NiCoCrAlYTa涂层与镍基高温合金基体互扩散行为研究

采用大气等离子喷涂技术(APS)在镍基高温合金GH536上制备Ni Co Cr Al YTa涂层。通过SEM、EDS等方法研究了Ni Co Cr Al YTa涂层与合金基材在1000℃下界面的元素或扩散行为及涂层组织演变规律。结果表明:随着氧化时间延长,涂层中的Co、Al及基材中的Fe、Mo发生了明显的互扩散,涂层中发生了β→γ’→γ的相转变。氧化500h后,元素Y、Ta扩散到了涂层氧化膜中,靠近界面处的涂层基体中出现了大量横向排列、尺寸在5μm左右的富Ta相,形成了一个扩散障,减缓了涂层与基材之间元素互扩散。     

一种镍基单晶高温合金的显微偏析行为

研究了一种新型镍基单晶高温合金DD98铸态组织的显微偏析行为.实验结果表明,当合金以枝晶凝固时,组织中存在显微偏析.其中元素Mo、Cr、Ti、Ta、Al在枝晶间富集,Ti、Mo、Ta、Cr的偏析较为严重,Al的偏析程度相对小一些,Ni、Co、W为枝晶干偏析元素,其中W的偏析最为严重;共晶中富集Al、Ta、Ti、Ni,贫Co、W、Cr、Mo.凝固速率对枝晶偏析有显著的影响.随着抽拉速率的增加,元素Al、Mo、Co、Ti的偏析程度增加,而Ta的偏析程度降低,其它元素的偏析程度变化不大.     

Ti基表面激光重熔Al涂层及高温氧化行为研究

为了提高纯Ti的高温抗氧化性能,采用电弧喷涂方法在Ti基表面制备Al涂层。采用激光重熔扫描Al涂层,使Ti层与Al层发生冶金反应,对其进行800℃,40h连续氧化,根据Ti与Al反应生成的金属间化合物,研究其高温抗氧化行为。结果表明:经过表面改性处理后的Al涂层可以显著地提高纯Ti的高温抗氧化性能;在激光重熔过程中,Al元素发生熔化扩散与Ti结合形成以Ti Al3为主的扩散层;在高温氧化过程中,涂层表面形成连续且致密的α-Al2O3,同时扩散层中的富Al相为Ti基表面提供充足的Al元素,进而对Ti基体提供有效的高温抗氧化保护作用。     

Ta含量对NiCoCrAlY涂层性能的影响

采用真空雾化的方法制备了Ta含量为0、2%及5%的NiCoCrAlYTa合金粉末,利用超音速火焰喷涂制备了三种涂层,研究了Ta对合金粉末微观组织及物相的影响,绘制了1050℃条件下涂层的高温氧化动力学曲线,研究了500h氧化试验后涂层组织和β相的分布,初步探讨了Ta元素对改善涂层抗氧化性能的作用机理。研究结果表明:Ta通过提高MCrAlY体系抗氧化元素的溶质浓度,促进了氧化膜的形成,随着Ta含量的增加,涂层的内氧化程度降低,涂层抗氧化性能提高。但含Ta涂层在长时间氧化条件下会生成CrTaO_4、AlTaO_4等尖晶石类氧化物,且Ta的氧化物PBR值较大,对涂层的抗热震性能不利。     

Ta 含量对 MCrAlY 抗氧化性的影响

相影响着MCrAlY涂层的抗氧化性,改善涂层中β相含量可以通过添加特定元素实现。Ta被认为是可以用来改善涂层抗氧化性的重要元素之一。本研究模拟考察了不同Ta含量对MCrAlY涂层相组分的影响,并在此基础上,开展了1000℃恒温氧化实验。研究结果表明,随着Ta含量的增加,涂层的贫铝区厚度减小,剩余的β含量增加,其分布也更靠近涂层表面;但较高的Ta含量加剧了Ta元素在涂层中的偏析。综合考虑,3%Ta含量的MCrAlY涂层抗氧化性最好。另外,本文还着重研究了优选Ta含量的MCrAlY的氧化过程。     

不锈钢基体表面CVD-Ta涂层组织和性能的研究

介绍了化学气相沉积(CVD)制备难熔金属Ta涂层的一般原理及方法。利用TaCl_5-H_2-Ar反应体系,采用化学气相沉积法在不锈钢基体表面沉积了Ta涂层。通过X射线衍射仪(XRD)和扫描电镜(SEM)手段,研究了CVD温度对Ta涂层的结构、沉积速率、显微组织的影响,分析了Ta涂层的显微组织结构和成分组成,对Ta涂层试样在强酸冲刷条件下进行了耐腐蚀试验,最后对Ta涂层试样的失效机理进行了分析。结果表明:在1000～1200℃范围内,随着沉积温度的升高,Ta涂层晶粒结晶性能逐渐变好,沉积速率逐渐增大,当沉积温度大于1100℃,Ta涂层和基体之间会出现较明显的扩散层;Ta涂层主要由分布均匀的钽元素和少量不连续的氧元素组成;涂层的失效的主要原因是由于Ta涂层纵向生长的柱状晶不致密,使得晶界处的氧化物率先腐蚀,使得钽涂层逐渐失去对基体的保护作用。     

Nb-Ti-Al合金及其硅化物涂层的高温氧化行为

采用电子束和真空自耗电弧熔炼法制备Nb-40Ti-7Al(质量分数,%)合金,利用料浆熔烧法在合金表面制备Si-Cr-Ti涂层,研究在1 400℃下合金与涂层的氧化行为。通过X射线衍射(XRD)、扫描电镜(SEM)、能谱分析(EDS)及电子探针微区分析(EPMA)研究基体与涂层氧化前后的组织形貌变化及成分分布。结果表明:Nb-40Ti-7Al合金在1 400℃氧化1～11 h后,氧化产物均主要为TiNb2O7、TiO2、Al2O3;氧化前,涂层主要由(Nb,Ti,Cr,Al)Si2主体层与(Ti,Nb,Al)5Si3过渡层组成,高温氧化后涂层表面形成含有Al2O3、TiO2的SiO2阻挡层;合金与涂层的氧化行为均遵循抛物线规律,合金在1 400℃氧化11 h的单位面积质量增量为161.98 mg/cm2,而涂覆涂层后单位面积质量增量降至9.56 mg/cm2,表明Si-Cr-Ti涂层具备良好的高温抗氧化性能。     

过渡金属元素在L10-TiAl中占位行为的热力学研究

从合金热力学的角度,采用一种普适化的三亚晶格热力学模型,辅助以第一性原理总能计算的方法,研究了常用于添加在L10-TiAl基金属间化合物中的12种过渡族金属元素的占位行为随Ti/Al比和温度的变化情况.结果表明,在1173 K,合金化元素含量固定为2％(原子分数),Ti/Al比从0.6增加至1.4时,Ti和Al本身具有很强的占位有序性.当温度固定为1173 K,Ti/Al比从0.6增加至1.4时,合金化元素按其占位行为可以分为两大类,其中,V,Ta,Mo,Mn,Cr,Zn和W元素随Ti/Al比的增加,其占位行为在Ti/Al=1附近出现了从占Ti位到Al位的突变;Zr,Nb,Tc,Co和Ag元素的占位行为随Ti/Al比变化没有明显变化.当Ti/Al=1,合金体系固定为Ti0.49Al0.49M0.02,温度从200 K增加至2000 K时,合金化元素按其占位行为同样可以分为两大类,其中,V,Ta,Mo,Tc,Co,Mn,Cr,Zn和W元素随温度升高,其占位行为从完全无序转变为具有明显的占位倾向性;Zr,Nb和Ag元素的占位行为随温度升高没有显著变化.比较表明,Ti/Al比对合金化元素占位行为的影响大于温度的影响.该结果与大部分文献报道的实验和计算结果吻合.     

TiAlN涂层制备过程中Ti,Al元素存在形式的演变分析

采用目前商用原子比为Ti50Al50的合金靶材,利用磁控溅射工艺,在硬质合金基体上沉积TiAl和TiAlN涂层。借助扫描电镜(SEM),X射线衍射仪(XRD)对Ti,Al元素在靶材和涂层中的存在形式作了分析,利用洛氏硬度试验机和纳米硬度仪对涂层的结合强度和硬度等力学性能做了测试分析。结果表明:Ti,Al元素在TiAl合金靶材中以纯Ti相和纯Al相存在,其中Ti原子颗粒镶嵌在Al原子的基体中;在TiAl涂层中以纯Ti单质相和Ti3Al合金相存在;在TiAlN涂层中以面心立方TiN相和密排六方AlN相存在。在涂层的制备过程中,靶材的溅射阶段属于靶材金属离子的产生过程,Ti,Al两种元素由靶材中双单质相结构转变为具有一定能量的离子流状态;涂层的沉积阶段属于Ti,Al两种元素的重新结合状态,无反应气体参与情况下形成合金化结构,反应气体的参与下Ti原子与N原子结合成TiN相,Al以置换TiN晶格中的Ti原子存在。Ti,Al元素的氮化作用导致涂层力学性能发生了变化,涂层硬度由12.8 GPa提高到23.5 GPa;涂层的结合强度由HF-1变为HF-2,均具有较好的结合强度。     

Si对MCrAlY涂层高温性能的影响

本文开展了在1000℃和1050℃条件下CoCrAlSiY涂层高温抗氧化动力学研究,绘制了CoCrAlY、Si含量2%及5%CoCrAlSiY涂层的氧化动力学曲线,研究了300hr氧化试验后涂层氧化膜的构成、涂层组织和β相的分布,初步探讨了Si元素对改善涂层抗氧化性能的作用机理。研究结果表明:Si元素通过影响氧化膜结构及形成动力学条件、抑制了涂层的内氧化发生,对提高CoCrAlSiY涂层在1000℃以上的抗氧化性能作用显著;Si有在晶界处的富集和提高氧化膜应力的趋势,过高的Si的含量会加剧负面效应,对涂层高温抗氧化性能不利。     

Oxidation of magnetite

The oxidation of large octahedral single crystals of magnetite extracted from chlorite shale at Shabrovsk talc mine (Middle Urals) is experimentally studied. Differential heating curves show that the processes occurring in the oxidative roasting of magnetite (Fe₃O₄) are highly reproducible. The mechanism of martensite oxidation is considered, as well as the temperature ranges corresponding to exothermal and endothermal reactions. The thermal effect of martensite oxidation is determined from that of a standard (CaCO₃) and the areas under the differential heating curves on the corresponding thermograms. Those areas are proportional to the thermal effect. The results obtained are of considerable interest: knowing the temperature range of martensite oxidation, the heat sources in the various technological zones of the conveyer roasting machines may be taken into account in establishing the roasting conditions, thereby optimizing the thermal conditions and reducing the fuel consumption.     

Oxidation of iridium

Iridium wires self-reistance-heated to temperatures in the range of 1675 to 2260°C (1948 to 2533 K) were oxidized in naturally convected oxygen at pressures in the range of 0.00132 to 1.32 atmospheres (134 to 1.34× 10⁵ Pa). The experimental results were closely corre-lated by a theoretical rate equation based upon control of the oxidation rates by diffusion of Ir(g), IrO₂(g) and IrO₃(g) through the gaseous boundary layer. Values were obtained for the standard-state free-energies of formation of IrO₂(g) and IrO₃(g), and their temperature dependencies were described by empirical equations.     

Oxidation of porous nanocrystalline titanium nitride. III. Oxidation mechanism

The air oxidation mechanism of nanocrystalline TiN at 500 to 900 °C is examined. It is shown that at t ≤ 800 °C the oxidation of titanium nitride is controlled by the diffusion of oxygen and at t > 800 °C the interdiffusion of titanium ions is observed. The oxidation properties of porous TiN are determined by the chemical interaction of oxygen and the reaction surface, which includes the external surface of samples and the internal surface of the pores into which oxygen penetrates. The time and temperature dependence of the weight increment complies with the porous material oxidation model. Active initial oxidation is due to the interaction of oxygen and large internal surface. Short-term self-heating of porous samples is also possible. At t ≤ 800 °C, the pores are obliterated with oxides with time, the internal reaction surface reduces, an external oxide film is formed, the oxygen diffusion and weight increment slow down, and the process stabilizes. With temperature increase, these processes are activated and lead to a smaller weight increment at the final stage (2 to 4 h) at 800 °C as compared with 600 °C. At t > 800 °C the pore obliteration rate increases, but due to the interaction of oxygen and titanium ions that diffuse into the external scale surface, weight increment continuously increases with both time and oxidation temperature. The phase composition of the scale also affects the oxidation mechanism of porous TiN. Oxynitride of terminal composition plays a protective role; the transformation of anatase into rutile is accompanied by a decrease in the oxygen diffusion rate; Ti₂O₃ formed in pores accelerates their obliteration. __________ Translated from Poroshkovaya Metallurgiya, Vol. 46, No. 3–4 (454), pp. 95–104, 2007.     

Oxidation of nickel sulfide

The oxidation of nickel sulfide whose atomic fraction of sulfur,x _s, is 0.40 to 0.44 was studied in a mixed O₂-N₂ gas stream at 923, 973, and 1023 K. The oxygen partial pressure was maintained at 2.0 x 10⁴ Pa. In the oxidation of nickel sulfide ofx _s = 0.40 and 0.41, a dense NiO layer was formed on the sulfide surface without the evolution of SO₂ gas, because of the low sulfur activity. Diffusion of nickel within the inner sulfide core toward the surface controlled the oxidation rate during the first one minute of oxidation. Subsequently, the oxidation rate was controlled by the diffusion of nickel through the formed NiO layer. In the oxidation of nickel sulfide ofx _s = 0.44 at 973 and 1023 K, the reaction proceeded irregularly to the interior of the sulfide core with the evolution of SO₂ gas, and a porous oxide layer was formed, due to the high sulfur activity of nickel sulfide. For the same reason, this oxidation was also accompanied by the dissociation of nickel sulfide. Under the experimental conditions ofx _s = 0.42, 1023 K and x_s = 0.44,923 K, the oxidation started with weight increase and without the evolution of SO₂ gas, and in the subsequent stage the weight decreased and SO₂ gas was evolved. K. HAJIKA, former Graduate Student     

Oxidation of a zirconia-toughened

A Ni₃Al composite reinforced with zirconia-toughened alumina fiber, PRD-166 fiber, was produced by pressure casting. The thermochemical stability of the composite at 1100 °C in vacuum and air was investigated by optical and transmission electron microscopy and energy- dispersive spectroscopy (EDS). Vacuum annealing resulted in precipitation of needle-shaped ZrB and cuboid-shaped Cr-rich, tentatively identified as Cr₇C₃, particles. Annealing in air led to the precipitation of large ZrO₂ particles at the fiber/matrix interface and fine ZrO₂ platelets in the matrix. A thin layer of A1₂O₃ was observed to cover the fiber/matrix interface and to envelop the ZrO₂ platelets. Diffusion of Ni through the A1₂O₃ layer and its oxidation and sub- sequent reaction with A1₂O₃ resulted in the formation of NiAl₂O₄ spinel around the ZrO₂ particles at the fiber/matrix interface. Further annealing resulted in the formation of a thin layer of Cr₂O₃ on the A1₂O₃ layer and precipitation of A1₂O₃ and Cr₂O₃ particles within the matrix. These particles subsequently reacted with NiO to form Ni(Al_xCr_1-x)₂O₄grains. Diffusion of oxygen through the fiber is believed to be responsible for the rapid oxidation of the composite.     

Oxidation of iron-ore pellets

The oxidation of magnetite in the roasting of iron-ore pellets is considered, with particular attention to the influence of various technological factors on the process. Laboratory data are used in optimizing the design and operational parameters of individual zones in conveyer roasting machines for the heat treatment of magnetite pellets.