两元P—型梯度结构热电材料FeSi2／Bi2Te3的制备与性能

采用热浸焊法用纯Sn作为过渡层制备了P－型FeSi2/Bi2Te3梯度结构热电材料并对其热电性能进行了测试,发现当热端温度在510℃以下时,梯度结构热电材料的平均Seebeck系数保持恒定,达220uV/K至250uV/K左右,显著高于单一均质材料（Bi2Te3和β－FeSi2)在相同温度范围内的平均Seebeck系数,梯度结构热电材料的输出功率较单种材料高1．5至2倍以上,且当材料经190℃,100h与200h的真空退火后,输出功率几乎不变,金相观察表明,在Sn层与两半导体界面处,没有明显的Sn 扩散迹象,说明在所试验的条件下,用Sn作为过渡层热稳定性较好。     

宽温区P-型热电材料的性能表征与设计

通过对Bi2 Te3 /FeSi2 叠层热电材料的性能建模计算 ,得出了该结构的平均Seebeck系数及内电阻与热端温度的关系可分别用两个三次多项式表征。在外阻为 0 .0 734Ω ,热端温度约 5 10℃时 ,Bi2 Te3 /FeSi2 叠层热电材料的最大输出功率值与实验值较为接近 ,在相同条件下均为计算得出的单段FeSi2 材料的 2 .5倍 ,说明该方法有效、可行。对用此方法建模设计多种单段材料组合成的梯度结构 ,计算发现以两种不同成分并经相近工艺制备的均质FeSi2 材料制成的叠层结构性能较优 ,与Bi2 Te3 /FeSi2 结构有相同的最大输出功率值。但从多方面分析表明 ,用两均质FeSi2 材料制成的宽温区热电材料更具潜力     

Bi_2Te_3和Bi_(0.5)Sb_(1.5)Te_3的机械合金化法制备及其热电性能

用机械合金法制备了Bi2 Te3和Bi0 .5Sb1 .5Te3两种热电材料。XRD分析表明两种材料分别在球磨 1 75h和 31 5h后完全合金化。机械合金化合金粉末冷压后在不同温度烧结并测量了热电性能 ,其中Bi0 .5Sb1 .5Te3材料480℃烧结样的最高Seebeck系数约为 2 0 0 μV/K。     

SPS法制备n-型Ag掺杂四元Ag-Bi-Se-Te 合金及其热电性能

采用放电等离子烧结(SPS)方法制备Ag掺杂四元Ag-Bi-Se-Te合金,并分析研究其热电性能.结果表明:掺杂Ag后,合金AgxBi(2-x)Se0.3Te2.7(x=0.005～0.04)的Seebeck系数均为负值,说明材料属于n-型半导体;当温度大约在428.0K时,x=0.04合金的Seebeck系数绝对值(|a|)出现最大值,其值为1.80×10-4V·K-1,比三元合金Bi2Se0.3Te2.7的最大值增大约16%;材料电导率随Ag含量的增加而下降.如果采用相同方法制备且成分按(Bi2Te3)0.9-(Bi2-xAgxSe3)0.1(x=0～0.4)设计的材料热扩散系数进行估算,当温度在477.0 K时,合金AgxBi(2-x)Se0.3Te2.7(x=0.04)的ZT值出现最大值,其值为0.75,比典型三元合金Bi2Se0.3Te2.7的最大值增大约0.09.     

溶剂热合成Bi2Te3基合金的结构与电学性能

用溶剂热法合成了二元Bi2Te3和三元Bi1.3Sn0.7Te3合金纳米粉末,并采用热压技术制备了块状热电材料.XRD分析结果表明:Bi-Sn-Te三元固溶体合金可以直接通过溶剂热合成获得单相产物,而非掺杂Bi2Te3合金需要通过热压等后热处理来实现产物的单一化;热压过程有助于促进反应的完全和晶型的完整,但会导致晶粒的长大.对试样电导率σ和Seebeck系数α的测量结果显示,Bi-Sn-Te三元固溶体合金比二元Bi-Te合金具有更好的电学性能.     

p—型FeSi2／Bi2Te3梯度热电材料的优值推证与界面温度优化

通过对两元 p-型梯度热电材料 Fe Si2 / Bi2 Te3界面温度的建模计算与实验验证 ,在固定热冷端温区内积分得出的 Z- ΔT值与界面温度 Ti 的关系曲线为 :Z- ΔT =0 .6 72 +11.7× 10 - 4Ti - 1.31× 10 - 6 T2i - 3.4 9× 10 - 9T3i该关系可用来表征两元梯度结构的热电性能。从拟合曲线上得出该梯度结构的最佳界面温度为 2 2 0℃～ 2 30℃ ,这与实验测出两单段材料 (Fe Si2 ,Bi2 Te3)长度比为 10∶ 1左右时所形成的界面温度较为接近。通过测试不同长度比的材料输出功率 ,也发现 10∶ 1梯度材料的最大输出功率较大 ,是相同温差下单段 β- Fe Si2 材料的 2倍～ 2 .6倍。     

退火处理对室温制备Bi0.5Sb1.5Te3薄膜热电性质的影响

利用射频磁控溅镀法在SiO2/Si基板上制备了Bi0.5Sb1.5Te3薄膜样品,并且测量了薄膜样品在不同退火时间与退火温度下的热电性质。结果表明,薄膜样品经30 h退火后的热电性质与1 h退火后的热电性质相差不大,这说明长时间退火并不是Bi0.5Sb1.5Te3薄膜的最佳退火时间。而在不同退火温度下,样品的塞贝克系数在275～300℃退火下降比较快,当退火温度为300℃时降至最小,约为181μV/K;而其电阻率则随退火温度的升高呈现出先减小后增大的趋势,退火温度为225℃时具有最小的电阻率,约为6.1 mΩ.cm。最后本文得出经225℃退火10 min后可得到最佳的热电性质,即薄膜样品的塞贝克系数为208μV/K,电阻率为6.1mΩ.cm,功率因子则为6.9×10-4W/(m.K2)。     

Ga、K双掺杂对N型Bi_2Te_(2.7)Se_(0.3)材料热电性能的影响

采用真空熔炼及热压方法制备了Ga和K双掺杂N型Bi2Te2.7Se0.3热电材料。XRD分析结果表明,Ga和K已经完全固溶到Bi2Te2.7Se0.3晶体结构中,形成了单相固溶体合金。SEM分析表明,材料组织致密且有层状结构特征。通过Ga和K部分替代Bi,在300~500 K的大部分温度范围内,Ga和K双掺杂对提高Bi2Te2.7Se0.3的Seebeck系数产生了积极的作用,同时双掺杂样品的电导率也得到明显的提高。Ga和K双掺杂样品的热导率都大于未掺杂的Bi2Te2.7Se0.3,Ga0.02Bi1.94K0.04Te2.7Se0.3合金在500 K获得ZT最大值为1.05。     

机械合金化法制备的Mn15Bi34Te51和La15Bi34Te51热电材料

用机械合金化法制备了Mn15Bi34Te51和La15Bi34Te51合金，XRD分析表明Mn15Bi34Te51和La15Bi34Te51分别在真空球磨150h和100h后实现合金化，La15Bi34Te51在真空球磨150h后形成了纳米结构的合金，镧原子的加入有助于Bi2Te3基合金的晶粒细化及非晶化。对La15Bi34Te51合金的XRD结构分析表明镧原子有可能进入了Bi2Te3层状结构的Te-Te原子层间。La15Bi34Te51合金Seebeck系数的测量表明当晶粒尺寸减小到纳米尺寸时，载流子散射机制有可能发生改变，导致了Seebeck系数的大幅上升。     

采用Sn-Bi钎料钎焊Bi2Te3基热电材料与无氧铜

Bi2Te3基热电材料需与电极Cu连接构成热电模块.采用无铅钎料Sn-Bi及钎剂实现了大气环境中分别直接钎焊p型(Bi,Sb)2Te3与无氧Cu和n型Bi2(Te,Se)3与无氧Cu.观察了接头的组织及Sn,Cu,Bi元素在接头处的线分布和面分布.通过研究表明,Sn元素与p型(Bi,Sb)2Te3的反应比与n型Bi2(Te,Se)3剧烈,在(Bi,Sb)2Te3与Sn-Bi界面处形成了5～7 μm的Sn反应层;Cu元素在Cu/Sn-Bi界面处也形成几微米的反应层;温度增加,两种反应的程度均有增加趋势.利用Gleeble1500D试验机测试了两种类型接头的抗剪强度,结果表明,(Bi,Sb)2Te3/Sn-Bi/Cu接头平均抗剪强度为5.1MPa,Bi2(Te,Se)3/Sn-Bi/Cu接头则为4.4 MPa,(Bi,Sb)2Te3/Sn-Bi/Cu接头强度分散性高于Bi2(Te,Se)3/Sn-Bi/Cu接头.接头主要断裂于反应层,反应层的成分、组织和厚度是影响接头强度的关键因素.     

Vitreous phase coating on glaserite-type alkaline earth silicate blue phosphor BaCa2MgSi2O8:Eu

A simple solid-state reaction was used to apply a vitreous-phase coating onto Eu²⁺-doped BaCa₂MgSi₂O₈ blue-phosphor particles. The vitreous phase was generated by liquid phase sintering at 1200 °C. The coated phosphor exhibited resistant to an acid dispersant. When a small amount of Al and La was added in raw materials, they were incorporated in the vitreous coating phase.     

Effect of Ti3SiC2 content on the corrosion behavior of Al/Ti3SiC2 composite coatings

The purpose of this study was to investigate the electrochemical corrosion properties of flame-sprayed Al and Al/(5, 10, 15)% Ti₃SiC₂ coatings in a 3.5% NaCl solution. Scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) were used for analyzing the microstructural characteristics of the coatings. For examining the corrosion behavior of the coatings, a potentiodynamic polarization test and electrochemical impedance spectroscopy (EIS) were used. After the potentiodynamic polarization test, the SEM micrograph of coatings indicated that Ti₃SiC₂ particles played a significant role in pitting corrosion. The results of potentiodynamic polarization tests revealed that Al/Ti₃SiC₂ coating is nobler than that of the pure aluminum coating. On the contrary, the addition of Ti₃SiC₂ particles reduced the process of thickening the passive layer. The results of the EIS tests demonstrated that the presence of Ti₃SiC₂ particles significantly enhances the corrosion resistance of the coatings.     

STRUCTURAL AND MAGNETIC PROPERTIES OF ( PrxSm1 - x ) Mn2Si2

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Tetragonal-cubic phase boundary in nanocrystalline ZrO2-Y2O3 solid solutions synthesized by gel-combustion

By means of synchrotron X-ray powder diffraction (SXPD) and Raman spectroscopy, we have detected, in a series of nanocrystalline and compositionally homogeneous ZrO₂-Y₂O₃ solid solutions, the presence at room temperature of three different phases depending on Y₂O₃ content, namely two tetragonal forms and the cubic phase. The studied materials, with average crystallite sizes within the range 7-10 nm, were synthesized by a nitrate-citrate gel-combustion process. The crystal structure of these phases was also investigated by SXPD. The results presented here indicate that the studied nanocrystalline ZrO₂-Y₂O₃ solid solutions exhibit the same phases reported in the literature for compositionally homogeneous materials containing larger (micro)crystals. The compositional boundaries between both tetragonal forms and between tetragonal and cubic phases were also determined.     

Al2O3／TiB2／SiCw陶瓷材料的高温氧化行为

采用热压烧结工艺制备了Ａｌ２Ｏ３／ＴｉＢ２／ＳｉＣｗ陶瓷复合材料，研究了ＳｉＣ晶须含量对其高温氧化行煌影响。用ＸＲＤ，ＳＥＭ，ＴＥＭ／ＥＤＳ分析了材料氧化后的相组成及显向结构，探讨了该材料的氧化机理。结果表明：不同ＳｉＣｗ含量的Ａｌ２Ｏ３／ＴｉＢ２／ＳｉＣｗ陶瓷材料在１４００℃空气中氧化３０ｈ的氧化增重符合抛物线规律。     

Microstructural evolution during controlled ball milling of (Mg2Ni+MgNi2) intermetallic alloy

Nearly dual-phase Mg–Ni alloy fabricated by ingot metallurgy (IM) and comprising 30 vol% Mg₂Ni and 61 vol% MgNi₂ intermetallic compounds (remaining 9 vol% of unreacted Mg) was mechanically (ball) milled under controlled shearing for 10, 30, 70 and 100 h. The majority of the medium- and small-sized powder particles exhibited a relatively homogeneous microstructure of milled Mg₂Ni and MgNi₂. A fraction of large-sized particles developed the ‘core and mantel’ microstructure after milling for 70 and 100 h. The ‘core’ contains poorly milled MgNi₂ particles and the ‘mantel’ is a thoroughly milled mixture of Mg₂Ni, MgNi₂ and, possibly, residual Mg. X-ray diffraction provides evidence of nanostructurization and eventual amorphization of a fraction of a heavily ball milled Mg₂Ni phase. The remnant Mg₂Ni developed a nanocrystalline/submicrocrystalline structure. The co-existing MgNi₂ phase developed a submicrocrystalline structure within the powder particles. The results are rationalized in terms of enthalpy effects by the application of Miedema’s semi-empirical model to the phase changes in ball milled intermetallics.     

MOCVD of YSZ coatings using β-diketonate precursors

Metallorganic chemical vapor deposition (MOCVD) was investigated as a more efficient means to fabricate yttria-stabilized zirconia (YSZ) for thermal barrier coating. The MOCVD precursors were Y(tmhd)₃ and Zr(tmhd)₄ (tmhd, 2,2,6,6-tetramethyl-3,5-heptanedianato) and delivered via aerosol-assisted liquid delivery (AALD). The maximum YSZ coating rate was 14.2 ± 1.3 μm h⁻¹ at 827 °C yielding a layered coating microstructure. The growth was first-order with temperature below 827 °C with an apparent activation energy of 50.9 ± 4.3 kJ mol⁻¹. Coating efficiency was a maximum of approximately 10% at the highest growth rate. While homogeneous nucleation remained a problem, the deposition of YSZ with only minor carbon content was achieved.     

ZnO and TiO2 1D nanostructures for photocatalytic applications

ZnO and TiO₂ 1D nanostructures (nanorods and nanotubes) were prepared by low-cost, low-temperature, solution-based methods and their properties and photocatalytic performance were studied. ZnO nanorod samples with titania and alumina shells were also prepared by solution-based methods, and their properties and photocatalytic performance were compared to that of bare ZnO nanorods. We found that ZnO and TiO₂ exhibited comparable photocatalytic performance. Faster dye degradation under simulated solar illumination was observed for ZnO, while under UV illumination faster degradation was observed for TiO₂. ZnO nanorods with titania shells exhibited inferior photocatalytic performance, while for alumina shells the performance was similar to bare ZnO. Reasons for observed differences are discussed, and the effect of the shell on photocatalytic activity is attributed to the changes in native defects at the ZnO surface/shell interface.     

Synthesis of MnO/C composites through a solid state reaction and their transformation into MnO2 nanorods

MnO nanospheres encapsulated in carbon (MnO/C) composites were synthesized through a one-step solid state reaction between potassium permanganate and salicylic acid at 700 °C, which could be transformed into MnO₂ nanorods after being annealed in ambient atmosphere. Their formation mechanisms and electrochemical performances as anodes in Li-ion batteries (LIBs) were investigated. The first discharge capacity of MnO/C composites was 585.9 mA h g⁻¹, while that of MnO₂ was 1269 mA h g⁻¹, indicating their potential applications in LIBs.     

75％TiO2-25％SiO2氧化物的机械合金化

金红石TiO2是常用的钛阳极耐蚀载体材料。鉴于SiO2具有更高的耐蚀性、耐磨性和稳定性，而且价格低廉。因此，本文尝试以锐钛矿TiO2和石英SiO2颗粒原料，采用机械合金化（MA）方法制备TiO2-SiO2二元氧化物。本文通过30小时机械合金化作用，制备了摩尔浓度为75％TiO2-25％SiO2二元氧化物载体材料。通过XRD、DTA和TEM分析并观测了所获材料的组织结构和晶粒形貌。结果发现在MA作用下，该载体材料中的锐钛矿TiO2显著细化，有部分纳米晶粒出现，SiO2晶粒细化效果相对较弱；透射电镜下，粉末颗粒呈理想的等轴形态；产生了锐钛矿TiO2向金红石TiO2的相变，其相变温度比采用常规方法下的相变温度明显降低了约350℃：获得SiO2、TiO2互溶的固溶体组织，特别是生成了采用常规方法难以获得的TiO2．SiO2非平衡间隙固溶体。