Al_3(Sc_(0.75)M_(0.25)(M=Ti,Y,Zr,Hf)金属间化合物有序化行为和力学性能的第一性原理计算

采用亚晶格模型,辅助以第一性原理总能计算,研究了Ll_2型Al_3Sc基金属间化合物中元素的占位有序化行为和力学性能。结果表明:Al_3Sc合金呈现完全有序化,其中Al占据3c亚晶格位置,Sc占据1a亚晶格位置;L1_2-Al_3(Sc_(0.75)M_(0.25))金属间化合物(M=Y.Ti,Zr,Hf)也呈现完全有序化,第三组元M均只占据1a亚晶格位置,这些元素的占位行为均不受温度的影响。L12-A1_3(Sc_(0.75)M_(0.25))金属间化合物均满足力学稳定性条件。当M为Y时,L12-Al_3(Sc_(0.75)M_(0.25))金属间化合物的剪切模量、体弹模量和杨氏模量和硬度下降;当M为Ti、Zr或Hf时,随着原子半径增大,剪切模量、体弹模量、杨氏模量和硬度逐渐降低,其中Ti的加入可使L12-Al_3(Sc_(0.75)M_(0.25))金属间化合物的塑性和韧性达到最好。     

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。     

三元共晶成分Al2O3/YAG/ZrO2粉体及陶瓷的制备与组织性能研究

本文采用醇水共沉淀法制备了三元共晶成分Al₂O₃/YAG/ZrO₂粉体,在600-1350_oC温度范围煅烧后研究其物相转变过程。经1300_oC煅烧后Al₂O₃/YAG/ZrO₂共晶成分粉体的物相由α-Al₂O₃、c-ZrO₂和YAG构成,且具有α-Al₂O₃相包裹c-ZrO₂相的特殊结构。将煅烧粉体在1550_oC下热压烧结,制备具有内晶型结构的共晶成分Al₂O₃/YAG/ZrO₂复相陶瓷,其致密度、室温抗弯强度、断裂韧性和高温(1000_oC)抗弯强度分别为98.8%、420 MPa、3.69 MPa.m_1/2和464 MPa,并对复相陶瓷组织结构的形成机理进行了探讨。     

Al9Fe0.7Ni1.3相对喷射沉积Al-Zn-Mg-Cu-Ni合金组织和性能的影响

本文利用喷射沉积技术合成含Ni的Al-Zn-Mg-Cu合金,合金中的Ni元素以亚微米球状Al₉Fe_0.7Ni_1.3化合物的形式存在。利用扫描电镜和电子背散射衍射、透射电镜以及拉伸测试研究了Al₉Fe_0.7Ni_1.3颗粒对合金固溶处理后组织和性能的影响。结果发现：Al₉Fe_0.7Ni_1.3颗粒主要在晶界附近分布,说明该颗粒在固溶过程中具有有力的抑制再结晶作用。固溶处理后,合金的拉伸强度为603 MPa,断裂延伸率为11.79%,主要断裂方式为穿晶延性断裂。实验结果表明亚微米球状Al₉Fe_0.7Ni_1.3化合物对合金性能有重要影响,可以产生细晶强化和Orowan强化,是合金发生穿晶延性断裂的主要原因。     

BN/Al2O3 复合粉末及其聚合物基复合材料的制备与导热性能

采用固-液相共混法制备了多种BN/Al₂O₃复合粉末,通过冻融法和表面修饰法对BN进行了改性处理,改变表面修饰剂类型和摩尔比得到了前驱体和烧结态BN/Al₂O₃复合粉末,并利用机械混合法制备了聚合物基BN/Al₂O₃复合材料,并测试分析了其导热性能。结果表明,经冻融处理的BN分散性和界面相容性明显优于未经冻融处理的BN。多巴胺对BN的改性效果优于聚乙二醇。采用多巴胺作为表面修饰剂且BN与Al(NO₃)₃的摩尔比为1:1时,能够得到纳米Al₂O₃均匀包覆的微米BN粉末,即BN/Al₂O₃微纳复合粉末,其聚合物基复合材料的导热系数可达0.62 W·m^-1·K^-1,是纯聚合物导热系数的3倍,是采用纯微米BN粉末制备的聚合物基复合材料导热系数的1.5倍。在BN表面附着的Al₂O₃可以形成层状热传导通道,能够有效提高聚合物基BN/Al₂O₃复合材料的热导率。     

Al0.7Sb2Te3三元靶材的结构性能表征

以原子比Al:Sb:Te=0.7:2:3的混和粉为原料,采用真空合成法与烧结-热等静压制备Al_0.7Sb₂Te₃三元靶材,通过XRD、FESEM、EDS、XPS等手段表征其性能,且重点采用XPS研究Al在Al_0.7Sb₂Te₃三元靶材的存在状态。结果表明：Al掺杂后,靶材主相Sb₂Te₃的晶格常数减小,且单质Al弥散相与Al_0.1Sb₂Te₃基体相共存,表明掺杂对靶材的组织结构确有影响;刻蚀深度从0增加至405.9nm,Al价态从以Al₂O₃的化合态为主逐渐过渡至以单质态为主,且Al以Al₂O₃形态为主的区域深度约90nm;刻蚀深度为405.9nm时,来自非氧化物的Al价态与来自AlSb的Sb价态联合表明：Al_0.1Sb₂Te₃中的Al通过有效化合形成AlSb影响着靶材的组织结构。     

功率对激光熔覆(Fe0.25Co0.25Ni0.25Cr0.125Mo0.125)86B14涂层组织均质性及磨损性能的影响*

目前激光熔覆缺少对涂层组织、相结构纵向均质性与性能关联的研究。采用激光熔覆技术,选取不同的激光功率,制备(Fe_0.25Co_0.25Ni_0.25Cr_0.125Mo_0.125)₈₆B₁₄ 高熵合金涂层;借助电子探针(EPMA)、扫描电子显微镜(SEM)、能谱仪(EDS)和 X 射线衍射仪(XRD)等观察涂层微观组织与物相纵向分布,利用显微硬度计和摩擦磨损试验机测试涂层不同深度部位显微硬度及磨损性能,分析激光功率对熔覆(Fe_0.25Co_0.25Ni_0.25Cr_0.125Mo_0.125)₈₆B₁₄ 涂层纵向组织、物相分布影响规律及磨损性能。结果表明：三种功率下,涂层均由 BCC+FCC 相、硬质相 Mo₂B 组成,Mo₂B 在枝晶间富集。随着功率的增加,涂层中底部显微组织由细枝晶向粗大的柱状晶转变。三种涂层硬度均由表及里先增加后降低,摩擦因数先降低后增加;但是当激光功率为 1.6 kW 时,涂层呈现以 BCC 相为主的 FCC+BCC 双相结构,且由表及里 BCC 相含量不断增加、Mo₂B 含量逐渐减少,涂层组织均质化最高,摩擦因数变化梯度最小,耐磨损性能最佳。激光功率会影响熔覆高熵合金耐磨涂层均质性,进而影响摩擦性能的稳定性。     

Al2O3/Ti2AlN复合材料在900℃,1000℃和1100℃空气中的氧化行为

利用综合热分析仪、背散射扫描电镜(BSE)和能谱分析(EDS)对Al₂O₃/Ti₂AlN复合材料在900 ℃,1 000 ℃和1 100 ℃/20 h空气中连续氧化20h后的氧化增重及氧化层截面进行了研究。结果表明：Al₂O₃/Ti₂AlN复合材料在空气中的氧化行为符合抛物线规律,在900 ℃,1 000 ℃和1 100 ℃/20 h氧化增重分别为2.78×10_-2 kg/m₂、10.4 ×10_-2 kg/m₂、21.9 ×10_-2 kg/m₂,抛物线速率常数相应为1.08×10_-8 kg₂/m₄s、1.44×10_-7 kg₂/m₄s、6.56×10_-7 kg₂/m₄s,氧化激活能为274 kJ/mol。氧化层主要由TiO₂和Al₂O₃组成的,连续的Al₂O₃次外层可以提高其抗氧化性能。氧化层结构的改变是由于氧化温度对Ti₄₊、Al₃₊由基体表面向外扩散和O_2-向内扩散的影响,以及TiO₂和Al₂O₃在不同温度下的形核生长速率导致的。对Al₂O₃/Ti₂AlN而言,控制材料与氧化气氛的界面是提高该材料抗氧化性能的关键。     

TiZrNiCu钎焊Si3N4-MoSi2复合陶瓷与Nb接头组织与力学性能

采用高温活性钎料TiZrNiCu对Si₃N₄-MoSi₂复合陶瓷和金属Nb进行真空钎焊试验,研究了其典型界面组织组成及形成机理,分析了钎焊温度和保温时间对钎焊接头界面组织及力学性能的影响规律。结果表明,接头典型界面结构为Nb/β-Ti/(Ti. Zr)₂(Cu, Ni)+β-Ti+(Ti, Zr)₅Si₃/TiN+(Ti, Zr)₅Si₃+MoSi₂/Si₃N₄-MoSi₂。钎焊温度和保温时间主要通过控制Si₃N₄-MoSi₂复合陶瓷母材中Si原子向钎料中扩散程度,来影响钎缝中(Ti, Zr)₅Si₃化合物的数量及分布,进而影响钎焊接头的抗剪强度。在920 ℃/10 min的工艺参数下,Si₃N₄-MoSi₂/Nb接头的室温抗剪强度最高达到112 MPa,选择最优参数条件下的Nb/Si₃N₄-MoSi₂钎焊接头在500 ℃和600 ℃条件下进行高温剪切实验,其高温抗剪强度分别达到123 MPa和131 MPa。     

Cu-Fe64Ni32Co4合金显微组织及热物理性能研究

本研究利用相图计算的CALPHAD方法和真空电弧熔炼技术,设计并制备了Cu_x(Fe_0.64Ni_0.32Co_0.04)_100-x(x=30, 45, 60, wt. %)系列合金。实验研究了该系列合金在不同热处理工艺时的显微组织,热导率以及热膨胀系数。研究结果表明：Cu-Fe₆₄Ni₃₂Co₄系列合金在600 °C和800 °C时效处理后均为fcc富铜相和fcc富因瓦(铁镍钴)相组成的各向同性的多晶合金。该系列合金在1000 °C淬火并在600 °C时效处理50 h后,其热膨胀系数变化范围为6.88~12.36×10_-6 K_-1;热导率变化范围为22.91~56.13 W.m_-1.K_-1;其热导率明显高于因瓦合金,其中Cu₃₀(Fe_0.64Ni_0.32Co_0.04)₇₀与 Cu₄₅(Fe_0.64Ni_0.32Co_0.04)₅₅合金的热膨胀系数可以与电子封装中半导体材料的热膨胀系数相匹配。     

Microstructure of Al3Sc with ternary rare-earth additions

The microstructure of ternary L1₂-Al₃(Sc_1?yRE_y) intermetallics, where RE is one of the rare-earth elements selected from five light (La, Ce, Nd, Sm or Eu) or two heavy lanthanoids (Yb or Lu), was investigated as a function of RE concentration for 0.02 ≤ y ≤ 0.75. Alloys with light RE show two phases: L1₂-Al₃(Sc,RE) and D0₁₉-Al₃(RE,Sc) (or C11_b-Al₄(Eu,Sc)). Alloys with heavy RE exhibit a single L1₂-Al₃(Sc,RE) phase. The maximum RE solubility in the L1₂ phase is very low (<0.4 at.%) for La, Ce, Nd and Eu, low (3.2 at.%) for Sm and complete solid-solution for Yb and Lu. Both lattice parameter and hardness of the L1₂-Al₃(Sc,RE) phases increase linearly with Sm, Yb or Lu concentration, and the magnitude of both effects correlates with the atomic size mismatch between Sc and RE.     

Conductivity of a new pyrophosphate Sn0.9Sc0.1(P2O7)1−δ prepared by an aqueous solution method

New pyrophosphate Sn_0.9Sc_0.1(P₂O₇)_1−δ was prepared by an aqueous solution method. The structure and conductivity of Sn_0.9Sc_0.1(P₂O₇)_1−δ have been investigated. XRD analysis indicates that Sn_0.9Sc_0.1(P₂O₇)_1−δ exhibits a 3 × 3 × 3 super structure. It was found that Sn_0.9Sc_0.1(P₂O₇)_1−δ prepared by an aqueous method is not conductive. The total conductivity of Sn_0.9Sc_0.1(P₂O₇)_1−δ in open air is 2.35 × 10⁻⁶ and 2.82 × 10⁻⁹ S/cm at 900 and 400 °C respectively. In wet air, the total conductivity is about two orders of magnitude higher (8.1 × 10⁻⁷ S/cm at 400 °C) than in open air indicating some proton conduction. SnP₂O₇ and Sn_0.92In_0.08(P₂O₇)_1−δ prepared by an acidic method were reported fairly conductive but prepared by similar solution methods are not conductive. Therefore, the conductivity of SnP₂O₇-based materials might be related to the synthetic history. The possible conduction mechanism of SnP₂O₇-based materials has been discussed in detail.     

L12型Co3Ti基金属间化合物有序化行为的热力学研究

采用亚晶格模型,辅助以第一性原理总能计算,研究了L12结构的Co3Ti基金属间化合物中元素的占位有序化行为。结果表明,Co3Ti化学计量比合金呈现完全有序化;对于xCo/xTi为3:1的Co72Ti24M4合金,第3合金组元M为Si或Ta时,M与Ti共同占据1a位置,M为Cu、Ni、Pd、Rh、V或W时,M与Co占据3c位置,而当M为Al、Cr、Ge、Mn、Sc或Y时,M在1a和3c位置的占位分数相同,这些元素的占位行为均不受温度影响;而当M为Fe、Hf、Mo、Nb、Ru和Zr的占位情况随温度发生变化。随原子核外层电子的增加,原子占位逐渐倾向于从1a亚晶格转向3c位置。亦预测了xCo/xTi偏离3:1的部分合金的占位分数随合金成分和温度的变化细节,预测结果与文献进行了比较,并澄清了文献上的分歧     

Preparation and characteristic of spherical Li3V2(PO4)3

Spherical Li₃V₂(PO₄)₃ was synthesized by using N₂H₄ as reducer. The products were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that single-phase, spherical and well-dispersed Li₃V₂(PO₄)₃ has been successfully synthesized in our experimental process. Electrochemical behaviors have been characterized by charge/discharge measurements. The initial discharge capacities of Li₃V₂(PO₄)₃ were 123 mAh g⁻¹ in the voltage range of 3.0–4.3 V and 132 mAh g⁻¹ in the voltage range of 3.0–4.8 V.     

Effect of ternary alloying elements addition on atomic ordering characteristics of Fe–Al intermetallics

The energetic and structural characteristics of atomic ordering processes in Fe_0.5(Al_1−nX_n)_0.5 intermetallics have been qualitatively analyzed based on the statistico-thermodynamical theory of ordering by means of a quasi-chemical method combined with electronic theory in the pseudopotential approximation. The effects of ternary impurities on order–disorder phase transformation temperature and the characteristics of atomic short-range order in Fe–Al type intermetallics have been calculated. Impurity elements in Fe_0.5(Al_1−nX_n)_0.5 where X=Ni, Co, Mn, Cr, Ti, Si, Zr, Hf, Nb, Ta, Re, Mo or W, are considered up to 1 at.% concentration. The results of the calculation indicate that the impurity elements, X, with regard to their lattice site occupancy characteristics (SRO) can be divided into two groups; X_I=Ni, Co, Mn or Cr element atoms substitute mainly for Al sublattice sites, whereas X_II=Ti, Si, Zr, Hf, Nb, Ta, Re, Mo or W element atoms substitute preferentially for Fe sublattice sites in Fe_0.5(Al_1−nX_n)_0.5 intermetallics. It has been found that the absolute values of partial ordering energies of the W^Al–X(R₁) and W^Fe–X(R₁) have a profound effect on the order–disorder transition temperature of Fe_0.5(Al_1−nX_n)_0.5 alloys that would either increase or remain unchanged depending on the type and content of the ternary substitutional alloying elements. The impurities X=Zr, Hf, Nb, Ta, Re, Mo or W which are preferentially distributed Fe sublattice sites are more effective in increasing order–disorder transition temperature in Fe–Al(B2) intermetallics. The results of the present calculation are in good qualitative agreement with experimental observation for most of the third component impurity elements X in Fe_0.5(Al_1−nX_n)_0.5 intermetallics.     

废旧锂离子电池中Li, Fe和V的回收及xLiFePO4-yLi3V2(PO4)3的制备

由于LiFePO_4和Li_3V_2(PO_4)_3材料的特征相近,制备方法类似,提供了一种从废旧LiFePO_4和Li_3V_2(PO_4)_3混合电池中回收Li、Fe和V,再制备xLiFePO_4-yLi_3V_2(PO_4)_3的方法。在空气气氛中600℃热处理1h后,去除粘结剂PVDF使活性物质与集流体分离。调节Li、Fe、V和P摩尔比,球磨、锻烧,配制不同比例的xLiFePO_4-yLi_3V_2(PO_4)_3(x:y=5:1,7:1,9:1)复合电极材料。表征了其形貌、结构和电化学性能,结果表明,回收制备的复合材料将同时具备LiFePO_4和Li_3V_2(PO_4)_3两种材料的电化学性能,能显著改善LiFePO_4的倍率性能。     

Structural, elastic and electronic properties of Mg(Cu1−xZnx)2 alloys calculated by first-principles

The structural, elastic and electronic properties of Mg(Cu_1−xZn_x)₂ alloys (x = 0, 0.25, 0.5,and 0.75) were investigated by means of first-principle calculations within the framework of density functional theory (DFT). The calculation results demonstrated that the partial substitution of Cu with Zn in MgCu₂ leaded to an increase of lattice constants, and the optimized structural parameters were in very good agreement with the available experimental values. From energetic point of view, it was found that with increase of Zn content the structural stability of Mg(Cu_1−xZn_x)₂ alloys decreased apparently. The single-crystal elastic constants were obtained by computing total energy as a function of strain, and then the bulk modulus B, shear modulus G, Young's modulus Y and Poisson's ratio ν of polycrystalline aggregates were derived. The calculated results showed that among the Mg(Cu_1−xZn_x)₂ alloys, MgCuZn exhibited the largest stiffness, while Mg₂Cu₃Zn showed the best ductility. Finally, the electronic density of states (DOSs) and charge density distribution were further studied and discussed.     

TEM and DFT investigation of CVD TiN/κ-Al2O3 multilayer coatings

This paper investigates the interfacial structure in hot-wall CVD TiN/κ-Al₂O₃ multilayer coatings using both HREM and DFT modeling. Two multilayers with different thicknesses of the TiN layers (50 and 600 nm) separating the κ-Al₂O₃ layers are analyzed. The general microstructure of the two multilayers is relatively similar. The TiN layer in the thicker TiN/κ-Al₂O₃ coating is thick enough to be several TiN grains high. This means that epitaxial columns, which are often found in the thinner TiN/κ-Al₂O₃ coatings, are not present. However, the orientation relationships at the TiN/κ-Al₂O₃ interfaces are the same in both multilayers. The HREM investigations show that κ-Al₂O₃ (001) planes can grow directly on flat (111) TiN faces, without any other phases or detectable amounts of impurities, such as sulphur, present. Where the TiN layers are more curved, γ-Al₂O₃ can be grown, at least partly stabilized by the cube-on-cube orientation relationship between γ-Al₂O₃ and the underlying TiN. The DFT calculations show very similar adsorption strengths for an O monolayer positioned on Ti-terminated TiC(111) and TiN(111) surfaces, with preferred adsorption in the fcc site. O adsorption on N-terminated TiN(111) is much weaker, with preferred adsorption in the top site. Calculated elastic-energy contributions yield a higher stability for κ-Al₂O₃ on TiN(111) than on TiC(111) and a higher stability for κ-Al₂O₃ than for α-Al₂O₃ on both TiC and TiN. This indicates that the observed higher stability of κ-Al₂O₃ on TiC(111) than on TiN(111) is not due to the lattice mismatch, while the preferred epitaxial growth of κ-Al₂O₃ over α-Al₂O₃ can be partly attributed to the mismatch.     

固相-水热法制备LiFePO4-Li3V2（PO4）3复合材料及其电化学性能（英文）

分别采用固相-水热法和球磨法制备磷酸亚铁锂-磷酸钒锂复合正极材料(LiFePO4-Li3V2(PO4)3)。电化学性能测试表明,LiFePO4-Li3V2(PO4)3复合正极材料的电化学性能远远高于 LiFePO4和 Li3V2(PO4)3单独作为正极材料的性能,并且以固相-水热法制备的复合材料性能优于以球磨法制得的复合材料。研究发现 LiFePO4-Li3V2(PO4)3复合材料有 4 个氧化还原峰,相当于 LiFePO4 和 Li3V2(PO4)3 氧化还原峰的叠加。采用固相-水热法制备的LiFePO4-Li3V2(PO4)3 复合材料形貌较为规则,且有新相物质产生,这是导致其电化学性能较好的原因。     

Improved high-Q microwave dielectric resonator using ZnO-doped La(Co1/2Ti1/2)O3 ceramics

The microwave dielectric properties and the microstructures of ZnO-doped La(Co_1/2Ti_1/2)O₃ ceramics prepared by conventional solid-state route have been studied. Doped with ZnO (up to 0.75 wt%) can effectively promote the densification of La(Co_1/2Ti_1/2)O₃ ceramics with low sintering temperature. At 1320 °C, La(Co_1/2Ti_1/2)O₃ ceramics with 0.75 wt% ZnO addition possesses a dielectric constant (_r) of 30.2, a Q × f value of 73,000 GHz (at 8 GHz) and a temperature coefficient of resonant frequency (τ_f) of −35 ppm/°C.