基于微束X射线荧光光谱的新型铸&锻GH4096合金涡轮盘成分分布解析

铸&锻GH4096高温合金涡轮盘拥有高承温能力、高强度、低裂纹扩展速率、高抗疲劳性能等优异性能,是航空发动机的关键热端部件。但由于其合金化程度较高、零件尺寸大、制备工艺复杂等,不可避免会出现成分和组织分布不均匀,一定程度影响涡轮盘的服役性能。微区X射线荧光光谱（μ-XRF）具有微区分辨率高、分析速度快、多元素同步分析、非破坏性等优点,被广泛应用于考古、地质、生物等领域,但对大尺寸高温合金构件的成分分布的研究较少,对于材料各原始位置处的成分定量分布表征也未见报道。本试验通过选择合适的测量条件、优化仪器定量方法,建立了基于微束X射线荧光光谱的新型铸&锻GH4096合金涡轮盘成分分布定量分析方法,并引入了原位统计分析方法对涡轮盘中Cr,Co,Mo,W,Ti,Al,Nb和Ni八种主要元素进行了定量统计分布解析。发现涡轮盘厚度的中心区域内Co,Mo和Ti三种元素从轮毂至轮缘存在较明显的弧形负偏析带,而Ni和Cr两种元素存在弧形正偏析带。另外,涡轮盘径向也存在一定的成分梯度分布,Co,Cr和W三种元素含量从轮毂到轮缘的呈现逐渐降低的趋势,而Mo,Ti和Nb三种元素含量则呈现逐渐上升趋势。对各元素最大偏析度、统计偏析度、统计符合度计算分析后可知,Cr,Co,Mo,W,Ti,Nb和Ni七种元素测量区域内整体偏析程度较小、统计符合度大,在材料元素设计值允许范围内具有较好的成分均匀性。使用火花源金属原位分析仪（OPA-200）对相同测试区域的元素进行了线分布分析,其分析结果与微束荧光光谱得到的分析规律具有较好的一致性,说明大尺寸涡轮盘在热处理过程中存在温度场分布,导致了各元素扩散行为以及显微组织分布的差异,因此不同部位的成分也存在一定偏析。通过对大尺寸的涡轮盘成分进行定量统计分布解析,对于评价新型铸&锻变形GH4096高温合金涡轮盘的成分分布均匀性,解析制备工艺与大尺寸构件成分、组织结构分布的相关性具有重要意义。     

(Bi1-x Agx)2(Te1-ySey)3粉体的机械合金化制备及其放电等离子烧结体的热电输运特性

采用机械合金化制备了n型(Bi1-x Agx)2(Te1-y Sey)3合金粉体,对其进行XRD分析表明Bi,Te,Ag,Se单质粉末,经2 h球磨后实现了合金化;SEM分析表明随着机械合金化时间延长粉体颗粒变得均匀、细小,颗粒尺寸在微米至哑微米数量级.采用放电等离子烧结制备了块体样品,研究了合金成分和球磨时间对热电件能的影响.结果表明材料的热电性能与掺杂元素有密切关系.Ag有利于提高功率因子和降低晶格热导率,球磨10 h的(Bi0.99Ag0.01)2(Te0.96Se0.04)3合金粉末的烧结块体具有最大的功率因子和最低的晶格热导率,并在323 K取得最高ZT值0.52.     

火花源原位统计分析技术对涡轮盘的成分分布分析

火花源原子发射光谱原位统计分布分析技术(OPA)是近十几年发展起来的一种大尺度金属截面的高通量成分分布分析技术,具有分析速度快、多元素信号同时定位采集、统计解析信息量大等独特优势,已被广泛应用于中低合金钢铸坯中的成分分布分析。采用火花源OPA技术对铸&锻变形FGH96高温合金航空发动机涡轮盘纵剖面中的主要合金元素Al,Cr,Co,Ti,W,Mo和Nb进行了成分分布分析,并通过适宜的校准曲线的拟合实现了七种合金元素的定量统计解析。采用直读光谱仪对纵剖面轮毂至轮缘的不同部位进行了定点分析,两种方法具有较好的一致性。结果表明,经过新的铸&锻工艺生产的变形FGH96涡轮盘中除了含量较低的Nb元素外,大部分元素的统计偏析度都小于5%。由于涡轮盘不同部位冷却方式的差异,导致轮毂和轮缘上某些元素分布的差异,其中Ti,Nb等碳化物形成元素在轮缘处存在一定的偏析,含量有所升高,而W,Mo和Co则在轮中部分布较不均匀,采用扫描电镜结合能谱分析的方法也观察到了轮缘处了大颗粒的Ti和Nb的碳化物的存在,进一步证实了涡轮盘边缘Ti和Nb偏析的存在。大尺度涡轮盘的元素成分分布分析结果对于FGH96合金涡轮盘新型铸&锻变形工艺的改进和性能提高具有重要的指导作用。     

(Bi1-x Agx)2(Te1-ySey)3粉体的机械合金化制备及其放电等离子烧结体的热电输运特性

采用机械合金化制备了n型(Bi_1-xAg_x)₂(Te_1-ySe_y)₃合金粉体,对其进行XRD分析表明Bi,Te,Ag,Se单质粉末,经2h球磨后实现了合金化;SEM分析表明随着机械合金化时间延长粉体颗粒变得均匀、细小,颗粒尺寸在微米至亚微米数量级.采用放电等离子烧结制备了块体样品,研究了合金成分和球磨时间对热电性能的影响.结果表明材料的热电性能与掺杂元素有密切关系,Ag有利于提高功率因子和降低晶格热导率,球磨10h的(Bi_0.99Ag_0.01)₂(Te_0.96Se_0.04)₃合金粉末的烧结块体具有最大的功率因子和最低的晶格热导率,并在323K取得最高ZT值0.52. 关键词： 1-xAg_x)₂(Te_1-ySe_y)₃合金')" href="#">(Bi_1-xAg_x)₂(Te_1-ySe_y)₃合金 机械合金化 放电等离子烧结 热电性能     

基于微束X射线荧光光谱的单晶叶片枝晶成分分布定量统计研究

镍基单晶高温合金是含有10～15种元素的复杂合金,具备优良的高温强度和耐腐蚀性。目前,先进燃气涡轮发动机的涡轮部件几乎都采用空心结构的单晶叶片。叶片服役过程中要承受超过其熔化温度数百摄氏度的高温和巨大离心应力,是工况条件最为恶劣的航空零件,被誉为“工业王冠上的明珠”,研制发展更耐高温的叶片材料以及改进叶片的冷却技术是提高涡轮进口温度的关键手段。新一代的单晶叶片中添加大量难熔元素(如Ta, W和Re等)用来提高承温能力,但这些元素在凝固过程中存在严重的枝晶偏析,导致组织内成分分布不均匀。通常采用复杂的多级热处理来溶解非平衡组织,减小偏析。枝晶间成分的详细表征对优化热处理工艺和叶片设计具有重要的意义。微束X射线荧光光谱是一种无损检测技术,制样简单,无需镀导电膜,可对样品进行多元素同时检测,多用于生物和考古领域,定量表征成分复杂的金属材料存在一定困难,应用案例较少。单晶高温合金具有特殊的十字枝晶组织,尺寸约为几百微米,微束X射线荧光光谱可以满足单晶叶片枝晶成分的详细表征和大区域面积的成分分布定量统计需求。本实验基于微束X射线荧光光谱技术,建立了镍基单晶高温合金枝晶成分定量统计分布表征方法,并...     

Cu-Al混合粉经过球磨后的27Al核磁共振谱与机械合金化反应

测量了ＣｕＡｌ 混合粉末经过不同时间球磨后的２７Ａｌ 核磁共振（ＮＭＲ） 谱，分析了２７Ａｌ ＮＭＲ 谱的特征参量随球磨时间的变化．根据２７Ａｌ ＮＭＲ 谱所提供的信息，研究了ＣｕＡｌ 混合粉末机械合金化反应的微观过程．ＣｕＡｌ 混合粉末的２７Ａｌ Ｋｎｉｇｈｔ 位移随球磨时间的增加而减小．对于ＣｕＡｌ 混合粉末，球磨不仅改变了２７Ａｌ 附近的化学短程序，而且也直接地影响了２７Ａｌ 的外层电子态，后者使传导电子的ｓ 态成分减小．实验结果表明，ＣｕＡｌ 混合粉末在球磨过程中发生了真正的合金化反应；经过９０ ｈ 球磨完成了合金化反应；用机械合金化法制备的ＣｕＡｌ 合金与用熔融法制备的同成分合金有相同的化学短程序     

爆炸压实制取W-Cu纳米复合材料的实验研究

采用机械合金化法制备了W-Cu合金粉末。将制备出的W-Cu合金粉末置于爆炸压制成型的装置中进行爆炸压实,得到了最高致密度达98%的W-Cu合金。利用X射线衍射(XRD)分析了W-Cu混合粉末的合金化过程,研究了W-Cu合金粉末的还原温度对压实坯致密度的影响。通过电子探针微量分析仪(EPMA)观察了样品内部的成分与元素分布,利用扫描电子显微镜(SEM)对样品断口形貌进行了观察,并对样品的维氏硬度和电导率进行了测量。结果表明,W-Cu合金化粉末在爆炸冲击波作用下能够结合成高致密体,复合材料具有高硬度、组织均匀、晶粒细小的特点。     

(Sb2Te3)0.75(1－x)(Bi2Te3)0.25(1－x)(Sb2Se3)x机械合金化粉体的制备及其冷压烧结样品的热电性能研究

采用机械合金化法制备了p型赝三元(Sb₂Te₃-Bi₂Te₃-Sb₂Se₃)合金粉体，对其进行XRD分析表明Te，Bi，Sb，Se单质粉末，经100h球磨后实现了合金化；SEM分析表明所得机械合金化粉体材料颗粒均匀、细小，颗粒尺寸在10nm到100nm量级.使用这种粉体制备了冷压烧结块体样品，在室温下测量了温差电动势率(α)和电导率(σ)，研究了烧结温度对材料热电性能的影响，结果表明在低于300℃的烧结温区，样品室温下的热电性能随烧结温度的升高不断提高，功率因子(α²σ)由未烧结样品的0.59μW cm^-1K^-2升高到在300℃下烧结样品的15.9μW cm^-1K^-2，这一结果对确定材料的最佳烧结温度具有重要意义. 关键词： 赝三元热电材料 机械合金化 冷压 烧结     

烧结过程中Ni-Al金属间化合物形成的内耗

Ni-Al金属间化合物是一类重要的高温结构材料,在多种领域具有明确的目标需求.粉末冶金技术是制备Ni-Al金属间化合物的一种重要选择.探索烧结过程中Ni-Al金属间化合物形成和转变过程,明确固相扩散反应发生温度和金属间化合物种类对调控烧结工艺和优化产品质量至关重要.本文采用内耗技术系统研究了Ni-Al粉末混合物压坯烧结过程的内耗行为.在内耗-温度谱上观察到一个显著内耗峰,随测量频率的增大而降低,但峰温无明显频率依赖性.同时,内耗峰随升温速率的增大向高温方向移动且峰值增加.分析认为,该峰与升温过程中金属间化合物NiAl3和Ni2Al3的形成有关,属于典型的相变内耗峰.此外,机械球磨可调控Ni-Al粉末混合物的微观结构,内耗峰随球磨时间增加向低温方向移动且峰值降低,表明固相扩散反应可在低温区域以较低速率进行.这与球磨过程中粉末颗粒的细化、粉末混合物的片层化、固溶度和表面能的提高以及缩短的原子扩散路径有关.同时也表明机械球磨可有效降低固相扩散反应起始温度进而降低烧结温度.     

Co SiO2颗粒膜的巨磁电阻效应

测量了Ｃｕ Ａｌ混合粉末经过不同时间球磨后的２７Ａｌ核磁共振（ＮＭＲ）谱,分析了２７ＡｌＮＭＲ谱的特征参量随球磨时间的变化．根据２７ＡｌＮＭＲ谱所提供的信息,研究了Ｃｕ Ａｌ混合粉末机械合金化反应的微观过程．Ｃｕ Ａｌ混合粉末的２７ＡｌＫｎｉｇｈｔ位移随球磨时间的增加而减小．对于Ｃｕ Ａｌ混合粉末,球磨不仅改变了２７Ａｌ附近的化学短程序,而且也直接地影响了２７Ａｌ的外层电子态,后者使传导电子的ｓ态成分减小．实验结果表明,Ｃｕ Ａｌ混合粉末在球磨过程中发生了真正的合金化反应;经过９０ｈ球磨完成了合金化反应; 关键词：     

Nanosize silicon nitride: characteristic of doped powders and of the related sintered materials

The paper reports on both the characteristics of ultrafine silicon nitride powder produced by plasma synthesis and the microstructure and properties of the relative sintered material. The powder, already containing yttria and alumina as sintering aids, has a bimodal particle size distribution and it is partly amorphous. The chemical composition and morphology of the particles are shown. Yttria and alumina were not found in separate particles but the elements constituting them (i.e., Y, Al, O) are either in solid solutions in the crystalline particles or dispersed within the amorphous portion of the powder. Dense materials were obtained by pressureless sintering at 1750 °C. Microstructure and composition of silicon nitride grains and of grain boundary phases are analyzed and discussed. When compared to a micro-sized Si₃N₄, nanoindentation tests clearly revealed the inverse Hall Petch relation. The nanosize Si₃N₄ shows a Young’s modulus which is almost independent on the peak load. PACS 81.05.J,M; 81.40; 81.05.Y; 81.05.J; 46.30.P     

X-ray diffraction studies on crystallite size evolution of CoFe2O4 nanoparticles prepared using mechanical alloying and sintering

Nanosized cobalt ferrite spinel particles have been prepared by using mechanically alloyed nanoparticles. The effects of various preparation parameters on the crystallite size of cobalt ferrite which includes milling time; ball-to powder weight ratio (BPR) and sintering temperature, were studied using X-ray diffractometer (XRD). Scherrer's equation was used to study the crystallite size evolution of the as-prepared materials. The results of the as-milled sample revealed that both milling time and BPR plays a role in determining the crystallite size of the milled powder. However, where sintering is involved, the sintering temperature results in grain growth, and thus plays a dominant role in determining the final crystallite size of the samples sintered at higher temperature (above 900 °C). From the vibrating-sample magnetometer (VSM) measurement it was observed that the coercivity of the as-milled samples without sintering is almost negligible, which is a type characteristic of superparamagnetic material. However, for the sintered samples, the saturation increases while coercivity decreases with increases sintering temperature.     

Analysis of ball-milled Mo powder using X-ray diffraction

X-ray diffraction measurements and analysis were carried out on ball-milled Mo powder. During the ball milling of Mo powder, several stages of deformation could be identified. After short durations of ball milling, still undeformed starting powder was present and the volume fraction of this was determined. The initial aggregates of deformed powder particles exhibited a deformation texture. On prolonged ball milling, the particle size decreased, the deformation texture disappeared and internal strains built up. By simulation and matching of the corresponding line profiles using a Monte Carlo type of line-profile simulation based on a simple three-dimensional model of the distribution of straight dislocations, an estimate of the dislocation density in the ball-milled particles was obtained.     

Local structure of core/shell nanocrystalline particles produced by surfactant-assisted ball milling of Fe powder in paraffin

Surfactant-assisted ball milling of the Fe powder in paraffin has been used for fabrication of core–shell nanocrystalline particles. The local atomic structure of the bulk and surface layers of the mechanically milled particles has been studied using X-ray absorption spectroscopic techniques with synchrotron radiation from the DORIS storage ring at DESY, Hamburg. Regardless of milling environment composition, the as-prepared powders were shown to be characterized by a significant drop in the EXAFS signal intensity and coordination numbers of the Fe–Fe pairs due to the formation of nanocrystalline state in the particles. It has been shown that an addition of perfluorononanoic acid as a surfactant has a more prominent effect on the structure of the shell layers. The effect is revealed as an appearance of light element atoms (O, F, C) in the local atomic environment of the Fe atoms due to formation of oxide, carbide and adsorbed structures of different types in the particle shell.     

Model for milling of powders

A model is proposed for mechanical milling of powders that relates the applied energy to average particle size D in the powders. It is shown that the milling energy is consumed for the rupture of interatomic bonds in crystalline particles and for the creation of an additional surface during powder fragmentation. The appearance of microstrains ɛ retards powder fragmentation. Average particle size D after milling decreases with increasing milling time t and decreasing particle size in the initial powder or its mass M. The calculated results are compared to the experimental data obtained on a tungsten carbide WC powder.     

Microstructure of nanocrystalline nonstoichiometric vanadium carbide VC0.875

A nanocrystalline powder of nonstoichiometric vanadium carbide VC_0.875 has been prepared by the high-energy ball milling method. The crystal structure, microstructure, morphology, and size distribution of particles of the initial and milled powders have been investigated using X-ray diffraction, laser diffraction, and scanning electron microscopy. For vanadium carbide, the model calculation of the particle size of a VC_0.875 nanopowder as a function of the milling duration has been performed for the first time. A comparison of the experimental and theoretical results has demonstrated that a nanopowder with an average particle size of 40–80 nm can be obtained by a 10-h high-energy ball milling of the initial vanadium carbide powder with an average particle size of ～6 μm.     

Synthesis of silicon nanocomposite for printable photovoltaic devices on flexible substrate

Renewed interest has been established in the preparation of silicon nanoparticles for electronic device applications. In this work, we report on the production of silicon powders using a simple ball mill and of silicon nanocomposite ink for screen-printable photovoltaic device on a flexible substrate. Bulk single crystalline silicon was milled for 25 h in the ball mill. The structural properties of the produced silicon nanoparticles were investigated using X-ray diffraction (XRD) and transmission electron microscopy. The results show that the particles remained highly crystalline, though transformed from their original single crystalline state to polycrystalline. The elemental composition using energy dispersive X-ray florescence spectroscopy (EDXRF) revealed that contamination from iron (Fe) and chromium (Cr) of the milling media and oxygen from the atmosphere were insignificant. The size distribution of the nanoparticles follows a lognormal pattern that ranges from 60 nm to about 1.2 μm and a mean particle size of about 103 nm. Electrical characterization of screen-printed PN structures of the nanocomposite formed by embedding the powder into a suitable water-soluble polymer on Kapton sheet reveals an enhanced photocurrent transport resulting from photo-induced carrier generation in the depletion region with energy greater that the Schottky barrier height at the metal-composite interface.     

Magnetic interactions and Preisach distributions of nanostructured barium hexaferrite

Barium hexaferrite (phase M) samples with different nanostructures were studied. Sample M1 is composed of nanocrystals of BaFe₁₂O₁₉ produced after milling the elemental oxides (Fe₂O₃ and BaCO₃) and heating in air atmosphere. Two more samples were produced by milling the same oxides and a 20% excess of -Fe. The resulting powder (composed of phase M and a 20% hematite) was heat-treated in different conditions, resulting in samples MF1 (with a partially sintered structure) and MF8 (with almost completely sintered structure).

In order to have an insight into the interactions in each sample, Preisach distributions were obtained using first-order reversion curves (FORCs) measurements. The Preisach distribution corresponding to M1 is a Gaussian-shaped one, with a maximum around 4.1 kOe. The distribution of MF1 has a narrow and high peak at 5.3 kOe, a number of overlapping small peaks down to 2.6 kOe and a distinct and low-intensity peak at 2 kOe. MF8 has a Preisach distribution with a succession of equally spaced distinct peaks from 4.2 to 1.5 kOe.

The found Preisach distributions suggest that the interactions occur among nanocrystals inside conglomerates with different number of particles.     

Dielectric behaviour of polycrystalline lead germanate

The dielectric behaviour of ferroelectric Lead Germanate (Pb₅Ge₃O₁₁) is reported in the frequency region 60 Hz-100 KHz for various particle size ranges from 40 to 300 μ m. The dielectric constant and conductivity decrease with decreasing particle size. The dielectric anomaly in small particle size unsintered samples disappears at lower frequencies, while at 100 KHz a broad diffuse phase transition is observed for all the samples, irrespective of particle size. A strong dielectric dispersion has been observed in the frequency range 60 Hz–100 KHz. The dielectric constant of sintered samples for the same panicle size range, and the dielectric anomaly which was absent at lower frequencies for unsintered samples re-appears in sintered samples. These results have been explained by assuming a high resistivity surface layer having a lower dielectric constant than the bulk at the boundary of particles.