含氟化物银钎剂去除304不锈钢表面氧化膜的机理

使用银钎剂（由K₂B₄O₇、H₃BO₃、KF或KHF₂组成）去除304不锈钢表面氧化膜,研究了银钎剂对304不锈钢表面氧化膜的去除机理。结果表明,700 ℃时,在钎剂成分中某一成分的单独作用下,K₂B₄O₇和KF不能去除304不锈钢表面氧化膜;在任意2种成分的协同作用下,只有K₂B₄O₇与H₃BO₃的混合物在700 ℃下不能熔化,其余二元混合物均能与钢板表面氧化物反应;自由能（ΔG_m^θ）和反应平衡常数（K^θ）的计算结果显示,钎剂去除氧化膜的主要原因是该过程中钎剂中的F替代氧化物中的O,该反应的平衡常数达到 1.3×10¹⁶⁷,自由能小于零,反应可以进行。XRD结果显示,在2θ=18°位置的峰形发生改变,说明KF被KHF₂替代后,钎剂去除氧化膜的机理发生变化。含有KF和KHF₂的3号钎剂在540 ℃时可以有效去除钢板表面氧化膜,与钎剂的反应产物具有非晶结构特征。     

AZ91D合金表面铈转化膜成膜工艺及其耐腐蚀性的研究

  通过正交试验确定了AZ91D 镁合金在CeCl₃H₂O₂体系中的最佳成膜条件.利用扫描电镜对转化膜进行形貌观察和成分分析,利用浸泡集气和电化学方法了膜层的耐腐蚀性能.结果表明,在最佳成膜条件下,形成的膜层均匀、致密.在3.5% NaCl溶液和0.15 mol/L H₃BO₃/0.05 mol/L Na₂B₄O₇缓冲溶液中的动电位极化测试表明,最佳条件下铈盐转化处理可使合金的腐蚀电位正移,腐蚀电流密度明显降低,起到一定的防护作用.     

ZrB2-玻璃陶瓷复合材料氧化分析

对ZrB₂-玻璃陶瓷复合材料氧化行为进行热力学分析,对氧化形成的氧化层进行物相分析和显微结构分析。结果表明：在1000°C-1400°C的反应温度范围内,ZrB₂氧化生成ZrO₂,B₂O₃玻璃相,氧化产物ZrO₂与SiO₂反应生成ZrSiO₄,当温度低于1177°C(1450K)时,氧化层主要包括ZrO₂,B₂O₃玻璃相,ZrSiO₄。当氧化温度超过1177°C(1450K)时,B₂O₃玻璃相蒸发,此时SiO₂玻璃相具有良好的流动性,氧化层主要包括ZrO₂,SiO₂玻璃相,ZrSiO₄。氧化过程中的反应产物B₂O₃玻璃相,ZrSiO₄和流动性良好的SiO₂玻璃相,均对氧气向基体的扩散均起到了良好的阻碍作用。     

粉末包埋渗铝与气氛渗铝对P92钢650℃饱和蒸汽氧化行为的影响

表面渗铝技术可以在不改变基体材料力学性能的基础上显著提高基体的抗高温蒸汽氧化性能。 利用低温粉末包埋和气氛渗铝两种方法在 P92 钢表面制备了铝化物涂层,并结合氧化增重法、扫描电镜观察及 XRD 分析,研究了两种工艺下铝化物涂层的 650 ℃饱和蒸汽氧化行为。 结果表明:P92 钢抗氧化能力不足,生成了由外层疏松层瘤状富铁氧化物与表面氧化膜下方内氧化物 FeCr₂O₄ 组成的双层结构氧化膜,外层富铁氧化膜在氧化 300 h 后发生剥落;低温包埋渗铝所得涂层为 β-FeAl 层,氧化 500 h 后试样表面形成极薄的保护性 α-Al₂O₃ 氧化膜(<0. 2 μm);气氛渗铝涂层为单层 Fe₃Al 结构,氧化 500 h 后试样外表面形成了 Fe₃O₄₊Fe₂O₃ 氧化膜,厚度为 1. 3 μm,靠近涂层表面生成单层连续 Al₂O₃ 氧化膜。 采用低温包埋和气氛渗铝均可提升 P92 钢的抗蒸汽氧化能力。     

BT25Y钛合金在600 ℃—800 ℃的高温氧化行为研究

研究了BT25Y钛合金在600 ℃、700 ℃和800 ℃下的高温氧化行为。采用连续氧化增重法,并结合氧化速度常数、氧化活度等理论计算了合金的氧化动力学和热力学规律;利用XRD、SEM和EDS等表征方法研究了氧化膜的相结构和表面、截面形貌及元素分布。结果表明：BT25Y钛合金在600 ℃和700 ℃均有较好的抗氧化性能,其连续氧化动力学曲线符合抛物线规律,氧化层由细小TiO₂和Al₂O₃组成,氧化膜可有效阻止氧渗入基体,降低氧化速度;BT25Y钛合金在800 ℃氧化严重,其连续氧化动力学曲线近似符合直线规律,氧化层由Al₂O₃层和TiO₂层交替组成,氧化膜疏松多孔,不能有效阻挡氧向基体一侧的扩散。     

Al2O3微粉添加量对镁合金微弧氧化膜特性影响研究

为了研究添加Al₂O₃微粉对AZ31A镁合金微弧氧化膜特性影响,在不同浓度Al₂O₃微粉电解液中对其进行了微弧氧化处理。利用扫描电镜(SEM)观察微弧氧化膜形貌,能谱仪(EDS)分析了膜层表面Ca、Mg、O、Al元素分布,X射线衍射仪(XRD)分析了相组成,测定了膜厚、硬度和氧化液中Al₂O₃表面电荷,讨论了掺杂改性机理。结果表明,加入Al₂O₃微粉后,氧化电压随Al₂O₃添加量增加先增加后降低;氧化膜表面孔洞数量和尺寸减小,膜层表面Ca元素分布逐渐减少,成膜效率降低,膜层致密度和表面疏松层硬度提高,氧化膜主要由MgO和MgO₄等相组成。     

不同Cr含量的Ni-Cr合金熔覆层的高温氧化和热腐蚀特性

采用激光熔覆技术制备了Cr质量分数为10%、20%和40%的Ni-Cr合金熔覆层,研究了其在900 ℃下的高温氧化特性和600 ℃下Na₂SO₄+25% K₂SO₄混合盐中热腐蚀特性。结果表明,Cr含量对熔覆层的高温特性起着关键作用。提高Cr含量对提升熔覆层抗硫酸盐诱导的热腐蚀能力比提升抗循环高温氧化能力更有效。Cr40涂层抗高温氧化和热腐蚀性能最佳。Cr10的氧化产物以NiO为主,极易脱落,内部氧化严重。虽然Cr40表面可以形成单一的Cr₂O₃层,但热应力和生长应力引起的富Cr氧化物内部开裂,使Cr40的抗循环高温氧化能力仅略好于Cr20。面对热腐蚀时,Cr10表面呈现层状NiO和Ni₃S₂叠层分布的腐蚀产物,内部腐蚀区也生成了Ni的硫化物。Cr20表面Cr₂O₃层被破坏,内部腐蚀严重,生成了CrS。Cr40表面生成了致密的Cr₂O₃保护层,有效地防止了进一步腐蚀。     

CoCrNiAlY涂层制备工艺对组织形态及高温氧化行为的影响

为了研究CoCrNiAlY涂层微观组织结构对高温氧化行为和剥落行为的影响规律,采用激光熔覆技术和等离子喷涂工艺在718高温合金表面制备CoCrNiAlY涂层,观察其微观组织形态。利用XRD和SEM对1150 ℃高温氧化试验样品进行氧化层物相分析和形貌观察。结果表明,激光熔覆制备的CoCrNiAlY涂层中形成了胞状亚结构的等轴晶凝固组织,相对于等离子喷涂制备的CoCrNiAlY涂层结构更致密,具有更优异的抗高温氧化性能。在高温氧化过程中,等离子喷涂CoCrNiAlY涂层生成了以Cr₂O₃结构为主的复合氧化膜。激光熔覆CoCrNiAlY涂层生成Al₂O₃结构的单一氧化膜,而且熔覆层中原位形成的Y₂O₃钉扎作用能有效提高氧化膜的抗剥落性。文中系统分析讨论了两种不同工艺制备的组织形态对高温氧化膜形成机制的影响,激光熔覆涂层在高温下主要是以界面扩散方式形成致密的Al₂O₃膜,等离子喷涂涂层在高温下以界面反应的方式快速形成Cr₂O₃复合氧化膜。     

磁致涡流效应对化成铝箔Al2O3-TiO2复合膜结构及性能的影响

以TiCl₄为前驱体溶液,通过磁场辅助电沉积法在腐蚀箔表面形成具有高介电常数的Al₂O₃-TiO₂复合氧化膜。系统研究了磁致涡流效应（MHD效应,Magnetohydrodynamics）对电解液中离子扩散行为及Al₂O₃-TiO₂复合氧化膜结构与性能的影响规律。采用XRD能谱、扫描电镜SEM以及EDS能谱等手段对氧化膜晶相、表面/截面形貌以及Ti元素分布进行表征。结果表明,随着磁感应强度B的增强,电解液中Ti⁴⁺向箔面及蚀孔内的扩散速率增大,复合膜层中锐钛矿型TiO₂含量提高,且其在箔面及蚀孔内部分布均一性提升。另外,氧化膜阳极升压曲线、Tafel极化曲线及交流阻抗曲线的分析结果表明,MHD效应提高了复合氧化膜介电常数,减少了阳极氧化阶段的形成电量,对应的化成箔比电容增大至58.29 μF/cm²,较之无MHD制备的Al₂O₃-TiO₂化成箔,其形成电量减少了24.6%,比电容增加了10.1%。     

Si对625合金激光熔覆层高温氧化特性的影响

利用循环氧化法,研究了不同Si含量（0%,1%,3%,质量分数）的625合金熔覆层在700、800、900 ℃下氧化144 h后的高温氧化行为。用XRD分析了氧化物相。通过SEM/EDS研究了氧化物表面和截面的形貌、元素组成和氧化膜的厚度。结果表明,不同温度下试样的氧化动力学都保持抛物线规律,随着温度的升高,氧化增重逐渐增加。通过观察,在900 ℃时,0% Si含量的625合金熔覆层出现了氧化膜大面积剥落的情况,3% Si含量的合金熔覆层氧化膜保持完整。在700 ℃时,随着Si含量增加,氧化膜表面的氧化颗粒尺寸减小且更加致密,同时促进了Cr₂O₃氧化物的生成。在700 ℃下,0 % Si含量的试样出现了大片的内氧化区域;1% Si含量的试样基体部分出现了2处条状的含Ni,Cr,Mo的氧化物相区;而3% Si含量的试样氧化后由于生成了富Si的内氧化层,这阻止了内氧化的发生。外层Cr₂O₃氧化膜和内层SiO₂的联合作用既阻止了O阴离子的渗入也抑制了Fe等金属离子的扩散,提高了合金熔覆层的抗氧化性。     

Dissolution susceptibility of the oxide species formed on mild steel during its oxidation in molten NaNO3-KNO3 eutectic mixture

Mild steel was oxidized in pure molten NaNO₃-KNO₃ eutectic mixture at temperatures of 300, 375, and 450 °C and in the presence of 0.05 molal KH₂PO₄, K₂Cr₂O₇, or Na₂O₂ as additives. The dissolution susceptibility of the formed oxide species was evaluated in H₂SO₄ acid solution using the potential-time and current-time measurements under the open-circuit conditions. It was found that the rate of dissolution depended on the composition of molten nitrate bath, used for oxidation of mild steel, and its temperature. This was attributed to the effect of the previous conditions of the nitrate bath on the nature and composition of the oxide species formed on the metallic surface. The more resistant to dissolution in H₂SO₄ solution were those electrodes that were oxidized in nitrate melt at 450 °C in the presence of K₂Cr₂O₇ or Na₂O₂ as additives.     

The initial stage of pitting corrosion on coated steels investigated by photon rupture in chloride containing solutions

A photon rupture method, film removal by a focused pulse of pulsed Nd-YAG laser beam irradiation, has been developed to enable oxide film stripping at extremely high rates without contamination from the film removal tools. In the present study, Zn-55mass%Al alloy and Al-9mass%Si alloy-coated steel specimens covered with protective nitrocellulose film were irradiated with a focused pulse of a pulsed Nd-YAG laser beam at a constant potential in 0.5 kmol m⁻³ H₃BO₃-0.05 kmol m⁻³ Na₂B₄O₇ (pH = 7.4) with 0.01 kmol m⁻³ of chloride ions to investigate the initial stage of localized corrosion. At low potentials, oxide films on both coated alloys were reformed after the nitrocellulose films were removed by this method. The oxide film formation kinetics follows an inverse logarithmic law, in agreement with Cabrera-Mott theory. However, at high potentials, localized corrosion producing corrosion products occurs at the area where nitrocellulose film was removed. Nevertheless, when the applied potential is less noble, the dissolution current of the Zn-55mass%Al-coated steel samples is higher than that of Al-9mass%Si-coated samples.     

Effect of Potassium Dichromate on the Passivation of Stainless Steel (AISI 321) in Sulphuric Acid

Abstract

The effect of potassium dichromate on the passivation of stainless steel in sulphuric acid has been investigated. Tests with K₂Cr₂O₇ up to 4N showed that passivation could be achieved in 3·4 N H₂SO₄ containing 0·1 N K₂Cr₂O₇, and that the quality of the passivating film increased with the concentration of K₂Cr₂O₇ and with the duration of the passivation treatment. Although passivity could be induced in these conditions at 30°C, at higher passivation temperatures the film quality diminished as shown by long-term decay studies after transfer of the metal to sulphuric acid solutions containing no dichromate. The metal could be passivated in all concentrations of H₂SO₄. Passivation was also possible in 3·4 N H₂SO₄ containing 0·2 N K₂Cr₂O₇ and up to 5% NaCl. However, the breakdown of the film produced in the presence of NaCl occurred earlier the higher the concentration of NaCl present during passivation.     

Growth and characterization of thin anodic oxide films on n-InSb(1 0 0) formed in aqueous solutions

Anodic oxide films were galvanostatically grown on n-InSb(1 0 0) surfaces at various pH in sodium hydroxide (0.1 M NaOH, pH=13), borate buffer (0.075 M Na₂B₄O₇ + 0.3 M H₃BO₃, pH=8.4) and phosphate buffer (0.3 M NH₄H₂PO₄, pH=4.4). Thickness, composition and morphology of the oxide films were determined by various surface analytical techniques such as Auger electron spectroscopy, X-ray photoelectron spectroscopy, scanning and transmission electron microscopy and atomic force microscopy. The oxides comprise mainly In₂O₃ and Sb₂O₃ and the oxide thickness increases with pH. Electrical properties of oxides indicate that the films may be useful as insulators in some device applications.     

The Effects of KCl, K2SO4 and K2CO3 on the High Temperature Corrosion of a 304-Type Austenitic Stainless Steel

The oxidation of 304-type (Fe18Cr10Ni) austenitic stainless steel was investigated at 500 and 600 °C in 5% O₂ + 40% H₂O. Prior to exposure the samples were sprayed with KCl, K₂CO₃ or K₂SO₄, the amount of salt corresponding to 1.35 ??mol K⁺/cm². For reference, salt-free samples were exposed in 5% O₂ + 40% H₂O and in 5% O₂ (N₂ was used as carrier gas). The oxidized samples were analyzed with SEM/EDX, XRD, IC and FIB. KCl and K₂CO₃ strongly accelerate the corrosion of 304L while K₂SO₄ has little influence on the corrosion rate and on the morphology of the corroded surface. KCl and K₂CO₃ react with the chromium-rich oxide on the sample surface, forming K₂CrO₄. The resulting chromium depletion of the protective oxide causes rapid oxidation and the formation of a thick duplex scale consisting of an outer hematite layer and a inner layer made up of FeCrNi spinel-type oxide. The differences in the corrosivity of the three salts are directly connected to their ability to form chromate on the surface and, hence, to the relative stability of the corresponding leaving groups (HCl, CO₂ and SO₃).     

Oxidation Behavior of High-Speed Steel Used for Hot Rolls

Non-isothermal oxidation kinetics of the high-speed steel (HSS) were studied by thermal gravimetric analysis. The surface and cross-sectional morphology of the HSS oxide film formed at different temperatures and durations were observed by scanning electron microscopy, and the corresponding chemical composition was analyzed by using energy dispersive spectrometer. The composition and structure of the oxide film were also investigated by X-ray diffraction. The results showed that the oxide scale of the HSS is mainly composed of Fe₂O₃, Fe₃O₄ and FeCr₂O₄. Temperature is the main factor on the quality of the oxide film. Below 600 °C, the oxidation rate of the steel is slow and the thickness of the oxide film is below 5 µm. However, the oxidation rate sharply increased as the temperature reaches 600 °C. Cr, Mo and V tend to concentrate at the scale/steel interface and form FeCr₂O₄ and other oxides.     

Correlation between the corrosion resistance and the semiconducting properties of the oxide film formed on AZ91D alloy after solution treatment

The corrosion resistance and semiconducting properties of the oxide film formed on the AZ91D alloy were evaluated. The alloy was tested in the as-cast condition and after a solution annealing treatment. Electrochemical impedance spectroscopy measurements and potentiodynamic polarization curves were obtained in a H₃BO₃ (0.05 M) + Na₂B₄O₇⋅10H₂O (0.075 M) solution with pH = 9.2 at room temperature. The semiconducting properties of the oxide film were evaluated using Mott–Schottky plots. The corrosion resistance of the AZ91D was reduced after the solution treatment while the semiconducting properties of the passive films were little affected.     

Effect of water on behaviour of Na2B4O7·5H2O and Na2B4O7 in HCl-CH3OH medium

The reactivity of Na₂B₄O₇·5H₂O and Na₂B₄O₇ in non-aqueous HCl-CH₃OH solvent system was investigated. The effects of H₂O, CH₃OH/B mole ratio and reaction time on the reaction at room temperature were examined. Experimental results show that when Na₂B₄O₇·5H₂O and Na₂B₄O₇ are the reactants, the dissolved B₂O₃ contents are observed to be 98.2% and 99%, respectively, in 5 min at the CH₃OH/B mole ratio of 4. The decrease of water in the reaction medium was observed to increase the crystallization of NaCl in the order of Na₂B₄O₇2B₄O₇·5H₂O. It was also observed that the boron solution obtained after the reaction could be hydrolyzed by the addition of H₃BO₃. The results show that HCl-CH₃OH system is a more effective solvent compared to H₂SO₄-CH₃OH both in the reactivity and the shortened reaction time.     

Evolution of Oxide Film of T91 Steel in Water Vapor Atmosphere at 750 °C

In order to investigate the evolution of oxide film on T91 steel, oxidation tests were conducted in water vapor atmosphere at 750 °C. The phase compositions and microstructures of the oxide scales for early stage oxidation were investigated by using glancing angle XRD and SEM equipped with EDS. The results showed that during the initial oxidation stage Cr-rich oxide film formed and then it covered the sample surface rapidly. The initial Cr-rich oxide film was mainly composed of FeCr₂O₄, (Fe,Cr)₂O₃ and Fe₂O₃. This oxide film acted as a barrier against outward diffusion of iron and inward diffusion of oxygen. During the initial oxidation stage, chromium in the sample surface was consumed gradually, and then a large amount of iron ions penetrated the oxide film and diffused rapidly to the sample surface, resulting in forming an outer “non-protective” Fe₂O₃ layer.