Sol-gel coatings for chemical protection of stainless steel

Sol-gel thin coatings of ZrO₂, SiO₂, 70SiO₂-30TiO₂ and 88SiO₂-12Al₂O₃ compositions (mole %) have been prepared from sonocatalyzed sols and deposited by dip-coating technique on 316L stainless steel foils. The influence of the coatings on the chemical corrosion of the substrate has been measured through potentiodynamic polarization curves in aqueous 15% H₂SO₄ solution between 25 and 50°C. The values of the corrosion potential, polarization resistance and corrosion rate have been determined. Analysis of the data combined with scanning electron microscopy studies indicate that the films act as a geometric blocking against exposure to the corrosive media and increase the lifetime of the substrate up to a factor 8.5.     

Bioactive and Protective Sol-Gel Coatings on Metals for Orthopaedic Prostheses

The aim of this work has been the preparation and evaluation of sol-gel coatings for clinical applications. Research was focussed in the development of highly corrosion resistant and/or bioactive sol-gel coatings onto AISI 316L stainless steel. Hybrid SiO₂ sol-gel coatings inhibited corrosion and Fe diffusion, although no signal of bioactivity was detected. The inclusion of Ca- and P-alcoxides in the sol composition did not promote bioactivity. Bioactive coatings were obtained from suspensions prepared by adding glass (CaO·SiO₂·P₂O₅) particles to an hybrid organic-inorganic SiO₂ sol. The dissolution of glass particles promoted in vitro induction of apatite along with a slight reduction in the corrosion resistance of coated pieces. By combining an inner SiO₂ hybrid film acting as barrier against corrosion with an outer coating containing bioactive glass particles, a significant improvement in the electrochemical behaviour was observed. This double-layered coating showed in vitro signals of bioactivity, and preliminary in vivo tests gave promising results.     

Silica-Zirconia Sol–Gel Coatings Obtained by Different Synthesis Routes

Homogeneous xSiO₂-(1−x)ZrO₂ coatings have been prepared onto glass-slides, monocrystalline Si and stainless steel (AISI 304) using sols prepared via acid and basic catalysis. Zirconium tetrabutoxide (TBOZr), zirconium n-propoxide (TPZ), tetraethoxysilane (TEOS) and methyltriethoxysilane (MTES) were used as precursors of zirconia and silica, respectively. The different parameters involved in the synthesis procedure, as molar ratios H₂O/alkoxides, NaOH/alkoxides, and sintering temperature have been analysed, correlating the stability and rheological properties of the sols. The evolution and structure of the sols and coatings have been studied by FTIR. Coatings have been prepared by dipping from acid and basic sols. Electrophoretic Deposition (EPD) technique has also been used to prepare coatings onto stainless steel from basic particulate sols in order to increase the critical thickness. A maximum thickness of 0.5 μ m was reached by both dipping and EPD process for 75SiO₂: 25 ZrO₂ composition. The critical thickness decreases with ZrO₂ amount depending strongly of the drying conditions. Si–O–Zr bonds have been identified by FTIR, indicating the existence of mixed network Si–O–Zr in the coatings obtained by the different routes. Crystallisation of ZrO₂(t) was only observed at high sintering temperature (900^∘C) by FTIR and confirmed by DRX.     

Structural and electrochemical characterization of sputter-deposited nitrided NiCr alloys

Nickel-based coatings are potential candidates for the protection of electrochemical dissolution of steel surfaces. Such coatings, elaborated by magnetron sputtering in a nitrogen atmosphere, offer good corrosion protection, good adherence as well as stability for metallic structures. NiCr alloys with almost constant composition have been deposited with different nitrogen contents on stainless steel and carbon steel surfaces. The coating uniformity, homogeneity, composition and crystallinity have been studied by scanning electron microscopy, energy-dispersive X-ray spectrometry, atomic force microscopy and X-ray diffraction techniques. The corrosion degradation behavior of all the samples was tested in NaCl and NaCl and CO₂ mixture exposures using electrochemical impedance spectroscopy measurements. Nitrided NiCr alloys on a stainless steel substrate resulted with better adhesion than carbon steel, by delaying the corrosion mechanism when exposed to NaCl and CO₂ solution. A comparison of the corrosion resistive behavior of the substrates (stainless steel, carbon steel) and the coatings is made by using the electrical capacitance concept from a double-layer model for the coating–metal interface.     

Bioactive Sol-Gel Coatings for Orthopaedic Prosthesis

Sol-gel materials have been proposed in last years for clinical applications. In this work, bioactive sol-gel coatings were prepared from suspensions of up to 25% wt. of bioactive glass (CaO·SiO₂·P₂O₅) particles in a hybrid sol obtained from TEOS and MTES. Thick dip-coatings showed in vitro bioactivity after a few days, but glass-particles dissolution promotes a slight reduction in the corrosion resistance. In order to overpass this problem, a two-stage sol-gel coating system that includes a first SiO₂ hybrid film, acting as barrier against corrosion, and an external bioactive layer from glass particle suspension is proposed. The obtained samples revealed significant improvement in their electrochemical behaviour, and showed in vitro bioactivity.     

Silica-Zirconia Coatings Produced by Dipping and EPD from Colloidal Sol–Gel Suspensions

SiO₂-ZrO₂ sols have been prepared via acid catalysis using a commercial colloidal suspension of zirconia and two silica alkoxides; tetraethoxysilane (TEOS) and methyltriethoxysilane (MTES). Suspensions with 10, 15 and 25-mol% of ZrO₂ were prepared. The stability of the suspensions was followed by rheological measurements showing that the amount of water incorporated with the colloidal suspension is the factor that limits the maximum ZrO₂ content. Coatings have been prepared by dipping using the suspensions up to 25-mol% ZrO₂ onto glass-slides at different withdrawal rates. EPD process has been used to prepare coatings onto stainless steel AISI 304 using the suspension with 25-mol% ZrO₂ at different pHs. The parameters associated with the EPD process (current density, electric field, potential and deposition time) have been evaluated. The critical thickness for a ZrO₂ addition of 25-mol% was 0.8 μm and it increased for diminishing ZrO₂ content.     

Sol–Gel SiO2-ZrO2 Coatings for Optical Applications

SiO₂-ZrO₂ based nanostructured multilayers films have been prepared by sol–gel processing from metallorganic precursors by low temperature inorganic polymerization reactions. Simultaneous gelation of both precursors was realized. Homogeneous and transparent films were obtained at room temperature by dip- and spin-coating on glass and silicon wafer substrates. Samples with successively deposited layers (1–3 layers) and successive thermal treatments have been also studied. Each deposited layer was thermally treated for 1 h at 300°C. The coatings were characterized by XRD, spectroellipsometry (SE), UV-VIS spectroscopy and AFM methods. The influence of substrates, number of coatings and number of thermal treatments on the optical and structural properties of the films was established. The thickness of three deposited SiO₂-ZrO₂ layers is about 496 nm on glass substrates and 413 nm on the silicon wafer substrate. The films deposited on glass are more porous than those deposited on silicon. The properties of optical waveguide prepared from SiO₂-ZrO₂ layers on silicon substrates will be discussed.     

Sol-gel ZrO2 coatings for chemical protection of stainless steel

ZrO₂ coatings deposited on 316 L stainless steel sheets were synthesized by sol-gel method using Zr(OC₃H₇)₄ as precursor and isopropanol, glacial acetic acid, and water as solvents for application with ultrasounds. Different solutions for dip-coating were prepared with compositions varying between 0.025 and 0.9 mol/dm³ of ZrO₂. X-ray diffraction shows that the films densified at 800°C are crystalline with a tetragonal structure. The thickness of the coatings varied from 0.35–0.75 m. The influence of the ZrO₂ coatings on the corrosion behavior of stainless steel substrates in aqueous NaCl was studied through potentiodynamic polarization curves at 1 mV/s. The values of the electrochemical parameters allow for an explanation of the role of the films in the increased resistance of steel against corrosion in moderately aggressive environments.     

Sol-gel coatings of BaO-TiO2-SiO2 compositions

New alkali resistant BaO-TiO₂-SiO₂ coatings have been developed via the sol-gel process. In the solutions and in the gels (T<300°C) an infrared absorption band at 930 cm^–1 gives the possible evidence of mixed Si-O-Ti bonds, which have not been found in the system SiO₂-TiO₂-ZrO₂. Baking the films at about 500°C for less than 1 h leads to stable layers with negligible residual carbon contents. Compositions near 20 BaO-40 TiO₂-40 SiO₂ showed the best performance.     

Preparation and Evaluation of Octadecyl-Bonded ZrO2/SiO2

ZrO₂/SiO₂ particles, which were prepared by a layer-by-layer self-assemble technique and consist of micrometer-sized silica spheres as cores and nanometer-sized zirconia particles as surface coatings, have a higher surface area and pore volume than other zirconia supports have. Further more it is more stable than silica is. In this paper we made a reversed-phase support by bonding octadecyltrichlorosilane on ZrO₂/SiO₂ particles, it had a comparable high carbon amount of 9.62% and good chemical stability being stable up to pH 11. The chromatographic behavior showed that the support acted as a true reversed chromatographic stationary phase and had a hydrophobic selectivity. Basic and aromatic compounds are well separated and the peaks are symmetrical.     

Protective coatings based on Mn-Co spinel for current collectors of solid oxide fuel cells

The method of electrostatic spray pyrolysis was designed to apply protective coatings based on Mn-Co spinel to ferrite stainless steels (Crofer22APU and 08Kh18T1). The comparative thermogravimetric (TG) studies of ferrite stainless steels with and without protective coatings were carried out. The electrochemical characteristics of protective coatings exposed to long current loading were studied. The formation processes of Cr₂O₃ oxide films were studied at the contact of ferrite stainless steel with La_0.8Sr_0.2MnO₃ ionic and electronic conductor. The coatings of Mn-Co spinel were shown not preventing formation of continuous oxide film on the stainless steel surface.     

Effect of PEG with different <Emphasis Type="Italic">M</Emphasis><Subscript>W</Subscript> as template direction reagent on preparation of porous TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> with assistance of supercritical CO<Subscript>2</Subscript>

Titania–silica composite have been prepared using polyethylene glycol (PEG) with different molecular weights (M _w), PEG20000, PEG10000, and PEG2000, as template in supercritical carbon dioxide (SC CO₂). The composite precursors were dissolved in SC CO₂ and impregnated into PEG templates using SC CO₂ as swelling agent and carrier. After removing the template by calcination at suitable temperature, the titania–silica composite were obtained. The composite were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, and nitrogen sorption–desorption experiment. Photocatalytic activity of the samples has been investigated by photodegradation of methyl orange. Results indicate that there are many Si–O–Ti linkages in the TiO₂/SiO₂ composite; the PEG template has a significant influence on the structure of TiO₂/SiO₂. In addition, the TiO₂/SiO₂ prepared with PEG10000 exhibited high photocatalytic efficiency. So this work supplies a clue to control and obtain the TiO₂/SiO₂ composite with different photocatalytic reactivity with the aid of suitable PEG template in supercritical CO₂.     

Investigations of MgF2 Optical Thin Films Prepared from Autoclaved Sol

MgF₂ thin films with ultra low refractive indices were obtained by sol–gel method using sols prepared from magnesium acetate and hydrofluoric acid. The sols were autoclaved in a Teflon cell at 100–180°C for 24 h and then coated on SiO₂ glass or CaF₂ crystal substrates by spin coating. Subsequently, the samples were heat treated at 150°C for 1 h. The optical properties of the thin films, such as refractive index and transmittance, were investigated in the UV region, especially in the deep UV (DUV, below 250 nm) region. Though the coatings consist of single layers, both samples exhibited high transmittance. In addition, they exhibit such antireflection effect over a very wide range of wavelength. Such a good antireflection effect was produced only by low refractive indices. It has also been confirmed that, even in the range of vacuum UV (VUV, 200–150 nm), CaF₂ samples with antireflection coatings could keep such a good antireflection effect.     

Sol-Gel Derived TiO2-SiO2 Fibres

TiO₂−SiO₂ fibres with 0, 5, 10 and 20 volume % SiO₂ have been prepared by drawing from a gel followed by sintering at different temperatures. Nearly one meter long fibres can be drawn easily in conditions of about 50% relative humidity. Addition of SiO₂ inhibits the crystallisation of TiO₂ and also the anatase → rutile transformation and improves the strength of the fibres. While the pure TiO₂ fibres are brittle, those with 5, 10 and 20 volume % SiO₂ are flexible and strong. Tensile strength values as high as 3 GPa have been achieved in the 10 volume % SiO₂−TiO₂ fibres. Fibres heated above 900°C are brittle. The shape of the cross section of the fibres is found to depend on their diameters.     

Surface analysis of sol-gel coatings on glass by secondary neutral mass spectrometry

Secondary neutral mass spectrometry (SNMS) has been used to profile coatings of the systems SiO₂ and 65SiO₂.20TiO₂.15ZrO₂ (STZ). The coatings have been deposited on float glass and heat insulating glass by dip coating from alkoxide solutions. The microporous gel coatings have been densified by heat treatment. The SBM method (separate bombardment mode) has been applied to characterize the systems and the HFM method (high frequency mode) to check for matrix effects in the SBM depth profiles. Both methods show sodium diffusion from the float glass substrate into the STZ coating and no significant sodium diffusion into the SiO₂ coating. Measurements of the coatings on the heat insulating glass indicate that the SnO₂ interlayer acts as a diffusion barrier. The diffusion of sodium from the float glass substrate into the STZ coating during consolidation has been analyzed by SBM-SNMS. The sputtering rate decreases with increasing consolidation. Due to large differences between sputtering rates of the substrate and of the microporous coatings, the calibration of sodium intensities from time to depth at the interface has not been possible. However, a correlation between the final temperature of heat treatment and the depth of the Na₂O depletion in the substrate surface under the coating can be obtained.     

Effect of Sintering Temperature on the Corrosion and Wear Behavior of Protective SiO2-Based Sol-Gel Coatings

Sol-gel hybrid organic-inorganic and inorganic SiO₂-based protective coatings with and without added 3 m glass particles were developed and tested for their corrosion and wear behavior of an stainless steel substrate (AISI316L). The corrosion resistance greatly increases by incorporating glass particles in the sols. The incorporation of particles in the coatings allows the synthesis of thicker crack-free coatings. On the other hand, the corrosion resistance increases for coatings with a higher organic content obtained at lower sintering temperature. These coatings are also highly stable in saline aqueous solutions. However, the wear resistance is badly affected by the hybrid character of the SiO₂ matrix. The optimum coating process in terms of corrosion and wear resistance, appears to be a hybrid system with a dense SiO₂ network achieved at intermediate sintering temperatures.     

SiO2@CdTe@Au复合纳米粒子的制备与非线性吸收特性

应用SiO₂纳米粒子、CdTe量子点和Au纳米粒子,采用逐层吸附法制备SiO₂@CdTe@Au纳米复合材料。同时对样品进行了测试和表征,从多个方面证明纳米复合材料成功制备。利用Z扫描技术测量了SiO₂@CdTe和SiO₂@CdTe@Au纳米复合材料在纳秒激光脉冲作用下的非线性吸收光学特性。实验结果表明：SiO₂@CdTe和SiO₂@CdTe@Au纳米复合材料均表现出饱和吸收特性。SiO₂@CdTe@Au较SiO₂@CdTe纳米复合材料具有更强的非线性光学特性,并对其机理进行了分析。     

系列硅铝比纳米薄层ZSM-5分子筛的合成和表征

以自制不对称双子季铵盐表面活性剂为模板, 在水热合成体系中控制合成系列硅铝比纳米薄层ZSM-5分子筛.采用X射线衍射(XRD)、N₂吸附-脱附、X射线荧光光谱(XRF)、扫描电镜(SEM)和²⁷Al魔角旋转核磁共振(²⁷Al MAS-NMR)对合成的样品进行了表征. 详细研究了晶化温度、晶化时间、结构导向剂(SDA)用量、碱度等对合成的影响和纳米薄层ZSM-5分子筛的形成过程. 结果表明: 分子筛硅铝比越高, 结构导向剂用量越大, 所需的晶化时间越短; 晶化温度越高, 晶化时间越短; 且不同硅铝比纳米薄层ZSM-5分子筛的形貌规整度、比表面积和介孔/微孔孔容比例随着硅铝比而变化.     

利用二氧化硅欧泊模板合成三维多孔金属镍

金属镍在高效催化剂、传感器、导电浆料、高密度磁记录材料、高性能电极材料等领域具有广阔的应用前景,在材料科学和凝聚态物理领域引起了广泛的研究兴趣。多孔金属镍结构由金属镍骨架及孔隙所组成,与致密块体镍相比,其内部具有大量的孔隙,因而具有诸多优异的特性,如密度小、比表面积大、光学性能优异等。多孔金属镍可用来制作过滤器、催化剂及催化剂载体、多孔电极等[1]。1987年Yablonovitch[2]和John[3]几乎同时提出了光子晶体这一新概念和新材料。构成三维模板的途径之一是在液体中自组装成具有光波量级的单分散胶体微球——胶体晶体,这…     

Sol-Gel Deposition of ZrO2 Films in Air and in Oxygen-Free Atmospheres for Chemical Protection of 304 Stainless Steel: A Comparative Corrosion Study

ZrO₂ coatings for corrosion protection were deposited on 304 stainless steel by sol-gel method using zirconium propoxide as precursor and densified in air and in oxygen-free (argon or nitrogen) atmospheres. XRD and IR data of the films were practically independent of the atmosphere used in the densification step showing that the ceramic oxide is properly formed from the precursor. The corrosion behavior of the stainless steel substrate was studied by potentiodynamic polarization curves in the absence and the presence of ZrO₂ coatings prepared in air, argon or nitrogen. The coatings extended the lifetime of the material by a factor of almost eight in a very aggressive environment, independently of the preparation procedure. The possibility of depositing pure or mixed oxide films by sol-gel methods in the absence of additional oxygen will allow the preparation of specific coatings onto oxygen-reactive substrates.