热氧化提高钛及钛合金表面性能的研究进展

热氧化作为一种引起广泛关注的钛及钛合金表面改性技术,具有工艺简单、原位生长、薄膜厚度大以及性价比高等特点。通过热氧化表面处理技术能够在钛及钛合金表面形成较厚的由钛氧化层和氧的扩散层组成的硬质氧化膜,氧化膜对材料起到有效的保护作用,提高了材料单一耐磨性、耐蚀性以及生物活性或综合表面性能。从热氧化工艺原理及其对钛及钛合金表面性能影响的角度,综述了热氧化对钛及钛合金表面硬度、耐磨性、耐蚀性、生物相容性等性能影响的研究进展,并对其以后的研究方向进行了展望。通过合理控制氧化温度、氧化时间、氧化气氛及冷却方式等工艺条件,从而得到连续、致密且疲劳性能较好的金红石型TiO_2和氧的扩散层是改善钛及钛合金性能的关键。将热氧化处理与其他工艺相结合,针对性地提高膜层厚度及材料的耐磨性、耐蚀性、生物性能等,以实现复合涂层的制备将是热氧化在钛及钛合金性能改善方面的研究方向。     

TC4钛合金热氧化层微米压痕/划痕试验研究

采用微米压痕实验测试了氧化层的硬度、弹性模量,研究了热氧化工艺对TC4钛合金表面热氧化层力学性能的影响;通过微米划痕实验考察了氧化层的临界荷载以及划擦行为.结果表明:热氧化处理后TCA表面生成由金红石TiO2和少量Al2O3所组成的氧化层,钛合金表面硬度和弹性模量显著增加,弹性模量与硬度的比值降低,表明热氧化工艺可改善钛合金的耐磨性.长时间的高温氧化可以增加氧化层的厚度,但在划擦过程中氧化层发生两次脱落,表明氧化层由外表层和次外层组成,外层结合力差,易发生一次脆性剥落.内层与基体的结合强度较高,但在较大载荷作用下会产生微裂纹,导致氧化层的二次剥落.     

表面氧化层对TiMn1.25Cr0.25储氢合金活化性能的影响

通过TiMn1.25Cr0.25合金粉活化前在空气中暴露不同的时间,探讨了表面氧化层的形成对其活化性能的影响。活化测试结果表明：合金的活化难度随着合金在空气中暴露时间的延长而加大。俄歇电子能谱(AES)结果表明,在空气中暴露后的合金表面形成了一层大约6nm-10nm厚的表面氧化层,正是这层氧化层的形成加大了合金的活化难度。扫描电镜(SEM)结果表明合金的活化过程与合金的碎化有着密切的联系。     

Formation Mechanism of Nanoparticles in Fe–Cr–Al ODS Alloy Fabricated by Direct Oxidation Method

This study presents the fabrication of 14CrFe-Cr-Al oxide dispersion strengthened(ODS) alloy by a direct oxidation process.In order to explain how oxide nanoparticles are formed in the consolidation process,the powders after oxidation are subjected to vacuum thermal treatment at high temperatures.Differential scanning calorimeter,X-ray photoelectron spectroscopy,scanning electron microscopy and transmission electron microscopy techniques are used to detect the generation,evolution of oxides on both the surface and interior of the powder,as well as the type of oxide nanoparticles in the fabricated ODS alloy.It is found that an iron oxide layer is formed on the surface of the powder during low temperature oxidation.And the iron oxide layer would be decomposed after thermal treatment at high temperature.In the consolidation process,the oxygen required by the reaction of alumina and yttrium oxide to produce nano scale Y-Al-O particles mainly derives from the decomposition of iron oxide layer at elevated temperature and the inward diffusion of oxygen.Using the direct oxidation process,YAlO_3 nanoparticles are dispersed in the grains and at the grain boundaries of Fe-Cr-Al ODS alloy.     

镁合金直接涂装工艺研究

试验研究了一种不需要转化膜等过渡层的镁合金表面直接涂装工艺。底漆是一种含有磷酸的活性涂料,镁合金表面允许有微量氧化物或水分存在。喷涂面漆后涂层总厚度为50μm～70μm,涂层附着力可以达到1级,中性盐雾试验240 h表面不起泡。     

机械镀合金镀层的研究进展

首先,概述了近年来国内外对机械镀合金层研究的发展历程,指出不同种类机械镀合金层在湿式与干式工艺中的研究难点,湿式机械镀研究主要集中于镀层形成机理、锌基复合镀层及表面活化剂等,干式机械镀主要集中于镀层的合金化及镀层合金材料的配制方面。其次,分析了2种不同工艺下合金镀层的形成机理及合金镀层的防腐机理,湿式镀层由金属粉依靠表面活性剂和沉积促进剂在先导金属的作用下稳定持续形成,从而在基体表面形成防腐屏障;干式镀层依靠合金包覆的丸粒高速喷射冲击基体而形成,合金层和其表面的氧化膜作为防护层。最后,基于合金镀层优良的耐蚀性能和机械镀工艺特点,给出了研究发展以合金粉为原料的湿式机械镀的倡议,并从活化与沉积稳定性、绿色与复合化、产业标准化等方向,提出了机械镀合金镀层在防腐材料领域的发展趋势及研究建议。     

Interfacial reactions between molten Al and a Co–Cr–Mo alloy with and without oxidation treatment

The effect of the formation of an oxide layer on the interfacial reactions between a Co–Cr–Mo alloy (CCM alloy) and molten Al is investigated. In the absence of an oxide layer, the CCM alloy reacted rapidly and an interfacial two-layer structure formed between the CCM alloy and molten Al. Upon oxidation, a uniform (Cr,M)₂O₃ (M: doped elements) oxide layer formed on the CCM alloy surface, which effectively inhibited the reaction between the CCM alloy matrix and molten Al for more than 2 h.     

Characterization of plasma electrolytic oxide formed on AZ91 Mg alloy in KMnO4 electrolyte

The aim of this work is to investigate microstructure, corrosion resistance characteristics and nanohardness of the oxide layer on AZ91 Mg alloy by applying different voltage with KMnO₄ contained solution. There are lots of closed pores that are filled with another oxide compound compared with the typical surface morphology with pore coated until 350 V of coating voltage. The thickness of oxide layer increases with increasing coating voltage. The oxide layer formed on AZ91 Mg alloy in electrolyte with potassium permanganate consists of MgO and Mn₂O₃. Corrosion potential of the oxide layer on AZ91 Mg alloy obtained at different plasma electrolytic oxidation(PEO) reaction stages increases with increasing coating voltage. The corrosion resistance of AZ91 Mg alloy depends on the existence of the manganese oxide in the oxide layer. The inner barrier layer composed of the MgO and Mn₂O₃ may serve as diffusion barrier to enhance the corrosion resistance and may partially explain the excellent anti-corrosion performance in corrosion test. Nanohardness values increase with increasing coating voltage. The increase in the nanohardness may be due to the effect of manganese oxide in the oxide layer on AZ91 Mg alloy coated from electrolyte containing KMnO₄.     

OXIDATION OF PM ALLOY Al-10Ti DURING SLIDING WEAR

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An approach to modeling simultaneous high-temperature oxidation and erosion

An approach is suggested for describing the rate of degradation of alloys subjected to the combined effects of high-temperature oxidation and erosion. The basis for this approach is essentially empirical, and is drawn from observations of the kinetics and scale morphologies of alloys in laboratory tests. The two major assumptions used are that the alloy surface is always covered by an oxide layer, and that only oxide (not alloy substrate) is removed by the erosion process. The mode of erosion is not explicitly defined. The rate of erosion, that is, the amount of oxide lost in a given erosion event, is taken to be proportional to the thickness of the oxide layer. The relationships developed have been found capable of accurately describing the shapes of oxidationerosion kinetic curves, and the predicted thickness of the steady-state oxide layers remaining on the alloys agreed reasonably with experimental observations.     

合金元素对新型Co-Al-W合金热腐蚀行为的影响

研究了由γ'-Co₃(Al,W)相沉淀强化的新型钴基Co-Al-W 高温合金在800℃、75% Na₂SO₄+25% NaCl熔盐中的热腐蚀动力学及合金元素Mo、Nb、Ta和Ti对合金热腐蚀行为的影响。研究发现,2Mo、2Nb、 2Ta和2Ti合金比9.8W合金具有更好的抗热腐蚀能力,Mo和Ti对提高合金耐热腐蚀能力的效果比Ta和Nb显著。加入合金元素的合金热腐蚀膜由三层组成,即主要由Co氧化物CoO和Co₃O₄组成的腐蚀膜外层,由合金元素、Al、 Co及W复杂氧化物组成的中间过渡层和由Al、Co氧化物组成的腐蚀膜内层。随着腐蚀时间的增加,中间过渡层厚度逐渐增加,热腐蚀膜内、外层厚度变化不大,但内层致密性逐渐增加。     

Electrochemical impedance characteristics of LC4 aluminum alloy treated with ZH1 technique

ZH1 technique was used to form a corrosion resistant layer on LC4 alloy. The composition of the layer was studied by X-ray photoelectron spectroscopy (XPS). It is found that the layer is composed of oxides of metals on the substrate, such as A12O3, ZnO, MgO2, CuO, and MnO2. The electrochemical impedance spectrums (EIS) of LC4 aluminum alloy specimen were measured in NaCl solutions to study the mechanism of the corrosion resistance of the alloy treated with ZHI technique. The results show that in NaCl solutions the capacitance of the Helmholtz layer and space charge layer of the oxide coating formed on the surface of LC4 alloy is less than that of a normal metal electrode while its ohmic resistance is relatively greater. At the same time, the thickness of the Helmholtz layer is 1-3 exponentially greater than that of a normal metal electrode. Compared with a normal metal electrode, all these characteristics make it more difficult for charges to transfer between the solution and the surface of the electrode. That is why the polarized current density of LC4 alloy treated with ZHI technique kept small in 3.5% NaCl solution within a wide range of potential, and why the polarized curves of LC4 alloy treated with ZH1 technique changed a little in 3.5% NaCl solution of different pH values.Moreover, according to the capacitance of the space charge layer (Csc) obtained at different potentials in 3.5% NaCI solution, I/Csc^2-E curve was laid out. It is found that there does not exist a simple linear relation between I/Csc^2 and the potential. Therefore, the oxide coating formed on LC4 alloy with ZH1 technique is not a semiconductor at room temperature.     

Oxidation Behavior of K4750 Alloy at Temperatures Between 750 ℃and 1000 ℃

This study investigated the oxidation behavior of a new casting Ni-based superalloy K4750 at 750 ℃-1000 ℃ in air for 100 h-1000 h by isothermal oxidation tests.The oxidation-kinetic curves were plotted by the static discontinuous weight gain method.Observation and identification of oxidation products were conducted using scanning electron microscopy(SEM),energy dispersive spectroscopy (EDS),electron probe micro-analysis (EPMA) and X-ray diffraction (XRD).X-ray photoelectron spectrometer (XPS) was also used to analyze the chemical state of elements and the distribution in depth.The results showed that the oxidation-kinetic curves of K4750 alloy basically obeyed the parabolic law.The average oxidation rate below 900 ℃ was less than 0.1 g/m2.h which meant the alloy was at a complete anti-oxidation grade,and the alloy was at an anti-oxidation grade at 1000 ℃.The predominant surface oxide was Cr2O3,and a double layer structure of the oxide scale was observed at all tested temperatures as time increased.The outer oxide layer contained continuous Cr2O3 and a small amount of oxides mixed TiO2 and NiCr2O4,while the inner oxide layer was composed with Al2O3.The oxidation process could be interpreted by the competitive oxidation of different elements.The diffusion rate of Ti through Cr2O3 layer increased with increasing temperature,and thus the generation of TiO2 was advantageous.The dispersed TiO2 reaching a certain amount destroyed the continuity of the surface oxide layer,which accounted for the reduction of oxidation resistance of K4750 alloy at high temperatures.     

Effect of CeO<Subscript>2</Subscript> Coating on the Isothermal Oxidation Behaviour of Ni-Based Alloy 230

Ceria coating was deposited on alloy 230 using an electro-deposition process in a cerium nitrate electrolyte. Reactive element effects were investigated by comparing the oxidation behaviour of the samples with and without the ceria coating. The prepared ceria coating reduced the oxidation rate and improved the adherence of the oxide layer. A thicker oxide layer with large spallation areas formed on the uncoated sample, while a thin and protective oxide layer was found on the coated sample after oxidation for 1000 h at 900 °C. The oxidation mechanisms of alloy 230 with and without ceria coating were discussed. Furthermore, as the ceria coating changed the grain shapes of chromium oxides from columnar to an equiaxed structure, discussion also advanced proposals regarding the mechanisms of formation of these different oxides. The equiaxed grains enhanced the adhesion of the oxide to the alloy surface.     

Ti-Cr合金的非等温氧化及着火预测(英文)

采用热重分析、XRD和SEM等方法研究Ti-Cr合金(0≤w(Cr)≤25%)从室温至1723K的非等温氧化行为及氧化膜的微观结构,探讨Cr元素对Ti-Cr合金抗氧化能力的影响机制。结果表明:当Cr含量小于某一临界值wC时,随着Cr含量的增加合金的抗氧化能力降低;当Cr含量高于wC时,随着Cr含量的增加合金的抗氧化能力提高;当温度高到1000K时,Ti-Cr合金的氧化仍符合抛物线规律,且主要发生钛的氧化;Ti-Cr合金氧化后基体中存在氧扩散层,氧化膜主要为金红石型TiO2,内层氧化膜出现富Cr现象,Cr氧化物的析出提高了Ti-Cr合金的抗氧化能力。金属和合金的着火是一个快速非等温氧化的过程,预测了Ti-Cr合金着火阶段的氧化机制。     

Ni-Cr-W合金在1100 ℃的氧化膜演变

对新型Ni-Cr-W合金在1100 ℃下不同保温时间下的恒温氧化行为进行了研究。采用扫描电镜（SEM）以及能谱（EDS）对合金热暴露后的表面氧化膜形貌、元素含量以及合金基体的恶化情况进行了分析,表面氧化膜的相组成通过XRD进行确定。结果表明：在氧化初期（<3 h）,合金表面生成的单层氧化膜主要由Cr2O3组成,随着氧化时间的延长（>7 h）,在Cr2O3外逐渐形成了一层具有尖晶石结构的NiCr2O4。一旦外表面被均匀致密的尖晶石膜所覆盖,双层氧化膜NiCr2O4·Cr2O3便能有效的减慢合金基体被进一步氧化。合金亚表层的恶化形式包括晶界的内氧化、空洞以及无碳化物区的形成。合金中高的W含量并没有明显恶化合金的抗氧化性能。     

Reactive molecular dynamics study of the oxidation behavior of iron-based alloy in supercritical water

A theoretical study of the oxidation behavior of iron-based alloy in the supercritical water (SCW) has been carried out based on ReaxFF force-field molecular dynamics simulation. An atomic model has been proposed to simulate the initial chemisorption reactions and atoms diffusion behavior across the oxide layer. Simulation results imply that Cr addition has an important effect on the oxidation behavior of iron-based alloy. In the initial stage of oxidation, H₂O prefers to adsorb on the Cr atom, and some species in the form of Cr(OH)₄ are observed on the FeCr alloy surface. Once an initial oxide layer is formed, further oxidation is controlled by the migration of vacancy. The O vacancies are formed at the oxide/FeCr alloy interface and migrate toward the steam, whereas Fe vacancies are formed at the oxide/steam interface and migrate toward the FeCr alloy. Attributed to the stronger binding energy of O–Cr bond than O–Fe bond, the Cr diffusivity in the oxide is less than Fe atoms. Thus, double oxide layers, including the inner Fe–Cr–O layer and outer Fe–O layer, are formed on the FeCr alloy, which is in good agreement with previous experimental observation.     

钛合金的高温固态渗氧-扩散固溶复合处理

为了提高钛合金的表面耐磨性能，发展了一种表面无氧化膜的高温固态渗氧．扩散固溶复合处理方法（OP-DS）。利用TGA，SEM，XRD，XPS及显微硬度计对OP-DS处理后的钛合金进行了研究。结果表明：OP-DS方法能显著提高合金表面层的硬度，硬化层深度随预渗氧时间的延长而增加；预渗氧处理时间对扩散固溶效果有很大的影响，适当的预渗氧时间可在表面形成无膜强化固溶层。从热力学及动力学角度对渗氧．扩散固溶机理进行了探讨。     

镁合金阳极氧化膜成膜过程的交流阻抗谱研究

采用阳极氧化工艺对AZ31镁合金进行表面处理,利用交流阻抗技术(EIS)研究了阳极氧化膜的成膜过程。结果表明,不同氧化时间氧化膜的阻抗谱变化具有明显的规律性,可以划分为4个阶段,并且各阶段之间存在显著差异。利用R(C(R(QR)))(CR)模型进行计算机拟合,得到的等效电路元件拟合值显示:随着氧化时间的延长,膜表面孔洞增多,粗糙度也随之增大;氧化膜阻挡层和多孔层的生长并不同步,而是一个动态变化的过程。     

High temperature oxidation of FeCrAl‐alloys – influence of Al‐concentration on oxide layer characteristics

The superior high temperature oxidation resistance of FeCrAl alloys relies on the formation of a dense and continuous protective aluminium oxide layer on the alloy surface when exposed to high temperatures. Consequently, the aluminium content, i.e. the aluminium concentration at the alloy–oxide layer interface, must exceed a critical level in order to form a protective alumina layer. In the present study the oxidation behaviour of six different FeCrAl alloys with Al concentrations in the range of 1.2–5.0 wt% have been characterised after oxidation at 900 °C for 72 h with respect to oxide layer surface morphology, thickness and composition using scanning electron microscopy, energy dispersive X‐ray spectroscopy and Auger electron spectroscopy. The results show that a minimum of 3.2 wt% Al in the FeCrAl alloy is necessary for the formation of a continuous alumina layer. For Al concentrations in the range of 2.0–3.0 wt% a three‐layered oxide layer is formed, i.e. an oxide layer consisting of an inner alumina‐based layer, an intermediate chromia‐based layer and an outer iron oxide‐based layer. In contrast, the 1.2 wt% Al FeCrAl alloy is not able to form a protective oxide layer inhibiting extensive oxidation.