锆对急冷凝固FGH96合金粉末显微组织和元素偏析的影响

采用金相显微镜(OM)、扫描电镜(SEM)及其附带的能谱仪,对不同Zr含量的急冷凝固FGH96合金粉末的显微组织、热学凝固参数和枝晶间合金元素偏析进行研究。结果表明:通过调整Zr含量,可以改变粉末颗粒内部树枝晶、胞状长大晶和微晶凝固组织的比例;粉末凝固组织形态主要取决于冷却速率T-、固液界面前沿温度梯度G和长大速度R;不同Zr含量的FGH96合金粉末颗粒中,Mo、Nb、Ti、Zr等元素富集于枝晶间,Co、Cr、W和Ni富集于枝晶轴,随Zr含量增加,Ti、Nb、Zr等元素的枝晶偏析程度减小。     

消除粉末高温合金中原始颗粒边界机制

采用SEM、TEM研究了高温合金粉末颗粒内部与合金中碳化物的类型和组成,采用热力学软件计算了不同Hf含量FGH4096的碳化物组成,结果表明,粉末高温合金中原始颗粒边界上的析出物为以TiC为主的MC型碳化物,MC型碳化物(TiC、ZrC、HfC、NbC、TaC)在镍基高温合金中按溶解度从大到小为TiCNbCTaCZrCHfC。TiC在FGH4096中的溶解度较HfC的大,雾化粉末快速凝固过程中,加入Hf的FGH4096合金碳化物析出量大于不加Hf的FGH4096合金碳化物析出量,HfC均匀形核于整个粉末颗粒中。在热等静压过程中,Hf与C的结合力强而形成HfC,最终在FGH4096合金中形成(Hf,Ti,Nb)C,致使C元素无法扩散至粉末颗粒表面形成TiC,避免了原始粉末颗粒边界的形成。加入Zr消除FGH4096中原始颗粒边界的机制与添加Hf的FGH4096相同。     

消除粉末高温合金中原始颗粒边界机制北大核心

采用SEM、TEM研究了高温合金粉末颗粒内部与合金中碳化物的类型和组成,采用热力学软件计算了不同Hf含量FGH4096的碳化物组成,结果表明,粉末高温合金中原始颗粒边界上的析出物为以TiC为主的MC型碳化物,MC型碳化物(TiC、ZrC、HfC、NbC、TaC)在镍基高温合金中按溶解度从大到小为TiC>NbC>TaC>ZrC>HfC。TiC在FGH4096中的溶解度较HfC的大,雾化粉末快速凝固过程中,加入Hf的FGH4096合金碳化物析出量大于不加Hf的FGH4096合金碳化物析出量,HfC均匀形核于整个粉末颗粒中。在热等静压过程中,Hf与C的结合力强而形成HfC,最终在FGH4096合金中形成(Hf,Ti,Nb)C,致使C元素无法扩散至粉末颗粒表面形成TiC,避免了原始粉末颗粒边界的形成。加入Zr消除FGH4096中原始颗粒边界的机制与添加Hf的FGH4096相同。     

高温氧化对FGH96高温合金粉末表面状态的影响

通过模拟FGH96高温合金粉末在热等静压固结阶段的高温加热过程，利用多种表面分析方法，研究高温氧化对粉末表面状态的影响。结果表明，近热等静压加热温度条件下的高温氧化过程显著改变了FGH96高温合金粉末的表面形貌、表面元素分布和析出相组成。随加热温度的升高和保温时间的延长，胞状晶为主、树枝晶为辅的表面凝固组织被氧化物/碳化物层所覆盖，高温氧化过程促进粉末基体内部的Ni、Ti、Zr、Nb、Al和C原子逐渐扩散到粉末表面，粉末表面预先存在的氧化物（ZrO2）为MC型碳化物（(Ti, Nb)C）的形核提供了结构条件。控制粉末表面氧化物的形成可以有效限制合金中形成原始颗粒边界缺陷。     

含Hf和Ta新型镍基高温合金粉末中碳化物相

对含Hf和Ta新型镍基高温合金FGH98Ⅰ等离子旋转电极(PREP)雾化原始和不同温度下预热处理粉末中的碳化物相进行了研究.结果表明:原始粉末中MC′型碳化物可分为两类,一类为富Ti、Ta和Nb,另一类为含Ta、Hf和Zr.两类碳化物均含有一定量非碳化物形成元素Co和Ni及中等强碳化物形成元素Cr和Mo,并以块状、粒状分布于枝晶或胞晶间;随着预热处理温度升高,粉末中富Ti、Ta和Nb的MC′型碳化物转变为MC型碳化物,且其所含Ti、Ta和Nb的总量增大;含Ta、Hf和Zr的MC′型碳化物发生分解和转变,析出稳定的M23C6、M6C和MC型碳化物,M23C6碳化物的析出和溶解温度为950℃和1150℃,M23C6和M6C碳化物共存温度为1000～1100℃.另外,粉末中微量元素Hf和Ta主要以碳化物和γ′相参与碳化物反应.     

微量元素Hf消除FGH96合金中原始粉末颗粒边界组织机制的探讨

粉末冶金高温合金中原始粉末颗粒边界组织(PPBS)由碳化物和少量碳氧化物组成。采用SEM、TEM以及AES等研究了粉末颗粒内、表面上以及合金中PPB上碳化物的结构和组成,依据热力学和扩散理论分析了Hf消除原始粉末颗粒边界组织(PPBS)的微观机制。结果表明:快速凝固粉末颗粒表面形成含有Ti、Nb、Cr、Mo、W的MC型亚稳定碳化物MC′,在HIP过程中粉末颗粒表面上的MC′相转变成稳定的MC相,以及粉末颗粒内的Ti、C元素向烧结颈处扩散,HIP后在粉末颗粒边界上形成富Ti和Nb的MC型碳化物(Ti,Nb)C。加入微量Hf后,在粉末颗粒内形成了更多更稳定的含Hf的MC型碳化物(Ti,Nb,Hf)C,C、Ti被"绑定"在碳化物(Ti,Nb,Hf)C中,抑制了C、Ti向烧结颈处扩散,从而抑制了MC型碳化物在粉末颗粒边界上的析出。     

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.     

镍基高温合金GH4151的偏析及相析出行为

摘要：利用电子探针(EPMA)、场发射扫描电镜（SEM）及差热分析（DTA）研究了GH4151合金的元素偏析行为、铸态组织特征以及析出相种类,并对合金凝固过程进行讨论。结果表明：GH4151合金凝固过程中,W元素偏聚于枝晶干,Mo、Nb、Ti元素偏聚于枝晶间,Co、Cr、Al元素几乎不发生偏析,Nb、Ti元素偏析较重。GH4151铸锭心部为粗大的等轴晶,主要析出相包括强化相γ′相、一次碳化物、η相、（γ+γ′）共晶相以及Laves相,其中枝晶间分布的η相、（γ+γ′）共晶相和Laves相为低温脆性相在凝固末期形成,扩大了合金的凝固区间,从而导致合金热裂敏感性增加。     

氩气雾化高温合金粉末的凝固组织特征

为深入了解高温合金粉末粒度细化对粉末涡轮盘性能的影响,对不同尺寸氩气雾化高温合金粉末的凝固组织特点进行了分析和研究.结果表明:AA粉表面和内部凝固组织主要为树枝晶和胞状晶组织,晶界和枝晶间分布少量富Ti、Nb的MC型碳化物.随着粉末尺寸的减小,冷却速率增大,组织从树枝晶向胞状晶转变,基体γ相晶面间距和点阵常数增加.小尺...     

镍基铸造高温合金中元素对一次碳化物MC的组成及其形态的影响

一次碳化物MC是镍基铸造高温合金的主要析出相之一。本文通过电子探针和金相分析方法探讨了合金元素对合金中MC的组成和形态的影响。MC的组成和形态主要决定于合金中的Nb/Ti比值,合金中的Nb/Ti值高,MC中的Nb/Ti值也随着升高,由富Ti的MC向着富Nb的MC转变,MC的形态也跟着由块状向着片状和骨架状转变。合金中加入～1％Hf、Zr或V,能改变MC的组成,置换其中的一部分Ti,并使MC由骨架状转变成块状。C_o和B对MC形态有影响,含0.15～0.20％B和16％C_o的合金,其MC富Nb但呈块状。碳量增加,MC急剧地由块状转变成片状和骨架状。根据碳化物生成自由能的大小和元素的枝晶偏析倾向,合金元素的碳化物生成次序为Zr、Hf、Nb、Ta、Ti和V.元素促使MC呈块状析出的能力按如下次序排列:Mg、Zr、Hf、V、Ti、B、Co、Ca、Cr、W、Mo、Al、Nb、Ce、C。     

Effect of Hf and Zr Contents on Stress-rupture and Fatigue Crack Growth Rate Performances in FGH96PM Superalloy

Four experimental FGH96alloys with various contents of Hf and Zr(0and 0.04%,0.3% and 0.04%,0.6% and 0.04%,0.3%and 0.06%,respectively)were produced using PREP(plasma rotating electrode process)+HIP(hot isostatic pressing)route.The unnotched and notched stress-rupture properties and fatigue crack growth rate(FCGR)of all the experimental alloys were investigated to study the effect of Hf and Zr.Relevant fracture morphology and microstructure were observed by scanning electron microscopy and transmission electron microscopy.The results revealed that appropriate content of Hf could lengthen stress-rupture life,eliminate notch sensitivity and slower FCGR.Microstructure analysis showed that the amount ofγ′phase should be increased or decreased by adjusting Hf and Zr contents,and MC carbide and oxide coupled growth should be increased by adding Hf content,which caused oxycarbide to precipitate along grain boundary and strengthen the alloy.It was found that excessive Zr in Hfcontaining FGH96alloy had certain deleterious effects on stress-rupture property because there was strong Zr segregation at prior particle boundary,leaving a long chain of large-size oxides along the boundary.The optimal content of Hf and Zr in FGH96alloy was 0.6%and 0.04%,respectively.     

热变形对FGH96高温合金原始颗粒边界的影响

通过Gleeble-1500热模拟试验机对热等静压成形FGH96高温合金进行热压缩试验,其中温度为1075℃,变形速率为0.001 s-1,变形量为70%。利用场发射扫描电镜、透射电镜和电子能谱研究了合金原始颗粒边界（prior particle boundary,PPB）的组成,讨论了原始颗粒边界在FGH96高温合金再结晶过程中的作用,并分析了合金热变形对原始颗粒边界的影响。结果表明:热等静压成形FGH96高温合金中的原始颗粒边界主要由Ti的碳化物和γˊ相共同组成;原始颗粒边界对合金热变形再结晶形核起促进作用,对晶粒长大起阻碍作用;合金热变形可以改善原始颗粒边界在组织中的分布,从而使晶粒长大过程顺利进行。     

粉末粒度和氧含量对HIP态FGH96合金组织的影响

对氩气雾化法制备的高温合金FGH96粉末进行了热等静压(HIP)处理,分析了粉末粒度和氧含量对HIP态合金组织的影响,研究了FGH96合金组织中PPB的类型、相结构和形成机制。结果表明,氩气雾化FGH96粉末的氧含量较低,平均氧含量约为50×10-6,随着粉末粒度降低,颗粒比表面积增大,促进了粉末氧含量的升高;粉末经HIP处理后氧含量具有遗传特征,原始粉末氧含量越高,HIP态合金氧含量也越高,且平均氧含量增至83×10-6;粉末尺寸和氧含量对合金致密化行为无明显影响,HIP态合金密度约为8.33 g·cm-3。小尺寸粉末制备的HIP态合金原始颗粒边界主要析出ZrO2和MC碳化物,而大尺寸粉末制备的HIP态合金原始颗粒边界主要析出大尺寸花瓣状γ’相和少量MC碳化物。粉末粒度和氧含量影响PPB析出,小尺寸粉末因氧含量高经HIP处理时颗粒边界处存在更多、尺寸更大稳定的ZrO2,ZrO2成为MC碳化物析出形核的核心,促进了大量MC碳化物的析出。     

氩气雾化法制备FGH96高温合金粉末颗粒的凝固组织

利用扫描电镜(SEM)对氩气雾化(argon gas atomization,缩写AA)工艺制备的FGH96高温合金原始粉末颗粒的粘结形式、凝固组织、表面和内部形貌及其形成机理进行研究.结果表明:AA法制备的FGH96合金粉末,在颗粒尺寸d≥40 μm时,颗粒之间出现凸起式粘结、包覆式粘结以及葫芦式粘结,其中凸起式粘结...     

Effect of titanium,niobium and zirconium on creep rupture strength and ductility of cobalt base superalloys

An attempt has been made to develop a cobalt base casting superalloy (30Cr-10Ni-7W-Co) having high creep rupture strength and ductility for first stage nozzles of gas turbines. In cobalt base superalloys, there was found to exist a close correlation between the creep rupture strength and MC type carbide forming elements such as Ti, Nb and Zr. In cobalt base alloys with 0.25 wt pct C, precipitation and coarsening of carbides can be reduced by addition of Ti, Nb and Zr. Therefore, by adding the optimum amount of Ti, Nb and Zr, precipitation of carbides in the alloy reaches such an amount as to give the highest creep rupture strength. Excess addition of Ti, Nb and Zr does not improve the creep rupture strength. By adding C, creep rupture strength of the cobalt alloy with Ti, Nb and Zr can be improved and becomes the highest at 0.40 wt pct. C. According to the experimental results, the creep rupture strength becomes the highest at a value of (Ti + Nb + Zr)/C (atomic ratio) of about 0.3. Contrary to the expectation, it was found in this experiment that the ductility in creep rupture tests increases with increasing carbon content up to 0.6 wt pct.     

粉末高温合金FGH97疲劳裂纹扩展行为

测定不同晶粒尺寸、γ'相以及不同Hf含量的粉末高温合金FGH97在650℃高温条件下的疲劳裂纹扩展速率,并将其与FGH95和FGH96两代粉末合金的疲劳裂纹扩展速率进行对比.用定量分析的方法对FGH97合金在疲劳断裂各个阶段的行为特征进行分析.较大晶粒尺寸的FGH97合金具有较低的裂纹扩展速率,合理的二次和三次γ'相匹配析出,可以获得较高的疲劳寿命;Hf元素的添加使合金的整体疲劳寿命增大;FGH97合金与FGH95和FGH96相比,具有较高的疲劳裂纹萌生抗力,更低的高温疲劳裂纹扩展速率.      

SHS Metallurgy of Composite Materials Based on the Nb–Si System

Composite materials (CMs) based on niobium with functional and alloying additives (Si, Hf, Ti, Al, etc.) have prospects for industrial approval in aviation propulsion engineering. The authors previously showed that such CMs can be synthesized in an autowave mode (combustion mode) using highly exothermic mixtures of Nb₂O₅ with Al, Si, Hf, and Ti. It was found that hafnium actively participates in the reduction of Nb₂O₅, which complicates its introduction into the CM. This study is directed at investigating the possibility to synthesize Nb-based composite materials with a high Hf content using methods of centrifugal SHS metallurgy. It is shown in experimental investigations using a centrifugal installation under the effect of acceleration of 40 g that the replacement of active Hf by its less active compounds Hf–Al or Hf–Ti–Si–Al in the composition of the Nb₂O₅/Al mixtures makes it possible to transfer the combustion of the mixture from the explosion-like mode into the steady-state combustion mode. The content of Hf in the CM increases with an increase in the size of Hf–Al granules from 0–40 to 160–300 μm from 1.3 to 3.8 wt %. The introduction of Hf–Ti–Si–Al granules with a particle size from 1 to 3 mm into the initial charge makes it possible to form cast CMs based on niobium silicides with a Hf content up to 8.1 wt %. The integral composition and distribution of base and impurity elements in structure components of cast CMs, as well as their phase composition, were determined using electron microscopy and X-ray phase analysis. CMs with the maximal Hf content (8.1 wt %) contain three structural components: (1) the base, which includes Nb, Si, and Ti; (2) intergrain boundaries containing Nb, Ti, and Al; and (3) inclusions based on hafnium oxide. Three phases are revealed in the X-ray diffraction pattern of the CM, notably, solid solutions based on Nb and Nb5Si3, as well as a minor amount of Nb₃Si.     

Surface hardening of nickel alloys by means of plasma nitriding

Surface hardening of Ni alloys by plasma nitriding was investigated by using tentative Ni binary alloys contained nitride forming elements such as Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, Mn, Fe, Al, or Si at the nitriding temperature from 673 to 1073 K. Surface hardness was different depending on the types of alloying elements, their contents, and their nitriding temperatures. Higher hardness than HV500 was obtained in Ti, V, Nb, and Cr containing alloys at 823 to 873 K, but other alloys showed lower surface hardness than HV400. The elements Ti, V, Nb, and Cr were the effective alloying elements for the surface hardening of nitrided Ni alloys. From transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis, the nitrided layer was composed of fine precipitate particles in the matrix of the nitrided layer. At the lower nitriding temperature, these particles were metastable fine particles or Ginier-Preston (GP) zone having coherency with the matrix, and these fine particles induced large microstrain in the matrix. However, at the higher nitriding temperature, equilibrium nitride particles were precipitated and coherency with the matrix was decreased. Therefore, the hardening of Ni alloys by plasma nitriding was due to the microstrain induced in the nitrided layer by the precipitation of metastable particles or GP.     

Calcium hydride synthesis of Ti–Nb-based alloy powders

The metallothermic (calcium hydride) synthesis of Ti–Nb alloy powders alloyed with tantalum and zirconium is experimentally studied under various conditions. Chemical, X-ray diffraction, and metallographic analyses of the synthesized products show that initial oxides are completely reduced and a homogeneous β-Ti-based alloy powder forms under the optimum synthesis conditions at a temperature of 1200°C. At a lower synthesis temperature, the end products have a high oxygen content. The experimental results are used to plot the thermokinetic dependences o formation of a bcc solid solution at various times of isothermal holding of Ti–22Nb–6Ta and Ti–22Nb–6Zr (at %) alloys. The physicochemical and technological properties of the Ti–22Nb–6Ta and Ti–22Nb–6Zr alloy powders synthesized by calcium hydride reduction under the optimum conditions are determined.     

温度对镍基高温合金粉末氧化行为的影响

通过化学分析、扫描电子显微镜观察、X射线衍射分析及X射线光电子能谱分析等方法, 研究了温度对镍基高温合金粉末氧化行为的影响。结果表明, 室温条件下, 粉末氧含量(质量分数)较低(0.012%), 粉末表面发生部分氧化, 表面存在Ni、Cr、Ti等元素的单质态和以Ni (OH)₂、Cr₂O₃、TiO₂为主的氧化物/氢氧化物; 当温度上升至150 ℃, 氧含量增加不明显; 随着温度进一步提高至250 ℃, 粉末氧含量明显增加, 达到0.034%, 粉末表面全部氧化, 表面主要由Ni (OH)₂、Cr₂O₃、TiO₂组成。温度对镍基高温合金粉末氧化行为影响显著, 合理控制温度可以获得低氧含量的粉末, 本研究所用镍基高温合金粉末大气条件下最高处理温度为150 ℃。