NH4F-(NH4)2SO4复合电解液中制备莲藕状TiO2纳米管阵列及光生阴极保护性能研究

采用二次阳极氧化法在NH₄F-(NH₄)₂SO₄复合电解液中制备近似莲藕状TiO₂纳米管阵列(TNTAs)。通过XRD、SEM、PL(光致发光光谱)等手段研究了不同阳极氧化电压下制备的TNTAs的结构、形貌以及光生载流子的分离率。同时,在模拟太阳光下,通过测试光生电流密度评估其光电化学性能,通过测试开路电位、Tafel极化电位和EIS拟合曲线评估对304SS的阴极保护效果。结果显示,当阳极氧化电压为25 V时,TNTAs莲藕状清晰,规整度较高,光生载流子分离率高,光生电流密度达到最高值为309.2μA·cm^-2,开路电位达到最低值-0.986 V(vs.Ag/AgCl)时,对304SS的阴极保护效果较好。     

TiO2的微观形貌对316L不锈钢的光电化学阴极保护性能的影响研究

通过控制水热反应过程中的钛酸四丁酯的浓度,有效调控了TiO₂光电极的形貌,同时研究了形貌对316L不锈钢的光电化学阴极保护性能的影响。实验结果表明,钛酸四丁酯的加入量为1.25mL时,TiO₂-2具有最大的光致电位降和光致电流密度,表明其对316L不锈钢具有最优的光电化学阴极保护性,电化学阻抗谱的结果表明,载流子的迁移能力的提升是其光电化学阴极保护性能提升的主要原因。     

Bi2S3/CdS/TiO2纳米复合材料的制备及对304不锈钢的光生阴极保护性能研究

通过超声辅助连续离子层吸附和反应法在TiO₂纳米管上负载CdS和Bi₂S₃,通过SEM、XRD、XPS等手段对材料的形貌、结构、元素组成和价态进行表征,在模拟太阳光下,系统研究TiO₂纳米复合材料的电化学性能。结果表明,负载CdS和Bi₂S₃的TiO₂纳米复合材料的光吸收范围扩展到可见光区,载流子的复合率也大大降低,光电流密度提升至850μA·cm^-2,是改性前的3.4倍;将其与304不锈钢耦合后,电位降至-0.99 V,比改性前的耦合电位低约70 mV,可以进一步提升对304不锈钢的光生阴极保护效果。     

熔盐电解法制备单一Sm2Fe17合金相的机理研究

选择在LiF-CaF₂-SmF₃熔盐体系中,采用熔盐电解法在1160℃下通过恒电流在Fe阴极表面获得了不同厚度(17.22～40.34μm)的Sm₂Fe₁₇合金层,同时通过循环伏安法与方波伏安法研究了Sm³⁺在W与Fe阴极上的电化学行为。结果表明,Sm³⁺无法单独沉积于W电极上,Sm³⁺在铁阴极上的还原为Sm⁰分为2步,首先在-0.33V(vs.Cr/Cr₂O₃)发生Sm³⁺还原为Sm²⁺的可溶-可溶型反应,然后当电极电势超过-0.78V(vs.Cr/Cr₂O₃)时Sm²⁺开始在阴极界面处上发生欠电势还原,在Fe电极表面生成Sm₂Fe₁₇合金,这是由于在Sm₂Fe₁₇合金中降...     

特殊形貌的PANI/CeO2的电化学制备

采用恒电位法,以石墨箔为工作电极,通过聚苯胺（PANI）和二氧化铈（CeO₂）的电化学共沉积,制备了PANI/CeO₂复合膜.利用SEM,TEM和电子衍射（EDP）观测了PANI/CeO₂复合膜的形貌和结构,利用Fourier变换红外光谱（FTIR）研究了PANI/CeO₂复合膜的组成,利用循环伏安法研究了PANI/CeO₂复合膜的电化学行为.研究了电化学沉积条件对PANI/CeO₂复合膜形貌的影响.结果表明,在1.1 V（vs SCE）进行PANI与CeO₂的电化学共沉积时,由于苯胺电化学聚合和CeO₂电化学沉积过程中均释放一定量的H⁺,PANI/CeO₂复合膜以"羊角"形貌存在;而0.8 V电化学沉积的复合膜则以纳米颗粒形式存在."羊角"形的PANI/CeO₂复合膜上形成很多上部宽大、底部稍窄的懊形空间,有利于客体粒子进入复合膜深处与活性组分充分接触,提高性能.复合膜的FTIR谱上出现了PANI的典型振动吸收,循环伏安测试结果表明复合膜主要呈现PANI的电化学性能.     

特殊形貌的PANI/CeO2的电化学制备

采用恒电位法,以石墨箔为工作电极,通过聚苯胺（PANI）和二氧化铈（CeO₂）的电化学共沉积,制备了PANI/CeO₂复合膜.利用SEM,TEM和电子衍射（EDP）观测了PANI/CeO₂复合膜的形貌和结构,利用Fourier变换红外光谱（FTIR）研究了PANI/CeO₂复合膜的组成.利用循环伏安法研究了PANI/CeO₂复合膜的电化学行为.研究了电化学沉积条件对PANI/CeO₂复合膜形貌的影响.结果表明,在1.1 V（vs SCE）进行PANI与CeO₂的电化学共沉积时,由于苯胺电化学聚合和CeO₂电化学沉积过程中均释放一定量的H⁺,PANI/CeO₂复合膜以"羊角"形貌存在;而0.8 V电化学沉积的复合膜则以纳米颗粒形式存在."羊角"形的PANI/CeO₂复合膜上形成很多上部宽大、底部稍窄的楔形空间,有利于客体粒子进入复合膜深处与活性组分充分接触,提高性能.复合膜的FTIR谱上出现了PANI的典型振动吸收,循环伏安测试结果表明复合膜主要呈现PANI的电化学性能.     

用于增强光电化学水氧化的Sb_2O_3/Sb_2S_3/FeOOH复合光阳极的构建（英文）

通过简单的溶液浸渍法以及化学水浴沉积法和后硫化处理制备新型Sb_2O_3/Sb_2S_3/FeOOH光阳极。X射线衍射、拉曼光谱和X射线光电子能谱分析表明成功制备Sb_2O_3/Sb_2S_3/FeOOH薄膜。SEM-EDS分析表明,FeCl_3溶液浸泡后的Sb_2O_3/Sb_2S_3薄膜表面变得粗糙,最优的浸渍时间为8 h。在模拟太阳光和偏压1.23 V(vs RHE)下,FeOOH助催化剂负载的Sb_2O_3/Sb_2S_3电极表现出0.45 mA/cm~2的光电流密度,为未负载FeOOH光电极的1.41倍。通过紫外-可见光谱、电化学阻抗谱和PEC测试表明,光电性能的提高是由于FeOOH的复合可增强光电极的光捕获能力、降低界面传输阻抗、提高载流子注入效率。     

多壁纳米碳管/TiO2复合薄膜的制备与光阴极保护性能研究

用溶胶凝胶旋涂工艺在304不锈钢表面制备了多壁纳米碳管MWCNT/TiO₂复合薄膜,用X射线衍射技术和电子显微技术研究了复合薄膜的物相组成与显微形貌,同时采用电化学分析手段,分别在250 W紫外灯和28 W节能灯的照射下,表征了MWCNT/TiO₂复合薄膜在3% NaCl溶液和海水介质中对304不锈钢的光阴极防腐蚀性能。研究结果表明,经450℃煅烧和加入管径为20~40 nm纳米碳管制备的MWCNT/TiO₂复合薄膜,不论是在紫外光还是白光激发下都表现出了比纯TiO₂薄膜更加优良的光电性能。同时也表明在3% NaCl溶液和海水介质中纳米碳管的引入都可有效增强TiO₂薄膜对304不锈钢的光阴极防腐蚀性能。     

Al2O3钝化层对a-IGZO薄膜晶体管电性能的增强机制研究

采用空心阴极增强脉冲激光沉积技术(HC-PLD)在室温制备高质量的Al₂O₃薄膜，作为非晶铟镓锌氧(a-IGZO)TFT器件的钝化层，显著增强了Al₂O₃/a-IGZO TFT器件的亚阈值特性，其原因在于空心阴极引入的氧等离子体抑制了Al₂O₃/a-IGZO界面处氧空位的形成。进一步研究发现，针对a-IGZO薄膜的180℃退火处理有利于消除弱结合氧并抑制深能级缺陷，提高载流子迁移率并降低阈值电压漂移；而针对Al₂O₃/a-IGZO TFT器件进行100℃退火处理有助于消除其界面附近的氧空位，降低载流子浓度，改善亚阈值特性。结合2步退火工艺所制备的Al₂O₃/a-IGZO TFT器件迁移率高达22.8 cm²·V^-1·s^-1，亚阈值摆幅为0.6 V·decade^-1，综合电性能优异。     

锌电积用Pb-Ag阳极MnO2镀膜的电化学性能

锌电积用Pb-Ag阳极存在析氧过电位高、表面铅易电化学氧化溶解,造成阴极电锌品质低等突出问题,如何减少阳极的溶铅污染并提升其催化析氧活性、降低反应能耗,成为亟待解决的难题。本文在Pb-Ag阳极表面电沉积一层均匀、致密的MnO₂薄膜,采用SEM、XRD和ICP等对MnO₂催化层的表面微观形貌、晶体结构和溶液含铅量进行分析;采用CV、LSV、EIS和Tafel等对Pb-Ag/MnO₂阳极的析氧催化活性和耐腐蚀性能进行分析。结果表明：在MnSO₄-H₂SO₄溶液中,当循环速率为200 mL/min、温度为80℃时,以4 mA/cm²电沉积120 min制备的Pb-Ag/MnO₂镀膜电极具有最佳的催化析氧和耐蚀性能;PbAg阳极经优化镀膜后,50 mA/cm²时其析氧过电位由936 mV降低为648 mV,腐蚀电流密度由7.03μA/cm²降低至0.66μA/cm^2<...     

X-ray diffraction study of Ba0.985Na0.015Ti0.985Nb0.015O3, Ba0.6Na0.4Ti0.6Nb0.4O3 and Ba0.3Na0.7Ti0.3Nb0.7O3 compositions

The Ba_0.985Na_0.015Ti_0.985Nb_0.015O₃, Ba_0.6Na_0.4Ti_0.6Nb_0.4O₃ and Ba_0.3Na_0.7Ti_0.3Nb_0.7O₃ compositions of the (1 − x) BaTiO₃–xNaNbO₃ (BTNNx) system have been studied by X-ray diffraction and by measurements of dielectric properties. The specimens with composition BTNN (x = 0.015, 0.40 and 0.70) have been refined by the JANA program from X-ray powder diffraction data. Ceramic samples with composition (1 − x) BaTiO₃ + xNaNbO₃ (where x = 0.015, 0.40 and 0.70) were prepared by calcinations from appropriate mixture of BaCO₃, TiO₂, Na₂CO₃ and Nb₂O₅. The calcined powder was sintered at temperature range 1200–1400 °C. As the composition x increased from 0.015 (and 0.70), the ferroelectric ceramics (x = 0.015, FE) with tetragonal phase changed to the ferroelectric relaxors (RFE, x = 0.40). RFE ceramics showed a peculiar diffuse phase transition and dielectric relaxation at the low temperature (down to 180 K) due to a frustration between RFE and FE state. These ceramics present the classical ferroelectric character when 0 ≤ x < 0.075 and 0.55 < x ≤ 1 and relaxor character when 0.075 ≤ x ≤ 0.55.     

Magnetic, electrical and plastic properties of Fe76Nb2Si13B9, Fe75Ag1Nb2Si13B9 and Fe75Cu1Nb2Si13B9 amorphous alloys

Influence of 1 h annealing in vacuum on magnetic, electrical and plastic properties of Fe₇₆Nb₂Si₁₃B₉, Fe₇₅Ag₁Nb₂Si₁₃B₉ and Fe₇₅Cu₁Nb₂Si₁₃B₉ melt spun ribbons were carefully investigated. It was shown that in all cases soft magnetic properties can be significantly enhanced by applying 1-h annealing at characteristic temperatures T_op. This optimization annealing causes that permeability increases more than 15-times and magnetic losses (tangent of loss angle) achieves a minimum in relation to the as quenched state. Using structural examinations (X-ray and HRTEM) it was shown that for the Fe₇₅Cu₁Nb₂Si₁₃B₉ alloy the optimized microstructure corresponds to a nanocrystalline αFe(Si) phase whereas in other alloys to a relaxed amorphous phase free of iron nanograins. As a consequence of this fact the Fe₇₆Nb₂Si₁₃B₉ and Fe₇₅Ag₁Nb₂Si₁₃B₉ alloys show higher plasticity in comparison to the nanocrystalline Fe₇₅Cu₁Nb₂Si₁₃B₉ alloy. Temperatures of the first stage of crystallization, and related diffusion parameters were determined using measurements of resistivity versus temperature with different heating rates.     

Fe2+-Ni2+-NH3-NH4+-C2O42-H2O体系的沉淀配合平衡热力学

针对草酸盐配位共沉淀热分解还原法制备超细铁镍合金粉过程中Fe2+-Ni2+-NH3-NH4+-C2O42--H2O体系的溶液平衡建立热力学分析模型,并根据模型进行相关计算,揭示反应体系中各物质随pH值、氨及草酸浓度的变化关系。结果表明:溶液中的Fe主要以[Fe(C2O4)n]2 2n络合物形式存在,而铁氨络合物含量很低。当氨含量较低时,溶液中的Ni主要以[Ni(C2O4)n]2 2n存在;氨含量较高时,在酸性条件下,溶液中的Ni主要以[Ni(C2O4)n]2 2n存在,在碱性条件下,则主要以[Ni(NH3)n]2+存在。低pH值下,Ni的沉淀率较Fe的高,而高pH值下,Ni的沉淀率则较Fe的低。     

New Zr6CoAs2-type compounds: Y6CoBi2, Ho6CoBi2 and Tm6CoBi2

Results of a powder X-ray diffraction investigation of new ternary compounds are reported. The compounds Y₆CoBi₂ [a=0.8312(1) nm, c=0.4144(1) nm], Ho₆CoBi₂ [a=0.8246(2) nm, c=0.4095(1) nm], and Tm₆CoBi₂ [a=0.8155(2) nm, c=0.4066(1) nm] crystallize in the hexagonal Zr₆CoAs₂-type structure (space group P6b2m No. 189). The Zr₆CoAs₂-type structure is a superstructure of the Fe₂P-type structure.     

Thermodynamics and phase diagrams in the binary systems Na2O-SiO2, Na2O-GeO2, Na2O-B2O3, Li2O-B2O3, CaO-B2O3, SrO-B2O3, and BaO-B2O3

We applied our model to the enthalpy of mixing data of the binary systems Na₂O-SiO₂, Na₂O-GeO₂, Na₂O-B₂O₃, Li₂O-B₂O₃, CaO-B₂O₃, SrO-B₂O₃, and BaO-B₂O₃. The most stable composition in the liquid, that is where the enthalpy of mixing is most negative, is with a metal-oxygen ratio of 4 to 3, for monovalent metals (Na and Li) and 3 to 4 for divalent metals (Ba and Ca) in liquid silicates or borates. The same applies to the CaO-SiO₂, CaO-Al₂O₃, PbO-B₂O₃, PbO-SiO₂, ZnO-B₂O₃, and ZnO-SiO₂ systems. The oxygen to metal ratio, its constant value in various types of systems, reflects and describes the structure of the liquid. Using the analyzed enthalpies of mixing data and the available phase diagrams, we calculated the enthalpies of formation of the various binary compounds. The results are in excellent agreement with data in the literature that were obtained from direct solid-solid calorimetry.     

Al2O3-Sm2O3-CeO2电解质的性能（英文）

采用溶胶-凝胶法和低温燃烧技术制备Ce1-xSmxO2（x=0,0.1,0.2,0.3）和掺杂Sm和（2%-8%）Al2O3的二氧化铈;研究其合成、结构、致密化、导电性和热膨胀等性能,并利用XRD研究其结构和相组成。结果表明,于1300°C烧结球团,获得致密的陶瓷,于1250°C在Ce0.8Sm0.2O0.2中加入2%和4%的Al2O3以促进烧结。利用扫描电子显微镜观察烧结后球团的表面形貌,使用双探针交流阻抗谱研究总离子电导率。     

电弧喷涂制备Fe65Cr20Mo7B3.5SiMn1.5W3涂层

在Q235低碳钢板上利用电弧喷涂工艺进行喷涂,以制得Fe65Cr20Mo7B3.5SiMn1.5W3涂层。喷涂材料为自行配制的丝材,按照35%的填充率将配好的粉填充到U型不锈钢外皮中,经过多道拉拔、挤压工艺制成Φ2mm的粉芯丝材。采用X射线衍射仪、扫描电镜、能谱分析仪、透射电镜对涂层的物相和组织形貌及成分进行了表征;采用差示扫描量热仪、显微硬度仪等设备对涂层的热稳定性及显微硬度进行了检测和分析。试验结果表明:涂层组织形貌呈典型的层状组织结构,由变形良好的带状粒子相互搭接堆积而成。涂层含有50.63%的非晶相,同时含有纳米级的晶相。涂层组织均匀、结构致密、孔隙率低,并且涂层硬度高达1040.5HV0.3,属硬质涂层,具有良好的热稳定性。     

Zur Kenntnis von RbBa3Ca4Cu3V7O28

Single crystals of RbBa₃Ca₄Cu₃V₇O₂₈ were prepared above the melting point of the reaction mixture. It crystallizes with hexagonal symmetry, space group C_6V⁴-P6₃mc, a 11.1751, c 12.434 Å, Z = 2. RbBa₃Ca₄Cu₃V₇O₂₈ is the second member of a new structure type of the copper-oxovanadates. Ba²⁺ shows an unusual 12-fold coordination. The two calcium positions are coordinated by trigonal prisms and octahedra respectively. The copper coordination is characterized by a stretched square pyramid. The Cu²⁺ ions are outside the centre nearly in plane of the pyramids.

Zusammenfassung

Einkristalle von RbBa₃Ca₄Cu₃V₇O₂₈ wurden oberhalb des Schmelzpunktes der Reaktionsmischung erhalten. Die Verbindung kristallisiert hexagonal, Raumgruppe C_6V⁴-P6₃mc, a 11.1751, c 12.434 Å, Z = 2. RbBa₃Ca₄Cu₃V₇O₂₈ ist das zweite Beispiel für einen neuen Strukturtyp der Kupfer-Oxovanadate, mit 12-fach koordinierten Ba²⁺ -Ionen. Die zwei Calciumpositionen sind trigonal prismatisch bzw. oktaedrisch koordiniert. Die Koordination der Cu²⁺-Ionen ist durch eine gestreckte Pyramide charakterisiert. Cu²⁺ ist auβerhalb des Polyederzentrums nahezu in der quadratischen Fläche der Pyramide angeordnet.     

Y2O3-BaO-SiO2-B2O3-Al2O3 glass sealant for solid oxide fuel cells

A glass based on Y₂O₃-BaO-SiO₂-B₂O₃-Al₂O₃ (named YBA) has been investigated as sealant for planar solid oxide fuel cells (SOFCs). The YBA glass has been systematically characterized by differential thermal analysis, dilatometer, scanning electron microscopy, impedance analysis, and open circuit voltage to examine their suitability as sealant. The coefficient of thermal expansion of YBA is 11.64 × 10⁻⁶ K⁻¹ between 323 and 873 K. The resistivity is 9.1 × 10⁴ Ω cm at 800 °C. The glass sealant is found to be well adhered with other cell components, such as electrolytes and stainless steels, at an optimum sealing temperature of 800 °C. All measured results showed that the YBA glass appears to be a promising sealant for SOFCs.     

Sinterability and dielectric properties of Ba0.55Sr0.4Ca0.05TiO3-CaTiSiO5-Mg2TiO4 composite ceramics

The composite ceramics of Ba_0.55Sr_0.4Ca_0.05TiO₃-CaTiSiO₅-Mg₂TiO₄ (BSCT-CTS-MT) were prepared by the conventional solid-state route. The sintering performance, phase structures, morphologies, and dielectric properties of the composite ceramics were investigated. The BSCT-CTS-MT ceramics were sintered at 1100 °C and possessed dense microstructure. The dielectric constant was tailored from 1196 to 141 as the amount of Mg₂TiO₄ increased from 0 to 50 wt%. The dielectric constant and dielectric loss of 40 wt% Ba_0.55Sr_0.4Ca_0.05TiO₃-10 wt% CaTiSiO₅-50 wt% Mg₂TiO₄ was 141 and 0.0020, respectively, and the tunability was 8.64% under a DC electric field of 8.0 kV/cm. The Curie peaks were broadened and depressed after the addition of CaTiSiO₅. The optimistic dielectric properties made it a promising candidate for the application of tunable capacitors and phase shifters.