nanoparticles and anti-corrosive acrylate monomer for scratch and corrosion resistance

Multi-functional hybrid coatings having both anti-corrosion and scratch resistance were prepared from modified silica nanoparticles and functional acrylates. To improve the dispersion properties of silica nanoparticles in the organic/inorganic hybrid coatings, the surface of the nanoparticles was modified with γ-methacryloxypropyltrimethoxysilane. The coating solution could be prepared by mixing modified silica nanoparticles, tetrasiloxane acrylate, di-acrylate monomer containing an anti-corrosion functional group, acrylic acid, and an initiator in a solvent. The mixture was then dip-coated on iron substrates and finally polymerized by ultraviolet (UV) irradiation. Corrosion and scratch resistance of the coated iron was evaluated by electrochemical impedance spectroscopy (EIS) and a pencil hardness test, respectively. From the EIS results, the coatings with tetrasiloxane acrylate and di-acrylate did not show any decrease in impedance or phase angle, even after 50 days' exposure to 0.1 M NaCl electrolyte, whereas the conventional acrylate coatings started to fail after only 24 h. A hybrid coating containing the amine-quinone functional group exhibited excellent corrosion protection properties with 4-5H pencil hardness.     

Synthesis of organic-inorganic hybrid sols with nano silica particles and organoalkoxysilanes for transparent and high-thermal-resistance coating films using sol-gel reaction

Organic-inorganic hybrid sols were synthesized from nano silica particles dispersed in water and from organoalkoxysilanes, using the sol-gel reaction. This work focuses on the effects of the three multifunctional organoalkoxysilanes dimethyldimethoxysilane (DMDMS), methyltrimethoxysilane (MTMS), and tetramethoxysilane (TMOS) to form a transparent and high-thermal-resistance coating film. The stability of the hybrid sol was evaluated as a function of the reaction time for 10 d through the variation of the viscosity. The viscosity of the silica/DMDMS and silica/MTMS sol was slightly increased for 10 d. The multifunctional organoalkoxysilanes formed dense silica networks through hydrolysis and condensation reaction, which enhanced the thermal resistance of the coating films. No thermal degradation of the silica/DMDMS sample occurred up to 600 degrees C, and none of the silica/MTMS and silica/TMOS samples occurred either up to 700 degrees C. The organic-inorganic hybrid sols were coated on the glass substrate using a spin-coating procedure. The organic-inorganic hybrid sols formed flat coating films without cracks. The transmittance of the hybrid sol coating films using MTMS and DMDMS was shown to be over 90%. The transmittance of the silica/TMOS sol coating film reacted for 10 d abruptly decreased due to faster gelation. The silica/DMDMS and silica/MTMS hybrid sols formed smooth coating films while the surface roughness of the silica/TMOS coating film markedly increased when the hybrid sol reacted for 10 d. The increase of the surface roughness of the silica/TMOS coating film can be attributed to the degradation of the stability of the hybrid sol and to the loss of transmittance of the coating film. It was confirmed in this study that the use of organic-inorganic hybrid sol can yield transparent and high-thermal-resistance coating films.     

微米SiO_2粒子对硅丙树脂防污涂料性能的影响

在涂料中添加微纳米粒子可改善其性能,目前有关微米粒子对涂料防污、防腐蚀性能影响的报道较少。用自制的硅丙树脂作为基料,通过添加微米SiO_2粒子制得了防污涂料。利用静态接触角、硬度、黏附力和电化学阻抗测试探究了微米SiO_2粒子对涂层性能的影响。结果表明:微米SiO_2可稳定硅丙树脂涂层的静态海水接触角和力学性能,并提高涂层的耐海水腐蚀性能,且当微米SiO_2粒子含量为16.7%(质量分数)时,涂层的静态海水接触角和耐蚀性能最好。     

MTES含量对Al2O3/有机硅/SiO2杂化涂层性能的影响

以正硅酸乙酯（TEOS）、甲基三乙氧基硅烷（MTES）、二苯基二甲氧基硅烷（DDS）和仲丁醇铝（ASB）为原料,制备Al₂O₃/有机硅/SiO₂杂化涂层,测试了涂层的物理性能、耐热和电化学阻抗,研究了MTES含量对其性能的影响。结果表明:随着MTES含量的增加,硬度和耐冲击性先增大后减小;柔韧性和附着力良好且变化不大;当n（ASB）:n（TEOS）:rn（MTES）:n（DDS）=1:3:9:1时,Al₂O₃/有机硅/SiO₂杂化涂层的耐热和耐蚀性能最佳。     

Hardness recovery of ceramic coated aluminium matrix composites using thermal-shock resistant sol-gel silica coatings

Sol-gel silica coatings increase wear and corrosion resistance of aluminium matrix composites, but a heat treatment stage at temperatures as high as 500 °C is usually required to consolidate the ceramic coating. Under these thermal conditions, sol-gel ceramic coatings tend to crack and the aluminium matrix hardness strongly reduces. Present paper describes how the combination of a certain sol-gel procedure accompanied with quenching treatment in silicone oil allows recovering most of the hardness of the substrate, while keeping undamaged the sol-gel silica coating deposited.