定向凝固Ag掺杂Mg3Sb2合金热电性能

通过定向凝固方法可以高效制备Mg₃Sb₂晶体,根据凝固理论计算了平界面生长临界速率,在此速率下可以有效抑制第二相Sb的析出。对不同的凝固速率下的Mg₃Sb₂晶体微观组织进行了分析,表明凝固速率为5μm·s^-1时可以有效减少Mg空位的出现,并在晶体中获得过量Mg原子,有利于更好地提升热电性能。通过消除晶界和Ag元素掺杂有效提升了Mg₃Sb₂晶体的载流子迁移率和浓度,在测试温度区间(300～800K)内,最大电导率值可达309S·cm^-1,同时保持了较高的Seebeck系数值,从而获得了更好的电子传输性能(PF_max=1.2mW·m^-1·K^-2),通过Hall测试和第一性原理计算对此结果进行了验证。Ag掺杂浓度为2.5at%下相应的热电优值最高可以达到0.67,此方法为Mg₃Sb₂基热电材料性能优化提供了新的...     

MAX相Ti3SiC2管材在高温高压水和过热蒸汽中的腐蚀行为

MAX相材料有作为事故容错燃料(accident tolerant fuel,ATF)包壳材料的潜力,为了全面了解MAX相材料在模拟正常工况下的腐蚀行为,使用基体为Ti₃SiC₂的MAX相陶瓷管材于400℃/10.3 MPa过热蒸气,360℃/18.6 MPa去离子水、3.5μL/L Li+1000μL/L B溶液和70μL/L Li溶液4种不同的水化学条件中进行腐蚀试验,采用XRD、SEM和FIB/TEM观察分析腐蚀前后样品的显微组织、晶体结构和成分。结果表明,Ti₃SiC₂管材在4种条件下的腐蚀速率均远高于参比Zr-4合金,腐蚀后主要检测到腐蚀产物TiO₂,且其表面疏松多孔,未形成保护性的氧化膜。     

Ce联合Nb/Co改性稀土尾矿催化剂NH3-SCR性能及脱硝机理研究

白云鄂博稀土尾矿含有Fe、Ce等利于催化脱硝的活性元素,作为天然矿物对环境友好且成本低,是做脱硝催化剂的天然原料,但稀土尾矿催化剂温度窗口较窄(350~450℃)。为拓宽稀土尾矿催化剂的温度窗口,用Ce、Nb、Co改性稀土尾矿,采用水热法制备了一系列Ce-M(Nb、Co)改性稀土尾矿催化剂,探究元素比例及元素种类对脱硝性能的影响。通过BET、XRD、XPS、H2-TPR和NH3-TPD对改性稀土尾矿进行表征分析,并利用In situ DRIFTS 技术对Ce-Co改性稀土尾矿的NH3-SCR机理进行了探究。结果显示,Ce-Nb(2:1)改性稀土尾矿在300~400℃脱硝效率最高为85%,Ce-Co(2:1)改性稀土尾矿在250~400℃脱硝效率能够达到90%。Nb和Co的加入提高了催化剂表面CeCO3F的分散度,暴露更多活性吸附位点。同时,元素之间的相互作用促进了电子的转移,Nb5+的形成阻碍了Ce4+的还原,调节了氧化还原性能,使得Ce-Nb改性稀土尾矿具有优异的N2选择性。而Co的加入提高了催化剂氧化还原能力,使得Co3+增加,进而提高Br?nsted酸性位的吸附强度,NH4+及Co3+-NH2能够首先与NO反应,形成NH3HNO及NH2NO等中间产物,催化剂表面同时遵循E-R机理和L-H机理,E-R机理占主导。     

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。     

单晶UBM在电子封装微互连中的研究进展

3D封装是未来电子封装制造技术领域的重要发展方向,3D封装中微凸点的尺寸将急剧降低,此时,芯片凸点下金属层(UBM)可能仅包含几个甚至单个晶粒。因此,UBM的晶体取向对界面金属间化合物(IMC)的形核和生长过程将具有显著影响,而界面IMC的特性会直接影响到凸点微/纳尺度互连的可靠性。因此,以单晶作为UBM研究界面物质的传输与IMC的生长规律,具有重要的理论和应用价值。本文对近年来以单晶Cu、Ni和Ag作为UBM焊点的界面反应进行综合分析,总结了单晶UBM上特殊形貌IMC晶粒的形成条件、界面IMC与单晶基体的位向关系、IMC的生长动力学过程、柯肯达尔空洞的形成规律、单晶UBM上IMC的晶体取向调控方法及晶体取向对无铅焊点力学性能和可靠性的影响,为评价单晶UBM凸点的力学性能和可靠性及提供指导。     

Synthesis and polymerizations of novel bisphosphonate‐containing methacrylates derived from alkyl α‐hydroxymethacrylates

The synthesis and polymerizations of four novel bisphosphonate‐containing monomers are reported. The monomers were synthesized from reaction of ethyl and tert‐butyl α‐bromomethacrylates with 3,3‐bis(diethoxyphosphoryl)propanoic acid or with tetraethyl 4‐hydroxybutane‐1,1‐diyldiphosphonate. Their thermal bulk polymerizations, photopolymerizations and copolymerizations with poly(ethylene glycol) methyl ether methacrylate were investigated. The homopolymerizations resulted in polymers with values of 25 000–83 000 g mol^?1; the copolymerizations yielded soluble polymers with 22–34% incorporation of the new monomers; the photopolymerizations gave some structure–reactivity correlation; and one of the homopolymers, upon hydrolysis of its bisphosphonate groups, could interact with hydroxyapatite. © 2013 Society of Chemical Industry     

DBDPE–Sb2O3复合阻燃LGFPP的热氧老化研究

采用十溴二苯乙烷(DBDPE)协同三氧化二锑(Sb2O3)组成复合阻燃剂DBDPE–Sb2O3(D–S)阻燃长玻纤增强聚丙烯(LGFPP),并采用热烘箱老化法研究了140℃条件下不同热氧老化时间对复合材料热氧老化性能的影响。结果表明,随着热氧老化时间的延长,LGFPP/D–S阻燃体系的氧指数值呈现出先升高后下降的趋势,垂直燃烧等级始终保持FV–0级的阻燃级别,复合材料的结晶度减小,力学性能逐渐下降。PP基体分子链的断裂以及玻纤与PP基体间发生界面脱粘是导致LGFPP/D–S复合材料宏观力学性能下降的主要原因。红外光谱表明,随着热氧老化时间的延长,试样表面会产生更多的生色基团使材料发生黄变,说明PP基体分子链的断裂加剧。     

One-step hydrothermal synthesis and microwave electromagnetic properties of RGO/NiFe2O4 composite

The reduced graphene oxide (RGO)/NiFe₂O₄ composite was synthesized by a facile one-pot hydrothermal route, which avoided the usage of chemical reducing agent. The reduction of graphene oxide (GO) and the crystallization of NiFe₂O₄ crystals happened in a one-step hydrothermal process. The morphology, microstructure and magnetic properties of the composite were detected by means of XRD, XPS, TEM, EDX, TG-DSC and VSM. The maximum R_L of the RGO/NiFe₂O₄ composite is −39.7 dB at 9.2 GHz with the thickness of 3.0 mm, and the absorption bandwidth with the R_L below −10 dB is up to 5.0 GHz (from 12.7 to 17.7 GHz) with a thickness of 1.9 mm. The introduction of RGO signally enhanced microwave absorption performance of the NiFe₂O₄ NPs. It is believed that such composite will be applied widely in microwave absorbing area.     

Phase equilibria and dielectric properties of Bi3+(5/2)xMg2−xNb3–(3/2)xO14−x cubic pyrochlores

Subsolidus pyrochlores with the proposed formula, Bi_3+(5/2)xMg_2−xNb_3−(3/2)xO_14−x (0.14≤x≤0.22) were successfully synthesised at the firing temperature of 1025 °C using conventional solid-state reaction. The excess Bi³⁺ charge was offset by removal of relative proportion of Mg²⁺ and Nb⁵⁺ together with creation of oxygen non-stoichiometry in order to preserve electroneutrality of the system. These samples were crystallised in cubic structure with space group of Fd3m, No. 227 and their refined lattice parameters were in the range of 10.5706 (3)–10.5797 (7) Å. The surface morphologies of the samples as confirmed by scanning electron microscopy analysis were of irregular shaped grains while their crystallite sizes of ~30–85 nm were calculated using the Scherrer equation and the Williamson–Hall method. No thermal event was discernable indicating these pyrochlores were thermally stable within a studied temperature range of ~30–1000 °C. The recorded dielectric constants of Bi_3+(5/2)xMg_2−xNb_3−(3/2)xO_14−x (0.14≤x≤0.22) subsolidus pyrochlores were generally above ~160 and their dielectric losses were in the order of 10⁻⁴–10⁻³ at the frequency of 1 MHz and temperature of ~30 °C. Meanwhile, these ceramic samples also exhibited negative temperature coefficient of relative permittivity between −528 and −742 ppm/°C in the temperature range of ~30–300 °C.     

Structural and electrical properties of BZT-added BNLT ceramics

Lead free piezoelectric ceramics (1−x)BNLT−xBZT with x=0.00, 0.06, 0.09 and 0.12 were prepared using a two-step mixed oxide method. Dielectric, ferroelectric and piezoelectric properties of the ceramics were improved by the addition of the BZT. XRD results show tetragonal symmetry structure of the BNLT–BZT ceramics. It was found that the tetragonality increases with increasing BZT content. The optimum composition is x=0.09, where the maximum values of the piezoelectric constant d₃₃ (~126 pC/N) and dielectric constant (~2400) were obtained at room temperature. This BNLT–BZT system can be a promising candidate for lead-free piezoelectric ceramics.