(Ca_(0.96)D_(0.04))MnO_3(D=Ca,Sr,Rb,Sm)氧化物的制备和热电性能

利用溶胶凝胶法制备出(Ca_(0.96)D_(0.04))MnO_3(D=Ca,Sr,Rb,Sm)氧化物粉末后,先分别采用氩气气氛的放电等离子烧结和空气气氛的常压烧结制备出CaMnO_3(CMO)块体,并对其进行相组成分析,选择出更为优异的CaMnO3块体制备方法。再进一步制备出(Ca_(0.96)D_(0.04))MnO_3(D=Sr, Rb, Sm)氧化物块体,最后对(Ca_(0.96)D_(0.04))MnO_3(D=Ca, Sr, Rb, Sm)块体的物相组成、显微组织和热电性能进行测试分析。实验结果表明:氩气气氛放电等离子烧结制备的CaMnO_3块体发生物相分解,原因是放电等离子烧结的烧结环境贫氧;空气气氛的常压烧结可以得到物相较纯净的(Ca_(0.96)D_(0.04))MnO_3(D=Ca, Sr,Rb, Sm)块体;在整个测试温度范围内,(Ca_(0.96)D_(0.04))MnO_3(D=Sr, Rb, Sm)的ZT值在873 K时达到最大,分别为0.11、0.08和0.07,相比于未掺杂试样提高了1.3～2.2倍。     

Fe2O3-CaO-TiO2 体系下铁酸钙的合成过程及TiO2 和CaTiO3 的影响

为了确定高钛型钒钛磁铁矿烧结过程中铁酸钙的生成是受TiO₂还是TiO₂和CaO形成的CaTiO₃影响,首先利用Fe₂O₃和CaO的纯试剂合成了铁酸钙,并研究了TiO₂和CaTiO₃对钛铁酸钙 （FCT） 形成的影响。在Factsage 7.0软件进行热力学计算的基础上,通过在空气气氛下进行烧结,获得了在1023~1423 K温度范围内、不同烧结时间的不同样品。通过X射线衍射和扫描电镜-能谱分析等表征手段,对烧结样品的物相转变和微观结构变化进行了表征。发现FCT的形成过程主要分为2个阶段：前一阶段为1023~1223 K温度范围内Fe₂O₃与CaO之间的反应,合成产物为Ca₂Fe₂O₅,反应方程式为“Fe₂O₃(s)+ 2CaO(s)= Ca₂Fe₂O₅(s)”;后一阶段为1223~1423 K温度范围内Ca₂Fe₂O₅和Fe₂O₃的反应,主要产物为CaFe₂O₄,反应为“Ca₂Fe₂O₅(s)+ Fe₂O₃(s)= 2CaFe₂O₄(s)”,该阶段尤其是温度为1423 K时,反应速率显著加快,随温度的升高CaTiO₃显著增加。然而,Ti元素在铁酸钙中的固溶很难实现,TiO₂与铁酸钙之间的反应不是形成FCT的有效途径。随着保温时间的延长,CaTiO₃和FCT相界中Fe元素含量增加。FCT主要是通过Fe组分在CaTiO₃中固溶形成的,主要反应是“Fe₂O₃+CaTiO₃(s)=FCT(s)”。     

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。     

Ba(Mg1/3Ta2/3)O3热障涂层的制备及抗热震性能研究

本文以BaCO₃、MgO、Ta₂O₅为原料,采用固相反应法合成了Ba(Mg_1/3Ta_2/3)O₃(简称BMT)陶瓷粉末,利用大气等离子喷涂技术制备了BMT/YSZ双层陶瓷涂层。利用XRD、SEM和金相显微镜检测了BMT粉体及涂层的物相组成和显微结构。采用水淬法考核了涂层的抗热震性能。结果表明：1450℃下煅烧4h可合成出具有复合钙钛矿结构的BMT粉末,粉末具有良好的高温相结构稳定性。等离子喷涂制备的BMT/YSZ涂层组织致密,涂层系统中各界面结合紧密。涂层在室温至1150℃间热震9次后发生片状剥落,剥落位置位于BMT层间,BMT材料低的断裂韧性和第二相Ba₃Ta₅O₁₅的存在是导致涂层失效的主要原因。     

纳米BaTiO3复合Cu1.8S块体的热电性能和力学性能研究

Cu_1.8S作为一种P型半导体热电材料,具有环境友好、原料丰富、价格低廉等优点而受到广泛关注。本研究采用机械合金化(Mechanical Alloying, MA)结合放电等离子烧结(Spark Plasma Sintering, SPS)工艺制备了一系列Cu_1.8S-x wt%BaTiO₃ (x =0,0.075,0.1,0.15,0.2)块体材料,研究了复合纳米BaTiO₃对Cu_1.8S的相结构、微观形貌、热电性能及力学性能的影响。结果表明,纳米BaTiO₃的加入不影响Cu_1.8S的相结构、晶胞参数和载流子浓度;纳米BaTiO₃均匀分布在Cu_1.8S基体的晶界处产生钉扎效应进而细化晶粒并产生气孔。Cu_1.8S-0.2 wt%BaTiO₃样品在773 K时获得最低的热导率2.2 Wm^_-1K^_-1,所有样品的ZT值基本保持不变约0.39 (773 K)。同时Cu_1.8S-x wt%BaTiO₃块体样品的维氏硬度由82 (x = 0)增加到87 (x = 0.2)。本研究表明在Cu_1.8S中复合纳米BaTiO₃可以在不影响材料热电性能的前提下有效提升块体样品的力学性能,为后续Cu-S体系热电性能和力学性能的协同提升提供了思路,有利于制备高机械性能且稳定耐用的Cu-S体系的热电器件。     

Ti3AlC2掺杂SPS法制备Ti2AlC/TiAl复合材料的研究

通过2TiC-Ti-1.2Al体系的原位热压反应制备了Ti₃AlC₂陶瓷,然后以59.2Ti-30.8Al-10Ti₃AlC₂(wt%)为反应体系,采用放电等离子烧结技术制备出Ti₂AlC/TiAl基复合材料。借助XRD、SEM分析了产物的相组成和微观结构,并测量了其室温力学性能。结果表明：原位热压烧结产物由Ti₃AlC₂和TiC相组成,Ti₃AlC₂呈典型的层状结构,TiC颗粒分布在其间。SPS法制备的Ti₂AlC/TiAl基复合材料主要由TiAl、Ti₃Al和Ti₂AlC相组成,Ti₂AlC增强相主要分布于基体晶界处,表现为晶界/晶内强化作用。力学性能测试表明：Ti₂AlC/TiAl基复合材料的密度、维氏硬度、断裂韧性和抗弯强度分别为3.85 g/cm₃、5.37 GPa、7.17 MPa?m_1/2和494.85 MPa。     

钙钛矿型La1-xSrxCoO3-δ粉体的制备及其在银基电接触材料中的应用

采用溶胶-凝胶法和粉末冶金工艺分别制备了颗粒状和网孔状La_0.5Sr_0.5CoO_3-δ(LSCO)粉体及其Ag-LSCO电接触复合材料。优化了溶液pH,溶胶预处理温度等工艺对LSCO粉体微结构的影响,并考察成型压力,烧结温度等对Ag-LSCO材料电学、力学性能的影响研究。采用扫描电镜、X-射线衍射仪、D60K数字金属电导率测量仪和HVS-1000型数显显微硬度计等对LSCO粉体及Ag-LSCO电接触材料进行了微观形貌、物相结构、电导率与硬度等性能表征。结果表明：以柠檬酸为单一胶凝剂,当pH为9.5,在700℃烧结8h可获得颗粒状LSCO_p粉体;而以柠檬酸和EDTA为复合胶凝剂时,于前驱体溶液pH=9.5,溶胶预处理温度200℃,烧结温度700℃,8h条件下合成网孔块体结构的LSCO_w粉体。经成型压力及烧结制度的优化结果可知,成型压力(1100MPa)、烧结温度900℃,6h 为制备Ag/LSCO_w电接触材料的最佳工艺参数。相比于Ag-LSCO_p电接触复合材料,Ag-LSCO_w表现出更低的电阻率(2.5μΩcm)。     

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。     

在优化Na2SiO3电解液制备的镁合金陶瓷膜的防护性能

    优化镁合金微弧氧化常用的Na₂SiO₃电解液并制备了白色陶瓷质微弧氧化膜,采用动电位极化曲线和电化学交流阻抗(EIS)等方法研究其防护性能.结果表明,与常用的Na₂SiO₃电解液制备的试样相比,优化的Na₂SiO₃电解液所制备试样的自腐蚀电流降低了3个数量级,并表现出较高的阻抗值;在3.5% NaCl溶液中浸泡发生点蚀的时间从24 h延长到240 h.SEM和XRD分析结果表明,在优化的Na₂SiO₃电解液中制备的AZ91D的陶瓷膜层孔隙减少,孔径也较小,且增加了低溶解度的Mg₅F₂(SiO₄)₂相和起钝化作用的MgAl₂O₄相.     

La2O3掺杂AgSnO2电接触材料的制备及性能研究

以Ag、Sn、La₂O₃粉为原料,采用机械合金法制备复合粉体。结合氧化法与粉末冶金工艺,对复合粉体进行氧化、压制、烧结。采用扫描电镜(SEM)和能谱仪、硬度计、金相显微镜、金属电导率测量仪等对复合粉体氧化前后的形貌以及电接触材料烧结前后的性能进行表征。结果表明：烧结后,电接触材料硬度较于烧结前明显下降。同时电接触材料随Sn含量增大,电阻率升高,密度反而下降。在一定的La₂O₃(0wt.%、0.75wt.%、1.5wt.%、2.25wt.%、3wt.%)含量范围内,La₂O₃掺杂量越高,密度越低。同时电接触材料经烧结后,随La₂O₃含量增加,其电阻率先降后升,在La₂O₃含量为0.75wt.%时,电接触材料的电阻率最低。     

Influence of MnO2 on the sintering behavior and magnetic properties of NiFe2O4 ferrite ceramics

The samples with small amounts of MnO₂ (0, 0.5, 1.0, 1.5, 2.0, and 2.5 wt%, respectively) were prepared via ball-milling process and two-step sintering process from commercial powders (i.e. Fe₂O₃, NiO and MnO₂). Microstructural features, phase transformation, sintering behavior and magnetic properties of Mn-doped NiFe₂O₄ composite ceramics have been investigated by means of scanning electron microscopy (SEM), differential thermal analyzer, X-ray diffraction (XRD), thermal dilatometer and vibrating sample magnetometer (VSM) respectively. The XRD analysis and the result of differential thermal analysis indicate that the reduction of MnO₂ into Mn₂O₃ and the following reduction of Mn₂O₃ into MnO existed in sintering process. No new phases are detected in the ceramic matrix, the crystalline structure of the ceramic matrix is still NiFe₂O₄ spinel structure. Morphology and the detecting result of thermal dilatometer show that MnO₂ can promote the sintering process, the temperature for 1 wt% MnO₂-doped samples to reach the maximum shrinkage rate is 59 °C lower than that of un-doped samples. For 1 wt% MnO₂-doped samples, the value of the saturation magnetization (M_s) and coercivity (H_c) is 15.673 emu/g and 48.316 Oe respectively.     

Large magnetic entropy change near room temperature in La0.7(Ca0.27Ag0.03)MnO3 perovskite

In this paper, the magnetic properties and magnetocaloric effect (MCE) of La_0.7(Ca_1−xAg_x)_0.3MnO₃ (x = 0, 0.1, 0.2, 0.7, and 1) powder samples are reported. Our polycrystalline compounds were synthesized using the solid state reaction method at high temperature. Magnetization measurements versus temperature showed that all our samples exhibited a paramagnetic to ferromagnetic transition with decreasing temperature. The Curie temperature, T_C, has been found to increase from ∼250 K for x = 0-270 K for x = 1. Ag doping weakens the first order phase transition, and at higher Ag doping, the phase transition is of second order. For the La_0.7(Ca_0.27Ag_0.03)MnO₃ composition, the maxima of the magnetic entropy changes from the applied magnetic field (ΔS_M) at 2 and 5 T are about 4.5 and 7.75 J/kg K, respectively, at the Curie temperature of ∼263 K. The relative cooling power (RCP) values without hysteresis loss are about 102 and 271 J/kg for the applied fields of 2 and 5 T, respectively. Due to the large ΔS_M, large RCP, and high Curie temperature, La_0.7(Ca_0.27Ag_0.03)MnO₃ is promising for application in potential magnetic refrigeration near room temperature.     

High dielectric constant of (Ba0.96Ca0.04)(Ti0.85Zr0.15)O3 multilayer ceramic capacitors with Cu doped Ni electrodes

A nickel paste with Cu dopant was used as the internal electrodes in multi-layer ceramic capacitors (MLCCs) using barium titanate (Ba_0.96Ca_0.04)(Ti_0.85Zr_0.15)O₃ ceramic (BCTZ) with copper endtermination. The sintering behaviors of the MLCC and the interfacial structure between the Ni/Cu electrodes and the BCTZ dielectrics have been investigated. The thermal shrinkage and sheet resistance of the Ni/Cu alloys sintered at 1220 °C for 2 h in a reducing atmosphere were measured using thermal analysis techniques (TMA) and four-point probe equipment. The composition distributions, microstructures and line defects were examined using microstructural analysis techniques (SEM/HRTEM) coupled with energy-dispersive spectroscopy (EDS). The Cu alloyed with Ni significantly improves the continuity of the electrode in the MLCC; this is due to there being no mutual trigger reaction between Ni and BCTZ dielectrics. In terms of the electrical properties, the results showed that Ni paste with Cu dopant improves the dielectric constant of the MLCC, but the dielectric loss (tan δ) is a slightly when higher compared to standard MLCC.     

Reaction-sintering method for ultra-low loss (Mg0.95Co0.05)TiO3 ceramics

Microwave dielectric properties and microstructures of (Mg_0.95Co_0.05)TiO₃ ceramics prepared by a new sintering method (reaction-sintering method) were investigated. A pure phase of (Mg_0.95Co_0.05)TiO₃ was obtained by the new method and excellent dielectric properties were observed due to uniformities of the microstructure and the phase. In contrast, the secondary phase (Mg_0.95Co_0.05)Ti₂O₅ was observed in samples prepared by conventional sintering method. In order to study the influence of secondary phase on the microwave dielectric properties quantitatively, the weight fraction of (Mg_0.95Co_0.05)Ti₂O₅ was calculated on the basis of Rietveld refinement. The pore-free?_r values of specimens prepared by two different methods indicated that porosity plays an important role in the ?_r values of (Mg_0.95Co_0.05)TiO₃ ceramics. Specimens sintered by reaction-sintering method at 1350 °C for 4 h possess excellent dielectric properties with an ?_r of 16.3, a Q × f value of 244,500 GHz, and a τ_f value of −53.5 ppm/°C.     

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。     

Effect of the sintering temperature on the properties of nanocrystalline Ca1−xSmxMnO3 (0 ≤ x ≤ 0.4) powders

Nanocrystalline Ca_1−xSm_xMnO₃ (0 ≤ x ≤ 0.4) manganites were prepared by a soft chemical method (Pechini method) followed by auto-combustion and sintering in air at 1073 or 1473 K. Single-phase powders with general composition Ca_1−xSm_xMnO₃ were obtained after 18 h annealing. The particle and grain sizes of the substituted Sm-manganites did not exhibit variation with samarium content, but increase with increasing the sintering temperature. All manganites show two active IR vibrational modes near 400 and 600 cm⁻¹ characteristic of the BO₆ octahedron vibrations.For the samples sintered at T_s = 1473 K, the partial substitution of calcium by samarium in the CaMnO₃ phase induces a marked decrease in the electrical resistivity, in the temperature range of 300-900 K, and at the same time a metal-to-insulator transition occurs; for T_s = 1073 K all the samples present semiconductor behaviour. With the increase of the annealing temperature the grain size increases and a metal-semiconductor transition appears. The results can be ascribed to the Mn⁴⁺/Mn³⁺ ratio and particle grain size. The effects of particle size on the electrical properties can be attributed to the domain status, changes in the Mn-O-Mn bond angle and Mn-O bond length.     

Charge compensation, electrical and dielectric behavior of lanthanum doped CaCu3Ti4O12

Mechanism of charge compensation on lanthanum, (La³⁺) substitution on Ca site in calcium copper titanate (CaCu₃Ti₄O₁₂), and its effect on resulting electrical and dielectric properties has been studied in the present investigation. For this purpose samples were prepared according to two stoichiometries viz. La_xCa_(1−3x/2)Cu₃Ti₄O₁₂ (x ≤ 0.09) and La_xCa_(1−x)Cu₃Ti₄O₁₂ (x = 0.03) by solid state ceramic route. The former represents ionic compensation while the later is in accordance with electronic compensation. Nature of charge carriers is identified by measuring Seebeck coefficient which is found to be negative in the entire range of measurement. In order to understand the mechanism of conduction, ac conductivity is measured as a function of temperature and frequency. Space charge polarization is the dominant polarization mechanism phenomenon at low frequency and high temperature while orientation polarization dominates at low temperature and high frequency. Impedance analysis confirms the formation of internal barrier layers which is responsible for high dielectric constant in these samples.     

Low temperature sintering and microwave dielectric properties of (Mg0.7Zn0.3)0.95Co0.05TiO3 ceramics with BaCu(B2O5) additions

The effects of BaCu(B₂O₅) additives on the sintering temperature and microwave dielectric properties of (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics were investigated. The (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics were not able to be sintered below 1000 °C. However, when BaCu(B₂O₅) were added, they were sintered below 1000 °C and had the good microwave dielectric properties. It was suggested that a liquid phase with the composition of BaCu(B₂O₅) was formed during the sintering and assisted the densification of the (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics at low temperature. BaCu(B₂O₅) powders were produced and used to reduce the sintering temperature of the (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics. Good microwave dielectric properties of Q × f = 35,000 GHz, ?_r = 18.5.0 and τ_f = −51 ppm/°C were obtained for the (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics containing 7 wt.% mol% BaCu(B₂O₅) sintered at 950 °C for 4 h.     

Size effects and interactions in La0.7Ca0.3MnO3 nanoparticles

La_0.7Ca_0.3MnO₃ (LCMO) nanoparticles with average diameter of 16-73 nm were prepared by reactive milling and thermal processing methods. Interaction and size effects on the magnetic properties of the LCMO nanoparticle samples were investigated. Phenomena related to the interparticle interaction, such as an un-overlapping of the M(H_ext,T)/M_S vs. H_ext/T scaling plots and a Curie-Weiss rather than Curie law behavior of the dc susceptibility at high temperatures were analyzed. The magnetization curves of interacting nanoparticles were well described by using the mean-field approximation. The dependence of the blocking temperature T_B on the strength of the interactions, magnetic anisotropy, as well as the thermal dependence of magnetization deviates from the expected Bloch law was also estimated.