微量元素Nb、C强化W-Lu2O3复合材料的组织及性能研究

采用机械球磨和放电等离子体烧结制备了W-Lu₂O₃和W-Nb-C-Lu₂O₃合金,通过场发射扫描电子显微镜(FE-SEM)、能谱(EDS)和透射电子显微镜(TEM)研究分析了合金复合粉末的形貌、合金烧结体表面形貌和断口形貌;测定了合金的致密度、热导率、硬度和强度。实验结果表明：在W-Lu₂O₃的基础上添加微量Nb和C对钨合金晶粒细化、致密化和强度提高有着明显的效果,W-Nb-C-Lu₂O₃合金的致密度比W-Lu₂O₃提高了5.75%,达到了95.12%,晶粒尺寸由8~13 μm细化到2~5 μm,W-Nb-C-Lu₂O₃合金比W-Lu₂O₃合金的显微硬度和强度得到明显改善。     

微量Y增强细晶W烧结行为和组织性能的研究

以“溶胶喷雾干燥-纳米原位复合”合成的超细/纳米W-0.3%Y复合粉末为原料,通过普通模压-预烧和在1800~1950℃下烧结制备细晶钨合金。检测了合金显微硬度和拉伸强度,并利用扫描电镜SEM和X射线能量色散谱(EDX)观察了断口形貌及显微组织,研究其烧结行为及断裂行为变化。结果表明：微量稀土Y以Y₂O₃二次相粒子的形式均匀弥散分布于W晶粒的晶内和晶界处,能有效抑制W晶粒的长大,显著细化晶粒,提高其力学性能。微量稀土Y的添加改变了W合金的断裂形式,由纯W的沿晶断裂转变为主要沿晶、部分穿晶的断裂方式。     

放电等离子烧结MoNbTaW难熔高熵合金

以纯金属元素粉末为原料,采用放电等离子烧结工艺制备了MoNbTaW难熔高熵合金,研究了烧结温度和保温时间等工艺参数对MoNbTaW难熔高熵合金的物相、晶体结构、烧结行为和力学性能的影响。结果表明,在烧结温度1800℃和保温5min即可形成BCC单相高熵合金;烧结温度是影响MoNbTaW难熔高熵合金致密度、晶粒尺寸和力学性能的主要因素;随着烧结温度的升高,合金的晶粒尺寸增大,致密度、硬度和和屈服强度均增高;烧结温度为2000℃时合金的致密度可达99.8%,化学成分无偏析,屈服强度为1314±14MPa,断裂韧性为(5～6)MPa.m_1/2,其断裂模式为解理断裂。     

退火对激光熔覆AlCoCrFeNiTi0.5高熵合金涂层组织和耐磨性的影响

对激光熔覆AlCoCrFeNiTi_0.5高熵合金涂层进行900℃退火,保温5h处理。主要对退火前后样品的微观结构和耐磨性进行研究。XRD结果表明,退火后的AlCoCrFeNiTi_0.5高熵合金涂层,其相组成有Co₃Ti和BCC结构的AlFe固溶相,出现典型的成分均匀的网状调幅分解组织;退火后的平均显微硬度达到989HV_0.5,比退火前提高了73.5%;耐磨性测试结果显示,退火后磨损量比退火前降低了92.5%,磨损宽度是退火前的50%。     

基于第一性原理的石榴石型Li7La3Zr2O12 固态电解质的设计与合成

基于密度泛函理论（DFT）的第一原理方法计算了四方相和立方相中2种不同的Li₇La₃Zr₂O₁₂（LLZO）固体电解质材料的能带结构,晶格参数,态密度和成键特性。基于理论计算结果,通过电子结构特性解释了四面体相的离子电导率低于立方相的离子电导率的原因。基于LLZO的第一性原理计算,设计了2种晶体结构的LLZO材料,并通过高温固相法制备并分析了不同烧结时间的LLZO颗粒的性能。探索了合成工艺参数对Li₇La₃Zr₂O₁₂性能的影响。立方晶Li₇La₃Zr₂O₁₂（C-LLZO）的平均晶格大小为a=b=c=1.302 246 nm,而四方Li₇La₃Zr₂O₁₂（T-LLZO）的平均晶格大小为a=b=1.313 064 nm,c=1.266 024 nm。在1000 ℃下烧结12 h的C-LLZO为纯立方相,在室温（25 ℃）下最大离子电导率为9.8×10^-5 S·cm^-1。T-LLZO在室温（25 ℃）下的离子电导率为5.96×10^-8 S·cm^-1,在800 ℃下烧结6 h具有纯的四方相结构,与计算结果基本吻合。     

超细晶粉末冶金CoCrFeMnNiGd0.15高熵合金的组织性能

采用机械合金化和放电等离子烧结的方法制备出超细晶CoCrFeMnNiGd_0.15合金,研究了CoCrFeMnNiGd_0.15高熵合金的组织与性能。结果表明,其组织为多相结构,基体为FCC固溶体相,析出相为稀土氧化物(Gd₂O₃)和富Gd、Ni、Mn的四方结构相。随着烧结温度的提高,析出相的含量不断增加且尺寸不断增大,合金的压缩屈服强度不断下降而塑性则不断上升。在900℃烧结时材料具有最优的综合力学性能,其压缩屈服强度(σ_0.2)、抗压强度(σ_max)、断裂时的塑性应变(ε_p)和维氏硬度分别达到1662 MPa、2518 MPa、30.6%和458 Hv。     

ZrB2增韧Al2O3陶瓷制备工艺及其对复相陶瓷力学性能影响

Al₂O₃陶瓷因具有很高的强度和耐蚀性受到广泛关注。但由于相对较差的韧性限制了其广泛应用。Al₂O₃陶瓷增韧的方式很多,本文采用微米ZrB₂来增韧氧化铝陶瓷,探讨复相陶瓷烧结工艺,并研究工艺参数对复相陶瓷力学性能及韧性的影响。结果表明：采用单因素法得到两种陶瓷最佳工艺参数分别是纯α-Al₂O₃陶瓷烧结温度为1500℃,成型压力为450MPa,保温时间为8h,球料比为1/2,保压时间为10min;ZrB₂(wt,20%)+α-Al₂O₃ (wt,80%)复相陶瓷烧结温度为1450℃,成型压力为450MPa,保温时间为8h,球料比为1/2,保压时间为10min。其中成型压力、烧结温度和保温时间对复相陶瓷硬度及致密度影响最大。ZrB₂的加入,在降低陶瓷烧结温度的同时,可以将纯α-Al₂O₃陶瓷的断裂韧性由5.2±0.3MPa.m^_1/2提高到6.7±0.2MPa.m^_1/2。     

稀土改性Fe-Al层表面Al2O3 薄膜的物相分布

在760 ℃下采用稀土改性包埋渗铝以及原位氧化方法制备Fe-Al/Al₂O₃复合涂层,研究了渗铝层和氧化膜的微观组织和相分布。结果表明,稀土改性渗铝层可分为3层：外层渗铝层、过渡层和内扩散层。渗铝层主要由FeAl相和Fe₃Al相组成。FeAl相主要集中在渗铝层的外层,为Al₂O₃氧化膜的选择性氧化提供了有利条件。氧化膜表面呈α-Al₂O₃脊状结构。此外,表面氧化铈的存在是由于氧化初期Ce向外扩散且与O₂的优先反应。氧化膜可分为2层,即纯α-Al₂O₃层和主要由α-Fe(Al)和Al、Fe、Ce的混合氧化物组成的过渡层。     

粉末冶金法制备Al x CuFeNiCoCr高熵合金及其性能

采用粉末冶金法制备了Al_xCuFeNiCoCr高熵合金。研究了铝含量对合金性能和组织的影响,并讨论了合金制备过程中晶粒性能的变化。结果表明,在球磨过程中合金晶粒细化,且合金晶粒尺寸随Al含量的增加而增大。在烧结过程中,合金中会产生新的晶粒,并首先吸收一定热量形成含Al的金属间化合物。在1200 ℃加热2 h后,获得具有简单晶体结构的相,证实了高熵合金的形成。根据获得的能谱,合金组成均匀,合金化程度高。然而,随着Al含量的增加,出现了少量具有高Al含量的高对比度区域。合金具有良好的高温抗氧化性能和抗电化学腐蚀性能。随着铝含量的增加,合金的高温抗氧化性能提高。当Al含量为1mol%时,自腐蚀电压为-235 mV。随着Al含量的增加,硬度也增加。结果表明,当Al含量为1mol%时,合金具有最佳综合性能。     

空气气氛下碳热还原筛分法制备Magnéli相Ti n O2 n -1

介绍了一种在空气气氛中通过碳热还原筛分法制备Magnéli相（Ti_nO_2n-1，4＜n＜10）低价钛氧化物的方法，研究了还原温度和还原时间对还原产物的物相、电阻率的影响。结果表明，提高还原温度和延长还原时间有利于将TiO₂还原为Magnéli相Ti_nO_2n-1。将Magnéli相Ti_nO_2n-1 (n=4，5) 粉末在1350 ℃下干燥20 min，通过扫描电子显微镜观察，其粒径为0.5~8 μm。在还原温度为1350 ℃时，还原产物的电阻率随还原时间的延长而显著降低。在1350 ℃下还原50 min的产物的电阻率最小，为79.3 Ω?cm，其物相组成几乎全部为Ti₃O₅。     

X-ray diffraction study of Ba0.985Na0.015Ti0.985Nb0.015O3, Ba0.6Na0.4Ti0.6Nb0.4O3 and Ba0.3Na0.7Ti0.3Nb0.7O3 compositions

The Ba_0.985Na_0.015Ti_0.985Nb_0.015O₃, Ba_0.6Na_0.4Ti_0.6Nb_0.4O₃ and Ba_0.3Na_0.7Ti_0.3Nb_0.7O₃ compositions of the (1 − x) BaTiO₃–xNaNbO₃ (BTNNx) system have been studied by X-ray diffraction and by measurements of dielectric properties. The specimens with composition BTNN (x = 0.015, 0.40 and 0.70) have been refined by the JANA program from X-ray powder diffraction data. Ceramic samples with composition (1 − x) BaTiO₃ + xNaNbO₃ (where x = 0.015, 0.40 and 0.70) were prepared by calcinations from appropriate mixture of BaCO₃, TiO₂, Na₂CO₃ and Nb₂O₅. The calcined powder was sintered at temperature range 1200–1400 °C. As the composition x increased from 0.015 (and 0.70), the ferroelectric ceramics (x = 0.015, FE) with tetragonal phase changed to the ferroelectric relaxors (RFE, x = 0.40). RFE ceramics showed a peculiar diffuse phase transition and dielectric relaxation at the low temperature (down to 180 K) due to a frustration between RFE and FE state. These ceramics present the classical ferroelectric character when 0 ≤ x < 0.075 and 0.55 < x ≤ 1 and relaxor character when 0.075 ≤ x ≤ 0.55.     

Magnetic, electrical and plastic properties of Fe76Nb2Si13B9, Fe75Ag1Nb2Si13B9 and Fe75Cu1Nb2Si13B9 amorphous alloys

Influence of 1 h annealing in vacuum on magnetic, electrical and plastic properties of Fe₇₆Nb₂Si₁₃B₉, Fe₇₅Ag₁Nb₂Si₁₃B₉ and Fe₇₅Cu₁Nb₂Si₁₃B₉ melt spun ribbons were carefully investigated. It was shown that in all cases soft magnetic properties can be significantly enhanced by applying 1-h annealing at characteristic temperatures T_op. This optimization annealing causes that permeability increases more than 15-times and magnetic losses (tangent of loss angle) achieves a minimum in relation to the as quenched state. Using structural examinations (X-ray and HRTEM) it was shown that for the Fe₇₅Cu₁Nb₂Si₁₃B₉ alloy the optimized microstructure corresponds to a nanocrystalline αFe(Si) phase whereas in other alloys to a relaxed amorphous phase free of iron nanograins. As a consequence of this fact the Fe₇₆Nb₂Si₁₃B₉ and Fe₇₅Ag₁Nb₂Si₁₃B₉ alloys show higher plasticity in comparison to the nanocrystalline Fe₇₅Cu₁Nb₂Si₁₃B₉ alloy. Temperatures of the first stage of crystallization, and related diffusion parameters were determined using measurements of resistivity versus temperature with different heating rates.     

Fe2+-Ni2+-NH3-NH4+-C2O42-H2O体系的沉淀配合平衡热力学

针对草酸盐配位共沉淀热分解还原法制备超细铁镍合金粉过程中Fe2+-Ni2+-NH3-NH4+-C2O42--H2O体系的溶液平衡建立热力学分析模型,并根据模型进行相关计算,揭示反应体系中各物质随pH值、氨及草酸浓度的变化关系。结果表明:溶液中的Fe主要以[Fe(C2O4)n]2 2n络合物形式存在,而铁氨络合物含量很低。当氨含量较低时,溶液中的Ni主要以[Ni(C2O4)n]2 2n存在;氨含量较高时,在酸性条件下,溶液中的Ni主要以[Ni(C2O4)n]2 2n存在,在碱性条件下,则主要以[Ni(NH3)n]2+存在。低pH值下,Ni的沉淀率较Fe的高,而高pH值下,Ni的沉淀率则较Fe的低。     

New Zr6CoAs2-type compounds: Y6CoBi2, Ho6CoBi2 and Tm6CoBi2

Results of a powder X-ray diffraction investigation of new ternary compounds are reported. The compounds Y₆CoBi₂ [a=0.8312(1) nm, c=0.4144(1) nm], Ho₆CoBi₂ [a=0.8246(2) nm, c=0.4095(1) nm], and Tm₆CoBi₂ [a=0.8155(2) nm, c=0.4066(1) nm] crystallize in the hexagonal Zr₆CoAs₂-type structure (space group P6b2m No. 189). The Zr₆CoAs₂-type structure is a superstructure of the Fe₂P-type structure.     

Thermodynamics and phase diagrams in the binary systems Na2O-SiO2, Na2O-GeO2, Na2O-B2O3, Li2O-B2O3, CaO-B2O3, SrO-B2O3, and BaO-B2O3

We applied our model to the enthalpy of mixing data of the binary systems Na₂O-SiO₂, Na₂O-GeO₂, Na₂O-B₂O₃, Li₂O-B₂O₃, CaO-B₂O₃, SrO-B₂O₃, and BaO-B₂O₃. The most stable composition in the liquid, that is where the enthalpy of mixing is most negative, is with a metal-oxygen ratio of 4 to 3, for monovalent metals (Na and Li) and 3 to 4 for divalent metals (Ba and Ca) in liquid silicates or borates. The same applies to the CaO-SiO₂, CaO-Al₂O₃, PbO-B₂O₃, PbO-SiO₂, ZnO-B₂O₃, and ZnO-SiO₂ systems. The oxygen to metal ratio, its constant value in various types of systems, reflects and describes the structure of the liquid. Using the analyzed enthalpies of mixing data and the available phase diagrams, we calculated the enthalpies of formation of the various binary compounds. The results are in excellent agreement with data in the literature that were obtained from direct solid-solid calorimetry.     

Al2O3-Sm2O3-CeO2电解质的性能（英文）

采用溶胶-凝胶法和低温燃烧技术制备Ce1-xSmxO2（x=0,0.1,0.2,0.3）和掺杂Sm和（2%-8%）Al2O3的二氧化铈;研究其合成、结构、致密化、导电性和热膨胀等性能,并利用XRD研究其结构和相组成。结果表明,于1300°C烧结球团,获得致密的陶瓷,于1250°C在Ce0.8Sm0.2O0.2中加入2%和4%的Al2O3以促进烧结。利用扫描电子显微镜观察烧结后球团的表面形貌,使用双探针交流阻抗谱研究总离子电导率。     

Zur Kenntnis von RbBa3Ca4Cu3V7O28

Single crystals of RbBa₃Ca₄Cu₃V₇O₂₈ were prepared above the melting point of the reaction mixture. It crystallizes with hexagonal symmetry, space group C_6V⁴-P6₃mc, a 11.1751, c 12.434 Å, Z = 2. RbBa₃Ca₄Cu₃V₇O₂₈ is the second member of a new structure type of the copper-oxovanadates. Ba²⁺ shows an unusual 12-fold coordination. The two calcium positions are coordinated by trigonal prisms and octahedra respectively. The copper coordination is characterized by a stretched square pyramid. The Cu²⁺ ions are outside the centre nearly in plane of the pyramids.

Zusammenfassung

Einkristalle von RbBa₃Ca₄Cu₃V₇O₂₈ wurden oberhalb des Schmelzpunktes der Reaktionsmischung erhalten. Die Verbindung kristallisiert hexagonal, Raumgruppe C_6V⁴-P6₃mc, a 11.1751, c 12.434 Å, Z = 2. RbBa₃Ca₄Cu₃V₇O₂₈ ist das zweite Beispiel für einen neuen Strukturtyp der Kupfer-Oxovanadate, mit 12-fach koordinierten Ba²⁺ -Ionen. Die zwei Calciumpositionen sind trigonal prismatisch bzw. oktaedrisch koordiniert. Die Koordination der Cu²⁺-Ionen ist durch eine gestreckte Pyramide charakterisiert. Cu²⁺ ist auβerhalb des Polyederzentrums nahezu in der quadratischen Fläche der Pyramide angeordnet.     

Sinterability and dielectric properties of Ba0.55Sr0.4Ca0.05TiO3-CaTiSiO5-Mg2TiO4 composite ceramics

The composite ceramics of Ba_0.55Sr_0.4Ca_0.05TiO₃-CaTiSiO₅-Mg₂TiO₄ (BSCT-CTS-MT) were prepared by the conventional solid-state route. The sintering performance, phase structures, morphologies, and dielectric properties of the composite ceramics were investigated. The BSCT-CTS-MT ceramics were sintered at 1100 °C and possessed dense microstructure. The dielectric constant was tailored from 1196 to 141 as the amount of Mg₂TiO₄ increased from 0 to 50 wt%. The dielectric constant and dielectric loss of 40 wt% Ba_0.55Sr_0.4Ca_0.05TiO₃-10 wt% CaTiSiO₅-50 wt% Mg₂TiO₄ was 141 and 0.0020, respectively, and the tunability was 8.64% under a DC electric field of 8.0 kV/cm. The Curie peaks were broadened and depressed after the addition of CaTiSiO₅. The optimistic dielectric properties made it a promising candidate for the application of tunable capacitors and phase shifters.     

电弧喷涂制备Fe65Cr20Mo7B3.5SiMn1.5W3涂层

在Q235低碳钢板上利用电弧喷涂工艺进行喷涂,以制得Fe65Cr20Mo7B3.5SiMn1.5W3涂层。喷涂材料为自行配制的丝材,按照35%的填充率将配好的粉填充到U型不锈钢外皮中,经过多道拉拔、挤压工艺制成Φ2mm的粉芯丝材。采用X射线衍射仪、扫描电镜、能谱分析仪、透射电镜对涂层的物相和组织形貌及成分进行了表征;采用差示扫描量热仪、显微硬度仪等设备对涂层的热稳定性及显微硬度进行了检测和分析。试验结果表明:涂层组织形貌呈典型的层状组织结构,由变形良好的带状粒子相互搭接堆积而成。涂层含有50.63%的非晶相,同时含有纳米级的晶相。涂层组织均匀、结构致密、孔隙率低,并且涂层硬度高达1040.5HV0.3,属硬质涂层,具有良好的热稳定性。     

Y2O3-BaO-SiO2-B2O3-Al2O3 glass sealant for solid oxide fuel cells

A glass based on Y₂O₃-BaO-SiO₂-B₂O₃-Al₂O₃ (named YBA) has been investigated as sealant for planar solid oxide fuel cells (SOFCs). The YBA glass has been systematically characterized by differential thermal analysis, dilatometer, scanning electron microscopy, impedance analysis, and open circuit voltage to examine their suitability as sealant. The coefficient of thermal expansion of YBA is 11.64 × 10⁻⁶ K⁻¹ between 323 and 873 K. The resistivity is 9.1 × 10⁴ Ω cm at 800 °C. The glass sealant is found to be well adhered with other cell components, such as electrolytes and stainless steels, at an optimum sealing temperature of 800 °C. All measured results showed that the YBA glass appears to be a promising sealant for SOFCs.