Development of Heteropolysiloxane Coatings on Electrogalvanized Steel

The development of heteropolysiloxane coatings on electrogalvanized steel by sol-gel processing has been studied from the sol state to the solid state using techniques such as 29Si NMR, SIMS, XPS, and the three point flexure test. It was possible, from the results obtained, to propose a simplified model for the coatings which brings into play two layers of differing molecular structure: an extremelly thin internal layer and an outer layer, respectively called the anchoring and volume layers.     

电镀锌钢硅烷-有机膦酸复合钝化膜的制备及性能表征

利用N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷(AAPTMS)、γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷(GPTMS)和1-羟基亚乙基-1,1-二膦酸(HEDP),在电镀锌钢基体上制备了一种新型硅烷-有机膦酸复合钝化膜.X射线光电子能谱、傅立叶变换红外光谱以及中性盐雾试验、动电位极化曲线和电化学阻抗谱测试表明:该复合钝化膜主体结构由Si—O—Si、Si—O—P等组成;120 h中性盐雾试验后白锈面积小于5%,达到铬酸盐彩色钝化膜水平;且其腐蚀反应呈现更为明显的阳极扩散控制特征,属于物理阻挡机制.     

Investigation of Glass-Like Sol-Gel Coatings for Corrosion Protection of Stainless Steel Against Liquid and Gaseous Attack

Glass-like sol-gel coatings have been investigated as corrosion protective coatings on stainless steel. Magnesium- and borosilicate coatings with thickness of about 100–700 nm and methyl-modified SiO2 coatings with a thickness of about 2 m were deposited on stainless steel plates by dip-coating. The coatings were densified between 400°C and 500°C in different atmospheres (N2, air) for 1 h. The corrosion protection against gaseous attack was investigated by accelerated corrosion tests, at 800°C in air for 1 h. A corrosion protection factor was calculated from the relation Fe/Fe2O3, determined by XRD on the surface of coated and uncoated samples. Methyl-modified SiO2 coatings showed a protection factor, which was 2 orders of magnitude higher than for the other coatings. Electrochemical investigations were performed on samples submerged in a NaCl solution for 200 h. The corrosion propagation, polarization resistance and impedance vector were measured. For accelerated corrosion tests, polarization intensity curves were determined for high potentials of up to 1 V. Again excellent results were obtained for the methyl-modified SiO2 coatings, which remained passive for 200 h. Results of the salt spray corrosion test, however, showed no corrosion protection by the sol-gel coatings. After 2000 h in the salt spray chamber the steel was corroded and the coatings peeled off. It is concluded that for the further development of these coatings an improved interfacial passivation will be required.     

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.     

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.     

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.     

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。     

铝化与白金铝化涂层对MAR-M247镍基超合金之抗热腐蚀性质影响研究

本文研究MAR-M247镍基超合金表面经铝化涂层或白金铝化涂层处理后,其热腐蚀效应对腐蚀速率与显微组织之影响,并藉试片质量增加量的变化评估抗热腐蚀的能力.铝化涂层之主要组成为-βN iA l相,而白金铝化涂层表面的主要组成为PtA l2相,利用盐喷覆法将Na2SO4被覆在试片表面,置于热处理炉中观测其热腐蚀性.实验得知,铝化涂层和白金铝化涂层均可明显抑制MAR-M247的热腐蚀,且后者之效果更明显,此两种涂层在910℃之Na2SO4环境中的抗蚀性均较MAR-M247合金为佳.     

Characterization of metallic layer composites by means of AES/depth profile analysis

The adherence mechanism of arc sprayed Ni layers on structure steel St37 is investigated. AES depth profiles are obtained on single Ni particles still adhering to the substrate after the Ni layer has been separated from it. A comparison of interface shapes and results of adherence measurements reveals Fe-Ni layered structures for the best adhering layers, whereas less adhering layers are characterized by narrower interfaces caused by diffusion. Areas with no adherence are covered with oxidic layers.     

Synthesis and Characterization of New Adhesion Promoter for Grafting Conducting Polymer on Oxide Substrate

For grafting polypyrrole layers on oxidic substrates, the synthesis and characterization of a new adhesion promoter 11‐(pyrrol‐3‐yl) undecyl trimethoxysilane (PyTMS) were described in this article. The oxidation potential of PyTMS was determined by cyclic voltammetry. The grafting behavior of such an adhesion promoter on oxidized surface and chemical deposition of polypyrrole over the modified oxidized surface were studied. The adsorbed layer on the oxidized substrates thus formed was determined by both contact angle measurements and X‐ray photoelectron spectroscopy. Chemical polymerization of terminal pyrrole moieties on such substrates yielded adhesive polypyrrole films, and SEM image showed that the morphology of the polypyrrole films was influenced by the experimental conditions.     

用于高性能涂料的无定型聚芳醚腈酮共聚物的制备及性能

通过亲核缩聚反应由酚酞、4,4′-二氟二苯酮和2,6′-二氯苯腈制备了一系列不同腈基含量的无定型聚芳醚腈酮共聚物。通过FT-IR、1 H-NMR、13 C-NMR、DSC、TGA等表征了聚合物的结构与性能。研究表明:随着腈基含量的提高,聚合物的玻璃化转变温度升高,在马口铁板上的附着力逐渐提高;该聚合物在有机溶剂中具有良好的可溶性和成膜性,聚合物涂层具有优异的综合性能。     

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.     

在冷轧钢板表面制备二乙烯三胺五甲叉膦酸-锌化学转化膜及其腐蚀防护性能的研究

本文通过调节二乙烯三胺五甲叉膦酸酯（DTPMPA）与Zn²⁺浓度以及溶液的pH值,将冷轧钢板浸泡于含有DTPMPA和Zn²⁺的混合溶液中即可在基体表面形成颜色均匀且具优异腐蚀防护性能的DTPMPA-Zn²⁺化学转化膜. 使用 SEM 和 EDS 研究了DTPMPA-Zn²⁺转化膜的表面形貌和元素组成,利用FTIR和XPS光谱方法探究了化学转化膜的表面官能团、化学组分及官能团与基底的结合方式,进而通过电化学阻抗谱（EIS）和极化曲线方法探究了DTPMPA浓度及成膜溶液pH值对化学转化膜的耐蚀性能的影响. 研究发现,DTPMPA与Zn²⁺共存时,二者发生螯合反应,并以Zn²⁺为交联剂通过多层组装在冷轧钢基体表面形成外观为蓝色的、厚度较为均匀的DTPMPA-Zn²⁺螯合物薄膜. 当成膜溶液的 pH=3.0、DTPMPA浓度为0.2%（除特别指出外,全文浓度均为质量百分数）、Zn²⁺浓度为0.044%时,化学转化膜展现出最优异的防腐性能,对基体的腐蚀保护效率可达91.6%.     

Synthesis and Characterization of Transparent Hydrophobic Sol-Gel Hard Coatings

It is challenging to make a transparent hydrophobic hard coating when soft hydrophobic additives are added into the coating system. Material non-homogeneity due to phase separation, non-durable hydrophobicity and deteriorated transparency are the main issues. In this paper, we describe a chemical formulation, which contains a pre-linked hydrophobic cluster and a silica hard matrix with silica hard fillers so that the hydrophobic property and hardness can be tuned separately and optimized. The transparency of the coating is found to be related to the effective modification of the reactive titanium tetraisopropoxide (TIP) precursor by ethyl acetoacetate (EacAc) and the right ratio between TIP and polydimethylsiloxane (PDMS) (≤0.5). The water contact angle is increased to a maximum of 133° when 50 Vol% of PDMS is added into the silica matrix. The hardness of coating is proportional to silica filler content and curing temperature, and inversely proportional to PDMS Vol%. 30 Vol% silica filler in silica matrix and curing temperature at 300°C result in the best hardness in this study. Hardness at 50 Vol% PDMS dropped to 0.2 GPa from 0.85 GPa of pure silica coating. The Vol% of PDMS and silica filler will be further optimized in our next stage experiments.     

钢铁表面Ni-Sn-P合金镀层组成及其耐蚀性

化学镀;钢铁表面Ni-Sn-P合金镀层组成及其耐蚀性     

Yttrium Acetate-Derived Particle Coatings for Mitigating Oxidation and Corrosion of Inconel 625

Sol paint that yields yttrium-based compounds was prepared by mixing four chemical ingredients, yttrium acetate tetrahydrate precursor, diethanolamine, isopropyl alcohol, and hydrochloric acid, and then applied as oxidation/corrosion resistant coatings for Inconel 625 substrates. Annealing the coatings at 500°C developed a coalescent microstructure of coarse particles consisting of amorphous yttrium carbonate as the major component and crystalline yttrium oxide (Y2O3) as the minor one. At 700°C, the yttrium carbonate was transformed into Y2O3 by decarbonation. Increasing the annealing temperature to 900°C led to the formation of the YCrO3 phase yielded by interaction between Y2O3 and the Cr2O3 which had arisen from the oxidation of the underlying Inconel; the YCrO3 phase created a particle coating with a densified microstructure. There were two key factors in mitigating the degree of oxidation of Inconel at 900°C in air: (1) an uptake of oxygen by Y2O3 in the coatings, and (2) a densified coating layer that suppresses the diffusion and permeation of oxygen through it. Furthermore, inhibiting the rate of NaCl-caused corrosion was not only due to the excellent coverage of particle coatings over the entire surfaces of the substrates, but also may be associated with a good adherence of the coatings to the substrates.     

“钢铁电化学腐蚀原理的再认识”项目式教学

以"钢铁电化学腐蚀原理的再认识"为项目，教师用"项目式教学"的方式引导学生深入地认识钢铁电化学腐蚀原理。详细介绍了教师如何确立项目，如何规划项目，如何实施项目。学生在原有金属腐蚀原理的基础上，又学习了氧浓差电池腐蚀，对原电池的原理有了更加深入的理解。根据氧浓差电池腐蚀的特点，学生提炼了一个合理的简易判据来判断氧浓差电池腐蚀。项目结束之后，学生利用思维导图重新构建了金属腐蚀和防护的知识结构。     

酸性溶液化学镀Ni-P-B合金及结构性能表征(英文)

联用次亚磷酸钠和硼氢化钠两种还原剂 ,从酸性镀液中沉积出不同硼含量的Ni_P_B镀层 ,并用原子力显微镜、X_射线衍射、透射电镜、动电位扫描等实验技术对其镀态结构及性能进行了表征。实验表明 ,镀液中硼氢化钠含量对沉积速度影响不大 ,但能显著影响镀层的化学组成。硼的共沉积使镍晶格点阵产生扭变 ,导致镀层晶粒增大 ,表面粗糙 ,颗粒分布不均匀 ,并使镀层由非晶态向微晶结构转变 ,且微晶成分随镀层中硼含量的增加而增多。Ni_P_B镀层的硬度随镀层中硼含量的增加而增大 ,热处理能显著提高镀层的硬度 ,且服从沉淀硬化机理。在 3.5wt%NaCl和 40wt%NaOH两种介质中 ,Ni_P_B合金的耐腐蚀能力优于Ni_P合金。镀层中硼含量越高 ,其耐腐蚀能力越强。     

Exploring the relationship between the surface chemistry and the corrosion behavior of electropolymerized polypyrrole films deposited on the surgical ISO 5832-1 stainless steel

In the present work, electropolymerized polypyrrole (PPy) films were obtained on the surface of the surgical ISO 5832-1 stainless steel. The films were obtained from solutions containing 0.1M and 0.5M of the monomer by cyclic voltammetry deposition. The correlation between the surface chemistry of the as-deposited films and the corrosion behavior of the coated substrate is explored. X-ray photoelectron spectroscopy was used to study the chemical state of the main elements in the PPy films. Electrochemical impedance spectroscopy and potentiodynamic polarization tests were employed to evaluate the corrosion resistance of the PPy-coated samples. The tests were conducted in phosphate-buffered saline solution at 37°C. The measured corrosion current densities were dependent on the doping level of the PPy film and decreased with the reduction of the doping level of the PPy layer.     

苯基硫脲对6063铝合金表面化学镀镍层电化学性能的影响

采用极化曲线及交流阻抗技术研究了不同浓度的苯基硫脲(稳定剂)对6063铝合金表面镍层的电化学性能的影响。极化曲线结果表明,镀液中加入苯基硫脲后的镀镍层比基体铝合金具有更正的腐蚀电位(Ecorr)、小孔(点)腐蚀电位(Epit)及更低的腐蚀电流(icorr)。为了解释镍层的电化学性能,建立了等效电路模型,并拟合出了表面电阻(Rcoat)及电容(Qcoat),电荷转移电阻(Rct)及双电层电容(Qdl)等腐蚀参数。交流阻抗研究结果表明,加入6～10 mg/L苯基硫脲后的镀镍层具有较高的表面电阻(Rcoat)、电荷转移电阻(Rct)及较低的表面电容与双电层电容(Qcoat与Qdl)。镀镍层的交流阻抗谱及极化曲线的测试结果表明,制备的镀层具有较好的耐腐蚀性能,并且相互吻合。采用扫描电子显微镜及能谱对化学镀镍层的表面形貌及成份进行了分析。结果显示,表面处于较均匀的状态,磷元素的质量分数超过10%。