Thermoelectric properties of p-type skutterudites YbxFe3.5Ni0.5Sb12 (0.8 ? x ? 1)

p-Type skutterudites, with nominal compositions Yb_xFe_3.5Ni_0.5Sb₁₂ (0.8 ? x ? 1), have been synthesized by induction melting with subsequent annealing, and their thermoelectric properties evaluated from 3.5 to 745 K to assess their suitability for thermoelectric-based waste heat recovery applications. We report results for the synthesis and measurements of Seebeck coefficient (S), electrical resistivity (ρ), thermal conductivity (κ), Hall coefficient (R_H) and effective mass (m^*/m₀) of Yb_xFe_3.5Ni_0.5Sb₁₂ (0.8 ? x ? 1). Powder X-ray diffraction and electron probe microanalysis show that this system has a narrow filling fraction range of x ∼ 0.84-0.86 for Yb in the crystallographic voids. All samples show positive R_H for the entire temperature range studied, with carrier concentrations ranging from 9.6 × 10²⁰ to 2.8 × 10²¹ cm⁻³ at room temperature. Relatively high values of S result in high power factors up to 17 μW cm⁻¹ K⁻² at room temperature. However, large values of κ and a sharp reduction in the S at high temperature due to bipolar conduction prevent the attainment of high thermoelectric figure of merit.     

A new TiB2 + CrSi2 composite – Densification,characterization and oxidation studies

A new composite of TiB₂ with CrSi₂ has been prepared with excellent oxidation resistance. Dense composite pellets were fabricated by hot pressing of powder mixtures. Microstructural characterization was carried out by XRD and SEM with EDAX. Mechanical and physical properties were evaluated. Extensive oxidation studies were also carried out. A near theoretical density (99.9% TD) was obtained with a small addition of 2.5 wt.% CrSi₂ by hot pressing at 1700 °C under a pressure of 28 MPa for 1 h. The microstructure of the composite revealed three distinct phases, (a) dark grey matrix of TiB₂, (b) black phase – rich in Si and (c) white phase – Cr laden TiB₂. Hardness and fracture toughness were measured as 29 ± 2 GPa and 5.97 ± 0.61 MPa m^1/2, respectively. Crack branching, deflection and bridging mechanisms were responsible for the higher fracture toughness. With increase in CrSi₂ content, density, hardness and fracture toughness values of the composite decreased. Thermo gravimetric studies revealed the start of oxidation of the composite at 600 °C in O₂ atmosphere. Isothermal oxidation of these composites showed better oxidation resistance by formation of a protective oxide layer. TiO₂, Cr₂O₃ and SiO₂ phases were identified on the oxidized surface. Effects of CrSi₂ content, temperature and duration of oxidation on the oxide layer formation are reported. Activation energy of the composite was calculated as ∼110 kJ/mol using Arrhenius equation. Diffusion controlled mechanism of oxidation was observed in all the composites.     

Thermoelectric properties of n-type Ca1−xDyxMn1−yNbyO3−δ compounds (x = 0, 0.02, 0.1 and y = 0, 0.02) prepared by spray-drying method

We report the high temperature thermoelectric properties of Ca_1−xDy_xMn_1−yNb_yO_3−δ (x = 0, 0.02, 0.1 and y = 0, 0.02) synthesized by spray-drying method. A maximum power factor (PF) value of 2.65 μW K⁻² cm⁻¹ is obtained at 1100 K for CaMn_0.98Nb_0.02O_3−δ. This represents an improvement of about 75% with respect to undoped CaMnO_3−δ sample at the same temperature. We also provide a complete structural characterization of the samples.     

cBN-WC-12Co硬质合金的SPS制备及强化机理研究左冬华,林晨光,谢兴铖,曹瑞军,林中坤

采用放电等离子体烧结（SPS）技术制备出cBN-WC-12Co硬质合金,分析了cBN的热稳定性,研究了cBN添加量和烧结温度对合金硬度和致密度的影响,并讨论了cBN强化机理。结果表明：cBN的热稳定性温度为1355℃,cBN-WC-12Co合金的烧结致密化最低温度在1150℃左右,当烧结温度为1250℃,cBN保持了较好的热稳定性,不发生相变;在相同烧结温度下,cBN-WC-12Co合金致密性均要好于WC-12Co合金;1150℃时合金C15的致密度和硬度（HV10）均达到最大值,分别为99.7%和1997;当cBN含量低于15vol%时,在一定程度上,cBN含量的增加有利于抑制合金中WC晶粒长大,并通过WC晶粒的毛细吸附促进合金致密化;合金中的cBN可以阻止裂纹等缺陷进一步扩展,有利于改善合金力学性能。     

Role of BaO/SrO layers in deciding the electronic structure of Cu0.3Co0.7Ba2−xSrxYCu2O7+δ (CoCu-1212) x = 0, 1 and 2

In this paper we report the change in electronic structure of Cu_0.3Co_0.7Ba_2−xSr_xYCu₂O_7+δ with change in structural pressure. Rietveld refined X-ray diffraction (XRD) pattern shows that the samples are phase pure. Decrease in lattice parameters with increasing x, confirms replacement by Sr ion at Ba ion site. The calculated tolerance factor of the systems is in accord with lattice parameter changes. The X-ray photoelectron spectroscopy (XPS) is made to find out the variation in ionic state of Co and Cu with ionic size variation in BaO/SrO layers. Effect of the same on the electronic structure and transport properties is explored. The XPS measurement reveals that Cu is in mixed 1+/2+ state and variation in valence state is non-monotonous with increasing x. Whereas Co is in mixed 3+/4+ state and with increasing x its valence state is increasing. The observed changes in electronic structure are subject of structural changes. The resistivity measurement shows that normal state conductivity decreases with increasing x. Resistivity behaviour indicates about holes in Cu/CoO_x planes taking part in charge transport. The magnetic measurement (M-T and M-H) shows that paramagnetic nature for all the compositions. The presence of Cu ions in Cu/CoO_x chains/planes results in paramagnetic behaviour.     

The effects of temperature and composition on the thermal conductivities of [(ZrO2)1−x(CeO2)x]0.92(Y2O3)0.08 (0 ? x ? 1) solid solutions

The thermal conductivities of [(ZrO₂)_1−x(CeO₂)_x]_0.92(Y₂O₃)_0.08 (0 ? x ? 1) solid solutions are studied in this paper. The incorporation of ZrO₂ and CeO₂ in the solid solution decreases the thermal conductivity compared with their end members (YSZ and YDC). The thermal conductivities of the solid solutions show clearly different temperature dependences in the ZrO₂-rich (0 ? x ? 0.5) region and in the CeO₂-rich region (0.5 ? x ? 1). The composition and the temperature dependence of the thermal conductivities are discussed based on established phonon scattering theories. We have concluded that the composition dependence of the thermal conductivity of this system is mainly controlled by the mass difference between Zr⁴⁺ and Ce⁴⁺, while the thermal conductivity-temperature relationship is dominated by the randomness of the defect distribution.     

内生型(Ti0.474Zr0.34Cu0.06Be0.126)100 - x Fe x (x=0, 2)金属玻璃基复合材料的动态力学行为

为了解内生β-Ti相的Zr/Ti基金属玻璃复合材料的动态力学性能和热力学稳定性,采用力学弛豫谱研究了(Ti_0.474Zr_0.34- Cu_0.06Be_0.126)_100-xFe_x（x=0,2）金属玻璃复合材料。通过引入Fe元素,提高了β-Ti相的稳定性。此外,还发现了一个异常的内耗峰,这是由于在亚稳的β-Ti相中析出ω-Ti所引起的。在玻璃化转变温度T_g以下,由于相变和非晶基体部分结晶的耦合效应,2种金属玻璃复合材料的储能模量均表现出异常过冲行为。所得结果为更好地理解内生亚稳β-Ti型金属玻璃复合材料的复杂动态力学弛豫行为提供了借鉴。     

Ce17Fe78-xB6Mx (M=Cu, Al, Ga; x=0-1.0)快淬合金永磁性能研究

本文基于熔体快淬技术,研究了低熔点元素Cu、Al和Ga添加对Ce₁₇Fe₇₈B₆合金磁性能的影响。三类低熔点元素的加入,均降低了合金的磁化强度,而矫顽力有一定程度的提升。其中,Cu和Ga元素添加可优化晶粒尺寸分布,且Ga添加对Ce₁₇Fe₇₈B₆合金矫顽力的提升最为有效。研究发现,Ce₁₇Fe₇₈B₆合金回复曲线轻微开口;当Ga添加量为0.75 at.%时,合金具有较优异的综合磁性能,回复曲线完全闭合。适量Ga元素添加明显增强了Ce-Fe-B基合金晶间短程交换耦合作用,减小了合金平均回复磁导率,有效降低了Ce-Fe-B基合金在周期性反向磁场中的能量损失。     

二维ZnO/ Bi3.9Zn0.4V1.7O10.5纳米异质结构的制备及其可见光催化活性

表面建造是提高半导体光催化活性的一种有效方法。本文利用Zn5(CO3)2(OH)6纳米片为基底沉积了BiVO4再通过煅烧成功制备了二维ZnO/Bi3.9Zn0.4V1.7O10.5复合纳米片。通过X射线衍射,透射电镜和元素映像技术表征了所制样品。结果显示随着锌与铋的原子比的上升,ZnO多孔片状的表面逐渐变成Bi3.9Zn0.4V1.7O10.5物质。但其比例高于1:0.02时,在片状Bi3.9Zn0.4V1.7O10.5的区域表面又生长出BiVO4纳米颗粒。漫反射光谱测试显示出ZnO/Bi3.9Zn0.4V1.7O10.5复合物随着锌与铋的原子比的上升其在400~600 nm可见光区的吸收逐渐增强。所制样品在可见光（波长大于420 nm）进行了光催化降解罗丹明B的测试,结果表明在所制样品中,锌与铋的原子比为1:0.0133的ZnO/Bi3.9Zn0.4V1.7O10.5纳米片虽然其可见光的吸收并没有明显增强但却表现出最佳的光催化活性。荧光与电化学测试得出了低含量BZVO的ZnO纳米片可见光催化活性的提高主要是因为表面ZnO/Bi3.9Zn0.4V1.7O10.5异质结构提高了光生载流子的分离与传送。这种二维材料的表面建造有利于光催化的进行。因此,此法可应用于其它二维纳米材料的建造以提高光催化活性。     

LaY0.1Fe11.4T0.1Si1.5（T=Cr,Mn,Fe,Co,Ni）合金的磁热效应

用电弧熔炼法制备了LaY0.1Fe11.4T0.1Si1.5(T=Cr,Mn,Fe,Co,Ni)系列合金。室温XRD分析与SEM成分分析表明,该系列合金中除存在一个明显的杂相峰(富La相,P4/nmm)和α-Fe相外,主相为NaZn13型立方相。除T=Cr外,Fe位原子替代使合金的晶格常数随着替代原子T的原子半径的减小而减小。磁性测量表明,该系列合金除T=Mn以外,随着替代原子T的原子半径减小,合金的居里温度(TC)有增加的趋势。在外磁场变化ΔB=1.5T时,利用Maxwell方程计算得出,该系列合金磁熵变最大值分别为5.1,13.0,20.7,12.7和7.4J·kg-1·K-1。由此可以看出,T=Fe时合金的磁熵变最大值最大,且该系列合金的磁熵变峰值随着外磁场增加向高温区不对称展宽;TC以上磁场引起的变磁转变是磁熵变峰值不对称展宽的原因。     

Ta1/Ta8Ni30Cr20Cu42/0Cr18Ni9储能焊接头组织与性能

针对钽与钢之间因物化性能差异大,储能焊接头易产生脆性金属间化合物等问题,依据熔核金属高熵化技术思路,以等摩尔比的Ta₂₀Fe₂₀Ni₂₀Cr₂₀Cu₂₀合金为熔核目标成分,依据焊接过程两种母材熔合比折合得到Ta₈Ni₃₀Cr₂₀Cu₄₂中间层合金,将其用于Ta1/0Cr18Ni9的储能焊连接. 结果表明,熔核金属的高熵合金化可有效地抑制熔核中脆性金属间化合物的形成,Ta1/Ta₈Ni₃₀Cr₂₀Cu₄₂/0Cr18Ni9储能焊接头形貌完整,熔核呈规则的杯形,长径约0.6 mm,整体向钢侧发生了偏移. 熔核组织以简单FCC固溶体为主相,兼有少量BCC固溶体. 熔核中心凝固组织以细小的等轴晶为特征,熔核与两侧母材熔合区则形成了平行生长的柱状晶,熔核区与母材结合良好. 在焊接电压1 000 V,电容500 μF,电极力30 N工艺条件下,接头平均抗剪强度372 MPa.     

(Zr55All0Ni5Cu30)0.97Ce0.03非晶合金在含Cl-介质中的腐蚀电化学行为研究

  用电化学技术方法研究了Zr₅₅Al_l0Ni₅Cu₃₀和(Zr₅₅Al_l0Ni₅Cu₃₀)_0.97Ce_0.03非晶合金在含Cl^-介质中的腐蚀电化学行为及添加稀土Ce的影响.结果表明：随Cl^-浓度增加,两种非晶合金的腐蚀速度加快;添加稀土Ce后提高合金耐蚀性;随极化电位的提高,两种非晶合金在0.05 mol/L Na₂SO₄及含Cl^-介质中均出现钝化特征,维钝电流密度随Cl^-浓度增加而减小;Zr₅₅Al_l0Ni₅Cu₃₀非晶合金的电化学阻抗谱由单容抗弧组成(Zr₅₅Al_l0Ni₅Cu₃₀)_0.97Ce_0.03非晶合金的交流阻抗谱在Cl^-浓度较低时呈单容抗弧特征,而随Cl^-浓度的增加,单容抗弧变为双容抗弧.     

Combinatorial approach to the growth of α-(Al1 − x,Crx)2O3 solid solution strengthened thin films by reactive r.f. magnetron sputtering

The development of new coatings with superior functionalities for high performance cutting tools is a key challenge in manufacturing. In this context, the synthesis of aluminium oxide and derivative oxide thin films is attracting large scientific and technical interests. The present paper addresses fundamental materials science-based aspects of the physical vapour deposition (PVD) growth of Al-Cr-O thin films at a substrate temperature of 500 °C. A combinatorial experimental approach was chosen to describe the growth and microstructure evolution of Al-Cr-O thin films by means of reactive r.f. magnetron sputtering. A segmented target consisting of two half plates of Al and Cr was used for the deposition carried out under stationary conditions in a laboratory-scale PVD coater. Opposite to the cathode five substrate samples were placed in a line. The r.f. cathode power was set to 500 W and the r.f. substrate bias was set to − 100 V. The total gas pressure was kept constant at 0.4 Pa for all experiments with a fixed ratio of oxygen to argon gas flow. Detailed results on the coatings composition, constitution, microstructure and properties as a function of the elemental composition are presented. X-Ray Diffraction (XRD), X-Ray Reflection (XRR), Transmission Electron Microscopy (TEM) and Electron Probe Microanalysis (EPMA) studies prove the growth of nanocrystalline, stoichiometric, metastable corundum-like solid solution strengthened α-(Al_1 − x,Cr_x)₂O₃ thin films with a high degree of crystallinity, grain sizes between 27 ± 6 nm (in the case of Al-rich coatings) and 44 ± 17 nm (in the case of Cr-rich coatings), Vickers micro hardness values up to 2620 ± 80 HV0.05 and thin film densities between 4.00 g/cm³ (in the case of Al-rich coatings) and 4.86 g/cm³ (in the case of Cr-rich coatings).     

NiFe1 . 98Nd0 . 02O4-Fe 双层吸波涂层设计及制备

目的制备高性能NiFe1.98Nd0.02O4-Fe双层吸波涂层。方法采用溶胶凝胶自燃烧法制备钕掺杂NiFe1.98Nd0.02O4。借助X射线衍射仪、扫描电镜和矢量网络分析仪对NiFe1.98Nd0.02O4和羰基铁的结构、形貌、电磁参数进行测试分析。采用遗传算法对NiFe1.98Nd0.02O4-羰基铁双层涂层的厚度进行优化设计。结果以环氧树脂为基体,以羰基铁和NiFe1.98Nd0.02O4为吸波剂的双层吸波涂层具备较好的吸波性能,厚度约1 mm,反射率在9.25~11.35 GHz范围内均小于-10 dB。结论 NiFe1.98Nd0.02O4层和羰基铁层在吸波性能上有很好的互补性,理论优化结果和实验结果相同。     

D022相强化型Ni2CoCrFeNb0.15高熵合金的变形机理

采用透射电子显微镜和扫描电子显微镜的背散射电子衍射及电子隧道衬度成像技术研究了D0₂₂相强化型Ni₂CoCrFeNb_0.15高熵合金在单轴拉伸变形过程中的织构演化、变形亚结构特征、位错与析出相交互作用以及断裂行为。结果表明：位错的平面滑移主导了该合金的单轴拉伸变形,D0₂₂超点阵相是促进位错平面滑移的主要因素。因位错的平面滑移模式产生的平面滑移带随着应变量的增加,其密度随之增加,平均间距随之减小。变形过程中先形成{001}织构,然后{111}织构增强,最终获得典型的{001}和{111}拉伸织构。当合金在单独拉伸变形过程中达到最大应力时,晶界处萌生裂纹并扩展为断裂主裂纹,导致塑性变形失稳。     

Influence of the oxygen content and the preparation method on the power factor of PrBaCo2O5+δ samples (0.54 ≤ δ ≤ 0.84)

In this work, we focus on the influence of the oxygen content and the preparation method on the power factor of different PrBaCo₂O_5+δ samples (0.54 ≤ δ ≤ 0.84). The samples have been initially synthesized by the Pechini method. Their oxygen content has been subsequently modified by annealing under argon/oxygen flow or by electrochemical oxidation/reduction. The oxygen stoichiometry has a high impact on the electrical conductivity and Seebeck coefficient of the resulting materials. Moreover, by adequately reducing their oxygen content while increasing their intergrain conductivity (by increasing the particle size and degree of sintering) the power factor of these samples can be drastically improved. The best result is shown by the PrBaCo₂O_5.54 sample, that was annealed at high temperature under argon flow, whose power factor is as high as 6.5 μW/K² cm⁻¹ at ∼135 K, more than two orders of magnitude higher than that shown by the initial PrBaCo₂O_5.76 reference sample.     

La3+,Ce4+共掺杂Sm2Zr2O7陶瓷的热物理性能

以Sm2O3,La2O3,ZrO2和CeO2为原料,采用固相反应法制备(Sm0.5La0.5)2(Zr0.7Ce0.3)2O7陶瓷。用X射线衍射(XRD),扫描电镜(SEM)分析样品的相成分和微观组织,用激光脉冲法和推杆法测量样品的热物理性能。结果表明,所制备的样品具有萤石晶体结构,且组织致密,晶界清晰,具有较低的热导率和较高的热膨胀系数。良好的热物理性能表明(Sm0.5La0.5)2(Zr0.7Ce0.3)2O7陶瓷有潜力用作热障涂层陶瓷层候选材料。     

Structure, magnetic, and magnetocaloric properties of amorphous and crystalline La0.4Ca0.6MnO3+δ nanoparticles

We report a systematic study of the effects of size reduction on the magnetic and magnetocaloric properties of amorphous and crystalline La_0.4Ca_0.6MnO_3+δ nanoparticles. The materials were synthesized using a modified wet chemical Pechini route, starting with nitrate precursors to produce the perovskite structure. Phase purity, structure, size, and crystallinity were investigated using XRD and TEM. Thermal treatments resulted in nanocrystals with average diameters of 25 nm, 50 nm, and 130 nm, as well as amorphous particles ∼10 nm in diameter. Magnetic measurements revealed broad, second order ferromagnetic transitions in the nanocrystals. As particle size increased from 10 nm to 130 nm, the Curie temperature shifted from 40 K to 255 K. Magnetization, magnetic entropy change (ΔS_M), and refrigerant capacity (RC) also increased with size in the nanocrystalline samples. For a field change of 5 T, the 130 nm particles exhibit a magnetic entropy change of 2.8 J/kg K and a large refrigerant capacity of ∼240 J/kg at 250 K. Interestingly, the 10 nm amorphous particles undergo the sharpest magnetic transition, leading to a larger value of ΔS_M than in the 25 nm or 50 nm crystalline particles. These results reveal that size reduction has a significant impact on the magnetic and magnetocaloric properties of La_0.4Ca_0.6MnO_3+δ.