Improvement in the oxidation resistance of TiAl by preoxidation in a SiO2-powder pack

The resistance of TiAl coupons to cyclic oxidation at 1300 K in a flow of purified oxygen under atmospheric pressure has been significantly improved by preoxidation. The preoxidation was performed by heating the specimens, buried in a silica powder and encapsulated in a silica tube under a vacuum of 1.3×10^–3 Pa at 1200 K for 100 ks. After 20 cycles (400 hr) of oxidation the mass gain was still very small, and correspondingly the scale thickened very slightly. This superior oxidation resistance is attributable to the formation of a scale very rich in alumina by the preoxidation under a very low-oxygen partial pressure. This low-oxygen partial pressure may be near the dissociation pressure of silica and much lower than that attained by modern vacuum pumps.     

Environmental corrosion resistance of porous TiAl intermetallic compounds

Porous TiAl intermetallic compound, as a novel substitute for current inorganic porous material, offsets the shortages of both ceramics and metals. The environmental corrosion resistance of porous TiAl intermetallic compound was investigated. The kinetic equation for the cyclic oxidation of porous TiAl alloy at 600 ℃ is determined to be Δm2=1.08×10-5t. After total oxidation of 140 h, porous TiAl intermetallic compound shows more stability of pore structure and the mass gain of TiAl alloy is 0.042 g/m2, which is only 10.6% that of porous 316L stainless steel. The kinetic equation for the cyclic corrosion behavior of porous TiAl alloy in hydrochloric acid with pH=2 at 90 ℃ is determined to be Δm2=5.41×10-5t-2.08×10-4. After 50 h exposure, the mass loss of TiAl alloy is 0.049 g/m2, which is only 14.8% and 5.57% that of porous Ti and stainless steel, respectively. The kinetic equation in hydrochloric acid with pH=3 is determined to be Δm2=2.63×10-6t-3.72×10-6.     

放电等离子烧结的钛铝合金组织及氧化性能研究

研究了TiH2-45Al-0.2Si-5Nb未球磨和球磨两种粉末的放电等离子烧结组织特征以及经1000℃、100h高温氧化后的氧化性能.结果表明,未经球磨粉末的烧结组织由层片状TiAl和Ti3Al相组成,而经球磨粉末的烧结组织由细小的颗粒状TiAJ和Ti3Al相组成.球磨粉末的烧结组织氧化速度低于未球磨粉末的烧结组织,形成了连续的Al2O3和TiO2混合氧化物层,具有良好的高温抗氧化性.     

TiAl基合金离子渗碳与高温抗氧化性研究

研究了辉光离子渗碳处理对TiAl基合金的渗层组织、表面硬度和抗高温氧化性的影响。实验显示,渗碳处理可在TiAl基合金的表面形成由碳化物和过渡层组成的复合相结构,经不同渗碳处理的试样,其表面硬度和抗高温氧化性均得到明显提高。     

Mechanism of isothermal oxidation of the intel-metallic TiAl and of TiAl alloys

The oxidation behavior of Ti36Al, Ti35Al-0.1C, Ti35Al-1.4V-0.1C, and Ti35 Al-5Nb-0.1C (mass-%) in air and oxygen has been studied between 700 and 1000°C with the major emphasis at 900°C. Generally an oxide scale consisting of two layers, an outward- and an inward-growing layer, formed. The outward-growing part of the scale consisted mainly of TiO₂ (rutile), while the inward-growing part is composed of a mixture of TiO₂ and -Al₂O₃. A barrier layer of Al₂O₃ on TiAl between the inner and the outer part of the scale was visible for up to 300 hr. Under certain conditions, the Al₂O₃ barrier dissolved and re-precipitated in the outer TiO₂ layer. This shift leads to an effect similar to breakaway oxidation. Only the alloy containing Nb formed a longlasting, protective Al₂O₃ layer, which was established at the metal/scale interface after an incubation period of 80–100 hr. During this time, Nb was enriched in the subsurface zone up to approximately 20 w/o. The growth of the oxide scale on TiAl-V obeyed a parabolic law, because no Al₂O₃ barrier layer formed; large Al₂O₃ particles were part of the outward-growing layer. A brittle 2-Ti₃Al-layer rich in O formed beneath the oxide scale as a result of preferential Al oxidation particularly when oxidized in oxygen. Oxidation in air can lead also to formation of nitrides beneath the oxide scale. The nitridation can vary between the formation of isolated nitride particles and of a metal/Ti₂AlN/ TiN/oxide, scale-layer system. Under certain conditions, nitride-layer formation seemed to favor protective Al₂O₂₃ formation at the metal/scale interface, however, in general nitridation was detrimental with the consequence that oxidation was generally more rapid in air than in oxygen.     

Effect of chromium on the oxidation resistance of TiAl intermetallics

The effect of 10 at.%Cr on the oxidation resistance of TiAl intermetallic compound at 800–1100°C in air was investigated. The results indicated that 10 at.%Cr equally substituting for Ti and Al in TiAl alloy had duplex effects on the isothermal kinetics of DAL At lower temperatures (800–900°C), Cr increased the oxidation rates as a result of the doping effect of Cr in the scale and at higher temperatures (1000–1100°C), especially at 1100°C, Cr significantly reduced the oxidation rates as a result of the formation of a continuous Al₂O₃ film on the surface. 10 at.%Cr only substituting for Ti in TiAl alloy remarkably reduced the oxidation rates at all temperatures by about two orders of magnitude. Moreover, 10 at%Cr significantly improved the cyclic-oxidation rsistance of TiAl alloy.     

低温真空扩散反应制备高性能TiAl合金粉

通过高能球磨均匀混合以及低温真空预烧工艺制备TiAl合金粉,原料为粒度43μmTi粉和9~12μmAl粉,研究不同温度下不同保温时间后Ti、Al混合粉的合金化程度。结果表明:高能球磨1h的Ti、Al混合粉在500℃保温2h,再在600℃保温3h能制得主要为TiAl相和少量Ti3Al相的合金粉,制备合金粉的平均粒径为20μm左右。     

Effects of additives on corrosion and wear resistance of micro-arc oxidation coatings on TiAl alloy

Ceramic coating was deposited on TiAl alloy substrate by micro-arc oxidation(MAO)in a silicate-aluminate electrolyte solution with additives including sodium citrate,graphite and sodium tungstate.The microstructures and compositions were analyzed by SEM,EDX and XRD.The corrosion and wear properties of the coatings were investigated by potentiodynamic polarization and ball-on-disc wear test,respectively.The results show that the MAO coatings consist of WO3,Ti2O3,graphite and Al2O3 besides Al2TiO5 and Al2SiO5.With additives in the electrolyte,the working voltage at the micro-arc discharge stage decreases,and the ceramic coating gets smoother and more compact.The corrosion current density of MAO coating is much lower than that of TiAl substrate.It can be reduced from 9.81×10-8A/cm 2to 3.02×10-10A/cm 2 .The MAO coatings composed of hard Al2O3,WO3 and Ti2O3 obviously improve the wear resistance of TiAl alloy.The wear rate is-3.27×10-7g/(N·m).     

Ti2AlC／TiAl复合材料的高温氧化性能研究

利用放电等离子烧结（SPS）技术，原位制备Ti2AlC／TiAl和Ti2AlC／TiAl（Nb，B）复合材料，并研究其在900℃和1000℃的高温氧化性能。研究发现，掺加Nb，B后复合材料的抗氧化性能明显提高，1000℃氧化30h时氧化层厚度为50μm～60μm，未掺入Nb，B时其厚度约为170μm。在氧化层和复合材料交界处结构疏松出现许多孔洞，Nb原子在高温时向表面层富集使复合材料抗氧化性能提高，富Nb层的存在即可以阻挡氧原子的继续渗入，又可以作为扩散障，减少Kirkendall效应；加入B后，组织明显细化，氧化反应初始阶段氧化物的形核增多。     

利用SiO2中间层提高铝化物涂层的高温防护性能

目的提高TiAl合金的抗高温氧化性能。方法采用料浆法和电沉积法在TiAl合金表面制备Al-SiO_2复合涂层。通过静态空气氧化测试评价复合涂层对TiAl合金抗高温氧化性能的影响,利用X射线衍射仪分析高温氧化前后涂层物相组成,借助扫描电子显微镜分析试样表面和截面微观组织和形貌。结果 1000℃氧化过程中,铝化物涂层具有一定的抗高温氧化性能,氧化100 h后增重为10.44 mg/cm~2。然而其表面仍然出现了淡黄色TiO_2氧化层,并且存在裂纹等缺陷,表面涂层物质在热处理过程中与基体组织发生了大量互扩散。Al-SiO_2复合涂层经过100 h氧化后,表面形貌基本保持不变,未观察到裂纹等缺陷,随着Si O_2中间层沉积时间延长,试样的抗高温氧化性能总体呈现上升趋势。-2 mA/cm~2下电沉积300 s制备的SiO_2涂层抗高温氧化性能显著提高,其氧化增重仅为3.03 mg/cm~2。结论 Al-SiO_2复合涂层能够有效地提高TiAl合金的抗高温氧化性能。     

XRD Investigations of the Phosphorus Effect on the Oxidation of TiAl Alloys by High-Resolution Methods

Recently it has been found that very small amounts (a few 100 ppm) of Padded to -titanium aluminide can significantly alter the oxidationbehavior between 973 and 1273 K. The mechanism responsible for this changeis, however, still not clear. In the present study, phosphorus wasincorporated into the surface of TiAl (containing 50 at.% Al) by ionimplantation and oxidation tests were carried out at 1173 K inair. Improvement of oxidation resistance is only temporary up to 100 hr forphosphorus-implanted TiAl. After 100 hr, the oxidation rate increases andbreakaway oxidation follows. XRD and EPMA showed that the breakawayoxidation is connected with massive nitride formation. Two different modelsare proposed which can explain the effect of phosphorus additions on theoxidation kinetics of TiAl during the protective stage within the first100 hr. The breakaway effect can be explained by penetration of air to themetal–oxide interface zone because of microcrack formation in theoxide scale, which was experimentally proved by acoustic-emission analysis.     

TiAl合金表面等离子喷涂层的形貌和抗氧化性分析

采用等离子喷涂方法在TiAl合金表面喷涂,得到由CoNiCrAlY粘结层和(ZrO2 Y2O3)陶瓷外层组成的双层结构的热障涂层。对涂层进行了高温抗氧化试验,并用SEM和金相法观察和分析了涂层的组织及形貌。结果表明,经喷涂后试样的高温抗氧化能力显著提高。     

Effect of Hf addition (0.24 w/o) on the oxidation behavior of TiAl at high temperatures

The isothermal oxidation behavior of TiAl coupons containing 0.24 wt.% Hf has been studied in the temperature range 1100 to 1400 K in a flow of purified oxygen at atmospheric pressure. The addition of Hf is very effective in decreasing the overall oxidation rate at temperatures up to 1300 K, although the oxidation rate was slightly increased during the initial period of about 10 ks, after which a very low oxidation rate was maintained. However, at 1350 K the effect becomes small, and at 1400 K it is inverted. The excellent oxidation resistance obtained is attributable to the formation of two alumina-rich layers in the scale; one is beneath the outer rutile layer and the other at the scale/substrate interface. In addition, no internal oxides were formed in the substrate up to 1300 K.     

Effect of a sputtered TiAlCr coating on the oxidation resistance of TiAl intermetallic compound

The effect of a sputtered TiAlCr coating on the oxidation resistance of TiAl intermetallic compound was investigated in static air. The bare TiAl alloy exhibited poor isothermal and cyclic-oxidation resistance at 800–1000°C due to the formation of TiO₂-base scales which tend to spall during cooling. A sputtered Ti-50Al-10Cr coating remarkably improved the oxidation resistance of TiAl, due to the formation of an adherent Al₂O₃ scale at 800–1000°C. After long-term oxidation (at 900°C for 1000 hr), TiAlCr coating still provided excellent protection for the TiAl alloy. Minor interdiffusion occurred due to the inward diffusion of Cr, while no Kirkendall voids were found at the coating/ substrate interface. In contrast, NiCrAlY and CoCrAlY coatings reacted extensively with the TiAl alloys. Moreover, the TiAlCr coating alloy is based on -TiAl and TiAlCr Laves phases, which may offer improved mechanical properties. The TiAlCr coating exhibited a better combination of oxidation resistance and substrate compatibility than conventional aluminide and MCrAlY coatings.     

Influence of alloy compositions on the halogen effect in TiAl alloys

F‐implantation concentration profile simulations were carried out and the influence of the ion fluence, implantation energy as well as the alloy composition were investigated. For alloys with Al contents between 40 and 50 at% the conditions to get the halogen effect were assessed by thermodynamic calculations. According to the thermodynamic predictions the implantation parameters were kept constant in this composition range. The implanted alloys were exposed in laboratory air over 4000 h. With the implantation parameters used (20 keV and 1 × 10¹⁷ F/cm²), the halogen effect was found to be efficient over 4000 h. The oxide growth kinetic constants were measured and vary between 1.2 and 2.7 × 10^?13 g²/cm⁴/s.     

机械合金化和微量添加剂对TiAl基合金显微组织及高温抗氧化性能的影响

研究了采用机械合金化方法制备TiAl基合金的工艺及其对显微组织的细化作用，概述了一系列添加剂对TiAl基合金高温抗氧化性能的影响。     

铜基体上渗铝层的高温抗氧化性能和组织变化(英文)

以铜为基体,采用电镀镍和浆料包渗铝法,在800°C渗铝12 h制备出组织为Ni2Al3的单相渗层。采用SEM、XRD和光学显微镜,研究在1000°C下空气中氧化25~250 h,Ni2Al3渗层的高温抗氧化性能与组织转变行为。结果表明:Ni2Al3渗层在1000°C氧化250 h后,氧化增重分别为纯铜和镍镀层的1/15和1/2。氧化时间在25 h内时,渗层表面仍有Ni2Al3相;氧化50 h后,出现NiAl相;当氧化时间增加到100 h时,Ni2Al3相完全转变为NiAl相。当氧化到250 h时,渗层仍具有良好的抗高温氧化性能。     

High-temperature oxidation of pure titanium in CO2 and Ar-10%CO2 atmospheres

The oxidation behavior of pure titanium has been investigated in the temperature range of 1000 K to 1300 K in CO₂ or Ar-10%CO₂. Optical microscopy, electron probe microanalyses, and X-ray measurements on the oxide scales formed during oxidation indicate that their structures are nearly independent of temperature and the corrosion atmosphere. The scales consisted of two layers, an external one and an internal one, having a rutile (TiO₂) structure. The parabolic rate law was confirmed for growth of the external scale and the permeation depth of oxygen in titanium with apparent activation energies of 266 and 226 kJ/mol, respectively. The rate-determining diffusion species in the oxidation processes are discussed.     

Preparation and crystalline phase of a TiO2 porous film by anodic oxidation

Anatase titanium dioxide is an active photocatalyst, but it is difficult to immobilize on the substrate. A crystalline TiO2 porous film was prepared directly on the surface of pure titanium by anodic oxidation in this work. Constant voltage and constant current anodic oxidation were adopted with sulphuric acid used as the electrolyte, pure titanium as the anode and copper as the cathode. The morphology and structure of the porous film on the substrate were analyzed with the aid of Field Emission Scanning Electron Microscopy （FESEM） and X-ray Diffraction （XRD）. The effects of the parameters of anodic oxidation （such as voltage, the concentration of sulphuric acid, anodization time and current density） on the aperture and the crystalline phase of the TiO2 porous film were systematically investigated. The results indicate that the increase of current density facilitates the augment of the aperture and the generation of anatase and mille. In addition, the forming mechanism of anatase and mille TiO2 porous films was discussed.     

TiAl合金表面Si-Co-Y扩散渗层的高温抗氧化性能

采用扩散共渗方法在TiAl合金表面制备了Si-Co-Y渗层,分析了渗层的组织结构、形成机理及其在950 ℃时的抗氧化性能。所制备的Si-Co-Y渗层组织致密,呈多层结构：主要由TiSi₂表层,TiSi₂+Ti₅Si₄+Ti₅Si₃混合组成的外层,Ti₅Si₃中间层和TiAl₂内层组成;渗层生长过程由Si的向内扩散控制,且遵循先沉积Si后沉积Co的有序过程。氧化实验结果表明,Si-Co-Y渗层具有良好的高温抗氧化性能,在950 ℃氧化100 h后表面形成了由SiO₂, TiO₂和Al₂O₃组成的保护性氧化膜;该氧化膜的生长遵循抛物线规律,氧化增重的抛物线速率常数约为6.3×10_-2 ^mg₂^/cm₄ ^h_1/2^,较基体合金低约一个数量级。