Sol-Gel-Derived Hybrid Coatings for Corrosion Protection

The corrosion resistance of sol-gel-derived, organic-inorganic, silica-based hybrid coatings was studied. Hybrid sols were prepared by copolymerizing tetraethylorthosilicate (TEOS) and 3-methacryloxypropyltrimethoxysilane (MPS) with a two-step acid-catalyst process. Hybrid coatings were dip-coated on 304 and 316 stainless steel substrates and annealed at 300°C for 30 minutes. The adhesion, flexibility, and biocompatibility of the coatings were examined. Hybrid coatings were found to be relatively dense, uniform and defect free. Electrochemical analyses showed that the coatings provided excellent corrosion protection by forming a physical barrier, which effectively separated the anode from the cathode. In addition, further experimental results revealed that the corrosion patterns are strongly dependent on the nature of the stainless steel substrates. Some possible mechanisms for corrosion breakdown associated with each type of substrate are also introduced.     

Sol-Gel Coatings for the Protection of Brass and Bronze

The effectiveness of sol-gel Ormosil coatings as barriers coatings has already been demonstrated, and it is natural to assume that such coatings can play a unique role in art conservation, where object corrosion and decay are often a major issue. The main feature of ormosil coatings that would make them preferable to polymers is their potentially higher stability to ultra-violet radiation, controlled porosity and good adhesion to many different substrates. The permeability to various gases can also be tailored with changes in the chemical structure. In previous work, we have applied the sol-gel process as part of a multiplayer coating in the conservation of the Last Judgment mosaic in Prague. In the present work, we explore the use of sol-gel organic-inorganic hybrid coatings on various copper alloy substrates frequently encountered in art conservation.     

Synthesis and Properties of Cerium and Titanium Oxide Thin Coatings for Corrosion Protection of 304 Stainless Steel

Powders and thin coatings of ceria and titania were synthesized from aqueous and solvent-based precursors. Thin coatings were deposited on polished 304 stainless steel coupons by dipping them in the appropriate sol-gel oxide precursors. The coatings were subsequently densified and crystallized at several hundreds of degrees. It was possible to obtain dense titania coatings by applying thin coatings of cerium dioxide prior to titania on stainless steel substrates. Underlayer ceria coatings proved to be pivotal in obtaining dense titania coatings and preserving the integrity of the stainless steel while going through the high temperature treatments. The effect of processing parameters such as the atmosphere of heat-treatment, and temperature on the microstructure and crystal structure of the films and powders of ceria and titania was investigated. X-ray diffraction was used to identify the crystal structure of films and powders upon heat-treatment. Electrochemical measurements in NaCl, and analytical techniques such as SEM and EDX were used to evaluate the corrosion performance and pitting morphology of coated samples. A composite coating of ceria and titania was able to prevent crevice corrosion and increase the pitting resistance of the 304 stainless steel relative to the uncoated substrate.     

Ormocer (ZrO2-PMMA) Films for Stainless Steel Corrosion Protection

The chemical protection of 316 L stainless steel coated with ORMOCER coatings of polymethylmethacrylate (PMMA) and ZrO₂ has been verified. The coatings were dip-coated on the substrates from sols prepared by mixing zirconium propoxide (ZrOC₃H₇)₄, isopropanol (C₃H₇OH), glacial acetic acid (CH₃COOH), polymethylmethacrylate and water under application of ultrasounds. The films were heat treated between 40 and 300°C in air up to 20 h. Their morphology was studied by electron scanning microscopy (SEM). Their anticorrosion behavior was analysed in 0.5M-H₂SO₄ solutions through potentiodynamic polarization curves at room temperature.The influence of the sol preparation, coating composition as well as of the duration and temperature of heat treatments on the corrosion parameters is reported. The films act as geometric blocking layers against the corrosive media and increase the lifetime of the substrate up to a factor 30.     

Sol-Gel Coatings on 316L Steel for Clinical Applications

SiO2 and SiO2-CaO-P2O5 coatings have been prepared by dipping electropolished stainless steel 316L samples and microscope glass slides in three different sol-gel solutions. Multilayered dense SiO2 coatings, and thick silica films obtained from equimolar contents of TEOS and MTES were used. The latter were able to strongly reduce both the corrosion attack on the steel and the iron diffusion to the sample surface. SiO2-CaO-P2O5 coatings were also obtained and applied onto the silica films, in order to provide a bioactive external surface for contact with living tissue. In-vitro evaluation of these coatings and films is discussed.     

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.     

有机-无机杂化溶胶-凝胶涂层对不锈钢毛细管柱的脱活作用研究

 用甲基三乙氧基硅烷和四乙氧基硅烷水解缩合后形成的有机 无机杂化溶胶 凝胶 (sol gel)涂层对国产气相用不锈钢毛细管柱进行脱活。通过气相法研究了不同老化温度下所得脱活涂层的行为。结果表明这种涂层不但对不锈钢柱内壁活性点有很好的遮盖作用 ,而且本身具有相当的分离能力。在 2 5 0℃下老化的涂层可使碳原子数在 12以下的正构烷烃达到基线分离 ,与未用涂层的不锈钢裸柱相比 ,吸附活性大大降低 ;但随着老化温度的升高 ,涂层在缩聚老化过程中产生不均匀微孔 ,对被分离物的作用力加强。     

Sol-Gel Coatings on Non-Oxide Planar Substrates and Fibers: A Protection Barrier Against Oxidation and Corrosion

Sol-gel coatings on non-oxide substrates can be used to prevent high temperature degradation and to improve wet corrosion resistance. Alumina coatings were investigated. The starting precursor was aluminium sec-butoxide, modified with chelating ligands such as 2,4-pentanedione or acrylic acid to prevent its precipitation in the presence of water. Stainless steel plates and Hi-Nicalon SiC fibers are often utilized in different kinds of applications and thus were selected as substrates. Thin films were deposited from the modified alkoxide solutions using dip-coating techniques. The parameters governing the process such as the aging of the sols, the viscosity, the withdrawal rate and the thermal treatment were investigated. The films were characterized (morphology, thickness) and showed an interesting behaviour as protection barrier in an aggressive medium.     

硫化锰夹杂溶解和微生物存在对不锈钢管发生点蚀

结合发电厂凝汽器不锈钢管内壁腐蚀部位分布规律和腐蚀外貌特征,分别对腐蚀部位沉积物、内壁蚀孔附近管材成分进行扫描电子显微镜观察和能谱分析,探讨了管材中MnS溶解与微生物对凝汽器不锈钢管腐蚀的电化学反应机理,发现二者在点蚀形成过程中具有协同作用,并在综合分析影响不锈钢腐蚀的各种因素的基础上,提出了不锈钢凝汽器在运行过程中应采取的防护措施。     

新型十二烷基三甲氧基硅烷/氧化石墨烯复合膜对430不锈钢耐蚀性能的影响

使用一步电沉积法在430不锈钢上制备出十二烷基三甲氧基硅烷(DTES)/氧化石墨烯(GO)复合膜。 拉曼光谱(Raman)与扫描电子显微镜(SEM)测试表明,氧化石墨烯均匀地混合在硅烷膜中,并用电化学交流阻抗与极化曲线方法对这种复合膜所保护的430不锈钢进行耐蚀性能测试。 结果显示,在3.5%NaCl溶液中,430不锈钢会发生腐蚀反应,而存在硅烷复合膜的430不锈钢的耐蚀性能显著地提高。 研究表明,由于氧化石墨烯出色的阻隔性能一定程度上弥补了硅烷膜的缺陷,而且延长了腐蚀介质通过硅烷基质的路径,因此复合膜有着对基底物质更强的保护性能。     

Structural Characterization by SIMS of Alumina Coatings on Stainless Steel

Al₂O₃ coatings were obtained by the alkoxide route and deposited on stainless steel using the dip coating technique. The starting precursor was aluminum sec-butoxide modified by acrylic acid in order to prevent its precipitation in the presence of water.Useful information for the structural organization of alumina coatings on stainless steel is deduced from SIMS analysis. SIMS data reveal that the coating structure brings into play two different layers: an outer alumina layer that is more or less doped, mainly by iron, and an internal layer corresponding to the alumina/steel interphase. Beneath the interphase, the presence of an oxidized steel layer on the substrate surface is detected.Whatever the coating, the alumina/steel interphase exhibits a nearly constant thickness. On the other hand, a thickness variation of the oxidized steel layer is observed between samples under study: this thickness increases with the curing time of the coating.     

Sol-Gel Derived Coatings for Outdoor Bronze Conservation

A new conservation treatment for outdoor bronze sculptures based on inorganic-organic copolymers (ORMOCER^®s) was designed which meets the special requirements defined for this field of conservation. Following a systematic research strategy, a great variety of starting compounds (main components: 3-glycidoxypropyltrimethoxysilane or γ-methacryloxypropyltrimethoxysilane), curing conditions, hardeners and additives were considered for modifying the sol-gel materials. The characterization of the lacquers included IR, GPC and viscosity measurements as well as water and epoxy titrations. Screening was carried out by evaluation of the protective effect on bronze substrates. The material properties of the coatings were adjusted to optimize adhesion and resistance against weathering. Particular emphasis was given to curing the sol-gel polymer at ambient temperatures while retaining reversibility even after aging.     

Protective Properties of a Sol-Gel Coating on Zinc Coated Steel

Galvanised and galvannealed steels are widely used due to their good corrosion resistance in aqueous solutions. However, when additional protection is required, organic coatings, corrosion inhibitors or conversion coatings are used to improve their corrosion protection. In this work, sol-gel coating was used to improve the corrosion behaviour of these two materials. This paper analyses the final protective properties of a sol-gel coating prepared by basic catalysis and its dependence on the sintering temperature and time of treatment. The influence of the sintering conditions on the galvanised and galvannealed substrates is a decisive factor for the coating quality and for the barrier affect against the aggressive media. While heat treatment time is the controlling factor for the galvannealed steels, the temperature is determining in the case of the galvanised. Corrosion mechanisms for sol-gel galvanised steels did not changed with respect to the uncoated steel. However for galvannealed steel, after coating the mechanism is not purely cathodic.     

敏化处理304不锈钢局部腐蚀行为的扫描微电极法研究

通过扫描微电极法研究敏化处理奥氏体不锈钢(304ss)的局部腐蚀行为,并结合传统电化学方法及光学显微镜进行测试观察. 结果表明,在10% FeCl3溶液未敏化处理(304ss-NS)或550 oC轻度敏化处理(304ss-S1)的不锈钢倾向于发生点腐蚀,而650 oC(304ss-S2)或750 oC(304ss-S3)深度敏化处理不锈钢则倾向于发生晶间腐蚀.     

海洋微生物对316不锈钢的电化学腐蚀行为

采用自腐蚀电位、电化学极化曲线、电化学阻抗谱技术研究了316不锈钢在无菌培养基介质和海水微生物接种培养有菌培养基介质中不同周期的腐蚀行为．结果表明,316不锈钢电极在有菌介质中比在无菌介质中的腐蚀电流密度大,腐蚀电位负移,微生物加速了不锈钢的腐蚀速度．随着浸泡时间的增加,有菌介质中的不锈钢电极极化电阻值逐渐减小,表明了海洋微生物的附着和繁殖加速了316不锈钢的腐蚀速率,降低了其在海洋环境中的耐蚀性．     

Effect of Potential Perturbation Polarization on the Stress Corrosion Cracking of Type 321 Stainless Steel

Ithasbeenwidelyacceptedthatelectrochemicalcorrosionreactionsareinvolvedinthe.stresscorrosioncrackingprocessesofmostmetaljaqueoussolutionsystems'.Accordingtothecharacteristicsofdynamicstrainatthecracktipofmetal,itisofgreatimportancetostudytheinfluenceofvariedpotentialsonthedynamicstrainprocessatcracktipbydifferentpotentialpertllrbationsbetweenanodicandcathodicpotCntials.SmoothcylindricaltensilespecimenwasusedinSSRT(strainrate4.l6x's-').Allexperimentswereperformedino.75molILHCl O.25molILNa…     

Characterization of the Passive Film and Corrosion of Martensitic AM355 Stainless Steel

Electrochemistry methods were used to investigate the influence of pH on the passive film and corrosion behavior of ultrahigh strength AM355 stainless steel in chloride-containing media. Analysis of the Pourbaix diagram indicates that AM355 stainless steel exhibits higher corrosion resistance in natural and near-natural environments than that in acidic and alkaline conditions. Electrochemistry measurements and composition analysis of the passive film show that pitting potential increased due to the enhanced repassivation capacity of AM355 stainless steel with increasing pH. The mixed MnS/oxide inclusions are the main pitting sensitive locations under all conditions. Morphological observations and energy-dispersive spectroscopy showed that the influence of the gap between the martensitic laths is significant with increasing pH. The inclusions, element concentrations, and microstructures weaken the resistance of ultrahigh-strength martensitic AM355 stainless steel against corrosion.     

Anticorrosive and Microbial Inhibition Performance of a Coating Loaded with Andrographis paniculata on Stainless Steel in Seawater

With the trend for green technology, the study focused on utilizing a forgotten herb to produce an eco-friendly coating. Andrographis paniculata or the kalmegh leaves extract (KLE) has been investigated for its abilities in retarding the corrosion process due to its excellent anti-oxidative and antimicrobial properties. Here, KLE was employed as a novel additive in coatings and formulations were made by varying its wt%: 0, 3, 6, 9, and 12. These were applied to stainless steel 316L immersed in seawater for up to 50 days. The samples were characterized and analyzed to measure effectiveness of inhibition of corrosion and microbial growth. The best concentration was revealed to be 6 wt% KLE; it exhibited the highest performance in improving the ionic resistance of the coating and reducing the growth of bacteria.     

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.     

双相不锈钢在水溶液中之腐蚀疲劳与动态应变时效

本研究主要探讨 2 2 %Cr双相不锈钢在含氯离子水溶液中之腐蚀疲劳裂缝成长行为 ,以及在慢应变速率拉伸试验过程中所发生的动态应变时效现象 .同时以 31 6L沃斯田体系不锈钢及4 30肥粒体系不锈钢作为比较 ,藉以探讨不同晶体结构对腐蚀疲劳及动态应变时效行为的影响 .实验结果显示 ,在 80℃ ,3.5wt%NaCl水溶液中 ,3种不锈钢并未发生应力腐蚀破裂 ,但其中 31 6L沃斯田体系不锈钢及 2 2 %Cr双相不锈钢却发生动态应变时效 ,且动态应变时效的发生与温度 ,应变速率及沃斯田体相的组织有关 .在NaCl水溶液中 ,采用预裂试片量测疲劳裂缝生长速率 ,其结果表明 ,4 30肥粒体系不锈钢之疲劳裂缝生长速率最快 ,而氢脆是加快裂缝生长速率的主因 ,就双相不锈钢而言 ,腐蚀疲劳裂缝的生长主要与该不锈钢所含之肥粒体相的氢脆现象有关