Synthesis, characterization, and thermostability of bis（2,2,6,6-tetramethyl-3,5-heptanedionato）barium（II）

The metal-organic chemical vapor deposition (MOCVD) technique is a promising process for high-temperature superconductor YBa2 Cu3O7-δ(YBCO) preparation. In this technique, it is a challenge to obtain barium precursors with high volatility. In addition, the purity, evaporation characteristics, and thermostability of adopted precursors in whole process will decide the quality and reproducible results of YBCO film. In the present report, bis(2,2,6,6-tetramethyl-3,5-heptanedionato)barium(Ⅱ) (Ba(TMHD)2) was synthesized, and its structure was identified by FTIR, 1 H NMR, 13C NMR, and ESI-MS spectroscopy. Subsequently, the thermal properties and the kinetics of decomposition were systematically investigated by nonisothermal thermogravimetric analysis methods. Based on the average apparent activation energy evaluated by the Ozawa, Kissinger, and Friedman methods, the volatilization process was discussed, and all results show that Ba(TMHD)2 is unstable and highly sensitive to the change of temperature during the whole evaporation process. Therefore, it is very important to choose suitable volatilization technology and conditions for avoiding Ba(TMHD)2 break-down (or thermal aging) during MOCVD process. Subsequently, the possible conversion function is estimated through the Coats-Redfern method to characterize the evaporation patterns and follows a phase boundary reaction mechanism by the contracting surface equation with average activation energy of 118.7 kJ .mol-1.     

Synthesis, characterization and thermostability of barium β-diketonate with tetraethylenepentamine ligand

The metal-organic chemical vapor deposition (MOCVD) technique is a promising process for high-temperature superconductor YBa2Cu3O7-δ(YBCO) preparation. In this technique, it is a challenge to obtain barium precursors with high volatility. In addition, the purity, evaporation characteristics and thermostability of adopted precursors in the whole process would decide the quality and reproducible results of YBCO film. In the present report, the barium precursor containing 2,2,6,6-tetramethylheptane-3,5-dionate and tetraethylenepentamine ligands (Ba(TMHD)-tetraen) was synthesized and identified by FTIR, 1H NMR, 13C NMR and ESI-MS spectroscopy. Subsequently the thermal property and the kinetics of decomposition were systematically investigated by combining non-isothermal thermogravimetric analysis methods (TGA), Ozawa, Kissinger and Friedman methods. On the basis of the apparent activation energy of the evaporation process, the thermostability and evaporation characteristics of the precursors were discussed. All results show that Ba(TMHD)-tetraen has higher volatility than Ba(TMHD)2, but it is unstable and highly sensitive to the change of temperature during the whole evaporation process. Therefore, it is very important to choose suitable volatilization technology and conditions for avoiding Ba(TMHD)-tetraen breakdown (or thermal aging) during the MOCVD process.     

Effect of cold rolling on glass transition of Zr_(55)Al_(10)Ni_5Cu_(30) bulk metallic glass

Zr55Al10Ni5Cu30 bulk metallic glass was prepared through water-cooled copper mold suction casting, and was rolled up to 95% in thickness reduction. The structures and thermal stabilities of the as-cast and as-rolled specimens were examined by X-ray diffractometer and differential scanning calorimeter. As the thickness reduction increases, the crystallization onset temperature, peak temperature and the apparent activation energy of crystallization almost keep constant, while the glass transition temperature decreases from 681 to 671 K and the apparent activation energy of glass transition increases from (404±26) to (471±29) kJ/mol. The glass transition process is markedly affected by the rolling induced changes of microstructure and structural relaxation.     

Polymer assisted thick single-layer YBa_2Cu_3O_(7-δ)films prepared with modified TFA-MOD method

Single-layer YBa2Cu3O7-δ（YBCO） films with the thickness of over 600 nm were fabricated by modified metal organic deposition using trifluoroacetate metal organic deposition（TFA-MOD） method on LaAlO3（LAO） substrates. Polyvinylbutyral（PVB） was added into the precursor solution to enhance the thickness of the single layer. The pyrolysis process was shortened to about 3 h due to the reduction of the fluorine content in the precursor solution.The effects of heating rate during the crystallization process on the microstructure and Jcvalues of YBCO films were investigated. The α-axis-oriented YBCO crystals dominate when the heating rate is lower than 20 °C·min^-1, while faster heating rate of 43 °C·min^-1 results in pure c-axis epitaxial growth. The Jcvalues of YBCO films increase linearly with heating rate increasing due to the increase of c-axis YBCO growth, and the critical current（Ic） value of 100 A·cm^-1 within a single-layer YBCO film is achieved.     

Kinetics of isothermal reduction of stainless steelmaking dust pellets

The stainless steelmaking dust pellets were reduced in isothermal temperature condition simulating the direct recycling practice in the stainless steel production and the kinetics of the reduction process was investigated.The pellets were formed after mixing the dust with carbon as the reducing agent and dolomite as the binder and smelting flux. An electric furnace was used to heat the pellets and an electrical microbalance was used to check the mass of the pellets in the reduction process. The reduction rate was calculated according to the data of pellet mass change in consideration of the evaporation of moisture, zinc and lead at high temperature. The results of the experi-ments show that the reduction process is in two consecutive stages. The reduction kinetic models were set up for each stage and the kinetic parameters such as activation energy and frequency factor were determined. The apparent activation energy of the first stage is 21.69 kJ/mol, and this stage is controlled by chemical reaction. The apparentactivation energy of the second stage is 17.35 kJ/mol, and this stage is controlled by the diffusion of carbon monox-ide through the resultants of reaction.     

Fabrication of lotus-type porous micro-channel copper by single-mold Gasar technique

A single-mold Gasar technique was developed to produce lotus-type porous micro-channel copper with uniform porous structure. In this paper the effect of withdrawal rate on the solid/liquid interface morphology and the corresponding porous structure was systematically investigated, especially the pore morphology, pore growth direction, porosity, and pore diameter of porous copper ingots. In addition, a temperature field simulation was carried out based on ProCast software to investigate the shape and movement velocity of the solidifying solid/liquid interface. The experimental results show that the solidification interface changes from convex to planar, then to concave shape with an increase in withdrawal rate. The average porosities of copper ingots are constant and independent of the withdrawal rate. The average pore diameter decreases with an increase in withdrawal rate.     

Microstructural evolution of directionally solidified DZ125 superalloy castings with different solidification methods

The properties of Ni-base superalloy castings are closely related to the uniformity of their as-cast microstructure,and different solidification methods have serious effect on microstructural uniformity.In this paper,the influences of high rate solidification(HRS) process(with or without superheating) and liquid metal cooling(LMC) process on the microstructure of DZ125 superalloy were investigated.Blade-shape castings were solidified at rates of 40 μm·s-1 to 110 μm·s-1 using HRS process and a comparative experiment was carried out at a rate of 70 μm·s-1 by LMC process.The optical microscope(OM),scanning electron microscope(SEM) were used to observe the microstructure and the grain size was analyzed using electron back scattered diffraction(EBSD) technique.Results show that for the castings by either HRS or LMC process,the primary dendrite arm spacing and size of γ’ precipitates decrease with increasing the withdrawal rate;the dendrites and γ’ precipitates at the upper section of the blade are coarser than those in the middle,especially for the HRS castings without high superheating technique.When the withdrawal rate is 70 μm·s-1,the castings by HRS with high superheating technique have the smallest PDAS with fine γ’ precipitates;while the size distribution of γ’ precipitates is more homogenous in LMC castings,and the number of larger grains in LMC castings is smaller than that in the HRS castings.Moreover,high superheating technique yields smaller grains in the castings.Both the LMC method and HRS with high superheating technique can be used to prepare castings with reduced maximum grain size.     

Epitaxial growth of MOCVD-derived YBCO films by modulation of Cu（tmhd）2 concentration简

Metal–organic chemical vapor deposition was applied to fabricate YBa2 Cu3 O7-d(YBCO) films on singlecrystal LaAlO3(001) substrates for its high deposition rate, easy adjustment on film composition, and low requirement on vacuum apparatus. The effects of Cu(tmhd)2 concentration in the precursor on the properties of YBCO films were systematically investigated. X-ray diffraction(XRD) reveals that the mole ratio of Cu/Ba in the precursor from 0.77 to 0.97 is helpful to improve the crystallization and out-of-plane orientation of YBCO films; however, it hardly affects the inplane texture. Scanning electron microscope(SEM) shows the dense, crack-free but rough surface, on which there are Cu–O and Ba–Cu–O outgrowths identified by energy-dispersive spectrometer(EDS). As the mole ratio of Cu/Ba increasing, the average size of Ba–Cu–O precipitates keeps increasing and the film composition becomes inhomogeneous at the mole ratio of Cu/Ba of 0.97. The 250 nm thick YBCO film prepared at the mole ratio of Cu/Ba of 0.91 shows the critical current density(Jc) of 4.0 MA cm-2(77 K, 0 T).     

ELECTROCHEMICAL NOISE ANALYSIS OF THE INFLUENCE OF THE Zn^2＋ IONS CONCENTRATION ON ZINC ELECTROPLATING

The influence of the concentration of Zn^2 ions on zinc electroplating process was investigated by means of electrochemical noise (EN) and cyclic voltammetry methods in conjunction with the scanning electron microscopy (SEM) technique. It was found that the EN generated during the electroplating of dentritic or large polymeric zinc deposit has large potential oscillation amplitude and positive potential drift while the compact zinc deposit possesses small noise amplitude and little potential drift. With the change of rate determining step from diffusion-control through mixed-contro! to activation-control, the maximum relative energy obtained from wavelet analysis defined from the region with larger scales to those with smaller scales, and the EDP (relative energy distribution plot) can be us, as “fingerprints” of EN to characterize the electroplating process and the deposit structure. The results also showed that electrochemical noise technique can give more information about the electrodeposit structure than other normal electrochemical measurements, such as linear potential sweep method and cyclic voltammetry, technique.     

Interfacial phase formation of Al-Cu bimetal by solid-liquid casting method

The solid-liquid method was used to prepare the continuous casting of copper cladding aluminium by liquid aluminum alloy and solid copper, and the interfacial phase formation of Al-Cu bimetal at different pouring temperatures (700, 750, 800 ℃) was investigated by means of metallograph, scanning electron microscopy (SEM) and energy dispersive spectrometry (EDS) methods. The results showed that the pouring temperature of aluminum melt had an important influence on the element diffusion of Cu from the solid Cu to Al alloy melt and the reactions between Al and Cu, as well as the morphology of the Al-Cu interface. When the pouring temperature was 800 oC, there were abundant Al-Cu intermetallic compounds (IMCs) near the interface. However, a lower pouring temperature (700 ℃) resulted in the formation of cavities which was detrimental to the bonding and mechanical properties. Under the conditions in this study, the good metallurgical bonding of Al-Cu was achieved at a pouring temperature of 750 ℃.     

(Y,Gd)2O3:Eu3+纳米粒子制备过程中的合成动力学

采用反向滴定共沉淀法制备出（Y,Gd）₂O₃:Eu³⁺前躯体,再在不同温度下煅烧,获得（Y,Gd）₂O₃:Eu³⁺纳米粒子,用XRD和SEM对样品物相组成及形貌进行了表征;用TG-DTA获得了佯品在不同升温速率下的热分解曲线.结果表明,前躯体在煅烧过程中的物相变化分为3个阶段,用Doyle-Ozawa法和Kissinger法分别计算出各个反应阶段的表观活化能,其平均值分别为191.54,557.05和236.58 kJ·mol^-1并建立了动力学方程;（Y,Gd）₂O₃:Eu³⁺晶粒生长活化能是35.58 kJ.mol^-1,纳米粒子形核过程中的晶粒长大由晶界扩散控制.     

{001}LaAlO_3衬底上沉积YBa_2Cu_3O_（7-x）薄膜的HRXRD研究

采用脉冲激光沉积技术（PLD）在{001}LaAlO3（LAO）衬底上生长YBa2Cu3O7-x（YBCO）薄膜,并通过极图、摇摆曲线以及倒易空间图谱等高分辨X射线衍射技术（HRXRD）对其微结构进行表征。结果表明,YBCO薄膜的晶粒取向主要为{001}YBCO//{001}LAO,〈100〉YBCO//〈100〉LAO,但还有2%的{001}YBCO//{001}LAO,〈110〉YBCO//〈100〉LAO取向。摇摆曲线结果表明,YBCO的面外取向有一定的漫散（宽度为0.75°）;薄膜面内存在90°±0.65°〈110〉孪晶畴结构,主要是由四方到正交的相变过程中较大的局部应力以及〈100〉和〈010〉方向应力差异引起的。     

光电化学响应分析Ni201在中性溶液中形成表面钝化膜的半导体性质

应用光电化学响应法和:Mott-Schottky曲线法,研究了Ni201在500℃空气中生成的氧化膜和在pH值为8.4的中性缓冲溶液中阳极氧化生成钝化膜的半导体性质,分析了Ni201表面钝化膜的结构和组成.Mott-Schottky曲线表明,Ni20l在该中性溶液中生成钝化膜的平带电位约为0.40 V,其在500℃空气中生成的氧化膜的平带电位约为0.15 V,前者的载流子浓度约是后者的34倍.在中性缓冲溶液中生成钝化膜的光电流谱表明,Ni201的结构由内层NiO和外层Ni（OH）₂构成,其带隙宽度分别为2.8和1.6 eV.其中,具有晶体结构的内层NiO的带隙宽度与Ni201在500℃空气中生成的氧化膜的带隙宽度2.4 eV相似.通过光电化学法和Mott-Schottky曲线建立Ni201表面钝化膜的电子能带结构模型,解释了其内层NiO和外层Ni（OH）₂同是p型半导体组成的钝化膜的半导体性质.     

镁合金AZ31表面无铬磷酸盐转化膜的制备、结构及性能

用化学沉积的方法在镁合金AZ31表面获得了无铬、无氟和无亚硝酸盐的环保型化学转化膜。 SEM,\linebreak EDS及XRD分析表明,以磷酸盐和无氟添加剂为主要成分,在镁合金AZ31表面获得了致密、均匀和无网状裂纹的磷化膜。磷化膜厚度为12μm~15 μm,主要物相为MnHPO₄•2.25H₂O, 主要元素成分为O,Mg,P,Mn和Al。磷化后的镁合金AZ31通过中性盐雾测试(NSS),72 h后未见腐蚀现象,浸涂氨基烘漆后的NSS测试达到204 h未见明显腐蚀,结果表明磷化膜具有良好的耐蚀性能。电化学极化曲线测试结果显示, 磷化后镁合金AZ31的E_corr比未处理的正移111 mV,I_corr至少降低了三个数量级,磷化膜通过抑制阳极溶解和阴极析氢过程,有效地提高了镁合金AZ31的耐蚀性能。     

阳极电沉积制备CeO2薄膜

用阳极电沉积技术在304不锈钢基体上制备CeO₂薄膜,用扫描电子显微镜（SEM）和X射线衍射（XRD）等手段探讨不同配体阳离子种类、配体浓度和O₂对镀层表面结构的影响规律。结果表明,CH₃COONH₄配体中的铵离子（NH₄⁺）对CeO₂薄膜晶粒的细化具有重要作用,镀液中高CH₃COONH₄配体浓度及镀液的脱氧作用有利于阳极电沉积CeO₂薄膜的致密化;在镀液组成为0.1 mol/L Ce(NO₃)₃和0.2 mol/LCH₃COONH₄、且镀液脱氧的实验条件下,获得了平整致密的纳米晶CeO₂薄膜,其晶粒粒径范围为5~10 nm。     

(Ti,Al)N涂层应力沿层深分布的调整及大厚度涂层的制备

利用电弧离子镀技术在不锈钢基体上制备了（Ti,Al）N涂层,研究了N₂分压改变对涂层残余应力沿层深分布及相关力学性能的影响.结果表明,低N₂分压下,（Ti,Al）N涂层残余应力沿层深分布较均匀,随N₂分压的增加,涂层应力沿层深呈"钟罩型"分布,且全膜厚的应力值也明显增大;通过对涂层生长结构及微观成分分析,初步探讨了应力分布机理.随N₂分压的增加,涂层硬度会显著增加,而膜/基结合力则大幅下降;采用改变N₂分压工艺制备（Ti,Al）N涂层,可有效调整涂层残余应力沿层深分布趋势,改善其力学性能,并可成功制备厚度在130μm以上的硬质涂层.     

Surface composition and electrochemical behavior of LiNi1/3Co1/3Mn1/3O2 cathode material with copper additive

LiNi_1/3Co_1/3Mn_1/3O₂（NCM） cathode material containing copper was prepared by co-precipitation method.The material was characterized by X-ray photoelectron spectroscopy（XPS） and galvanostatic cycling.XPS data indicate that surface compositions of the samples containing copper are different from the bare NCM.Copper on surface of particles was enriched,while nickel and lithium content was reduced.The electrochemical performance of NCM was affected by the change of surface compositions.Cycling performance charged to the cutoff voltage of 4.6 V was improved by introducing copper into the material.The effects of copper content on electrochemical behaviors of NCM at 4.5 V were discussed.     

电泳沉积法在Ni-W基带上制备YBa_2Cu_3O_(7-δ)超导厚膜(英文)

研究La0.4Sr0.6TiO3(LSTO)缓冲层和YBa2Cu3O7-δ(YBCO)超导厚膜的低成本制备技术。采用X射线衍射分析LSTO和YBCO膜的晶体取向,利用标准四引线法分析LSTO薄膜的导电性能和YBCO厚膜的超导性能。首先采用金属有机沉积法(MOD)成功在Ni-W基带上制备取向较好、表面光滑致密的LSTO缓冲层;然后采用电泳沉积(EPD)技术制备YBCO超导厚膜。研究电泳沉积电压和沉积时间对YBCO涂层性能的影响。结果表明:138V下电泳沉积35 min所制备的YBCO涂层,临界电流密度可达600 A/cm2(0 T,77 K)。     

(NiCoCrAlYSiB+AlSiY)复合涂层热腐蚀行为的研究

采用电弧离子镀（AIP）技术在镍基单晶高温合金基体上制备了NiCoCrAlYSiB涂层（普通涂层）和（Ni-COCrAlYSiB+AlSiY）复合涂层,研究了高温合金基体与2种涂层分别在900和700℃下的涂盐（Na₂SO₄+K₂SO₄和Na₂SO₄+NaCl）热腐蚀行为.结果表明:高温（900℃）热腐蚀条件下,基体合金表面主要生成NiO;普通涂层表面上要生成Cr₂O₃,而且涂层内部出现内氧化和内硫化现象;复合涂层表面主要生成Al₂O₃,外层出现程度较轻的内氧化,涂层表层Al含量仍然较高,维持表面Al₂O₃膜的形成和修复.低温（700℃）热腐蚀条件下,基体合金表面主要生成NiO;普通涂层表面主要生成Cr₂O₃,涂层内部出现严重的内氧化;复合涂层表面也出现了内氧化,高Cr的内层未受腐蚀,有助于提高涂层的抗腐蚀性能.