Inert anodes for AI smelters: Energy balances and environmental impact

This paper assesses the energy and environmental consequences of retrofitting aluminum electrolysis cells with inert anodes. The energy consumption and the CO₂ emissions are calculated based on assumptions of what the cell voltage may be. It is crucial not to ignore the cell voltage increase that may be necessary to maintain the heat balance of the cell, and also the sources of electrical energy that would provide the incremental power. Thus, a global environmental analysis of the impact of retrofitting cells with inert anodes is needed. For more information, contact Halvor Kvande Hydro Aluminium Metal Products, N-0240 Oslo, Norway; +47-22-53-9155; fax +47-22-53-7778; e-mail halvor.kvande@hydro.com.     

The possible reduction of alumina to aluminum using hydrogen

Theoretical considerations based on published thermodynamic data show that condensed aluminum should not be formed by direct reaction between hydrogen and alumina. Nevertheless, laboratory experiments by the authors and observations reported by others in the literature have led to the hypothesis that hydrogen dissolved in molten aluminum can possibly reduce alumina to aluminum at high temperature (700–1,700°C). For more information, contact H. Kvande, Hydro Aluminium, N-0246 Oslo, Norway; telephone 47 22 73 9155; fax 47 22 73 7778; e-mail Halvor.Kvande@hydro.com.     

Effect of bias voltage on microstructure and properties of Ti-doped graphite-like carbon films synthesized by magnetron sputtering

Ti-doped graphite-like carbon (GLC) films with different microstructures and compositions were fabricated using magnetron sputtering technique. The influence of bias voltages on microstructure, hardness, internal stress, adhesion strength and tribological properties of the as-deposited GLC films were systemically investigated. The results showed that with increasing bias voltage, the graphite-like structure component (sp² bond) in the GLC films increased, and the films gradually became much smoother and denser. The nanohardness and compressive internal stress increased significantly with the increase of bias voltage up to −300 V and were constant after −400 V. GLC films deposited with bias voltages in the range of -300--400 V exhibited optimum adhesion strength with the substrates. Both the friction coefficients and the wear rates of GLC films in ambient air and water decreased with increasing voltages in the lower bias range (0--300 V), however, they were constant for higher bias values (beyond −300 V) . In addition, the wear rate of GLC films under water-lubricated condition was significantly higher for voltages below −300 V but lower at high voltage than that under dry friction condition. The excellent tribological performance of Ti-doped GLC films prepared at higher bias voltages of −300--400 V are attributed to their high hardness, tribo-induced lubricating top-layers and planar (2D) graphite-like structure.     

Effects of Ni Content and Solution-Aging Treatment on Multi-Stage Transformations of TiNi Shape Memory Alloys

Effects of Ni content and solution-aging treatment on transformation type and transformation temperature of Ti100-xNix (x=33.3-75) alloys were investigated by differential scanning calorimeter (DSC). The results show that one-stage transformation B2→B19′ of the solution-quenched Ti100-xNix alloys occurs. The martensitic transformation temperature TM is constant at x = 40-49, decreases sharply at x = 49-52, increases gradually at x = 52-56, and is constant again at x = 56-70. The alloys after aging at 773 K for 3.6 ks and 36 ks will have the occurrence of one-stage transformation B2→B19′ at x = 40-50.5, and the TM is constant first and then decreases suddenly with increasing of x; when x = 50.5-52, the alloys have the occurrence of two-stage transformation B2→R→B19′ and the TM decreases gradually with increasing of x; when x=53-70, the alloys have the occurrence of three-stage transformation and the TM1 and TM2 all increase first and then keep constant with increasing of x. All alloys after aging at 773 K for 360 ks have the occurrence of one-stage transformation B2→B19′ except for Ti49Ni51 and Ti47Ni53 alloy, which will have the occurrence of two-stage transformation B2→R→B19′ and three-stage transformation, respectively     

Preparation of ZrO<Subscript>2</Subscript> dielectric layers by subsequent oxidation after Zr film deposition with negative substrate bias voltage

ZrO₂ dielectric layers were prepared by a two-step process, a deposition of pure Zr film with and without a negative substrate bias voltage and a subsequent oxidation of the Zr films. We focused on the effect of the negative substrate bias voltage on the Zr film deposition and the subsequent oxidation of the Zr films. As a result, the Zr film deposited at the substrate bias voltage of −50 V (Vs = −50 V) was found to have a high intensity peak of Zr (100) and a uniform and smooth surface. From the capacitance-voltage and current-voltage measurements of the ZrO₂ films, a high dielectric constant of 21 and the equivalent oxide thickness (EOT) of 2.6 nm were obtained on the oxidation layer of the Zr film deposited at Vs = −50 V. On the other hand, a low dielectric constant of 15 and the EOT of 3.6 nm was obtained on that of the Zr film deposited at Vs = 0 V. The leakage current density of the ZrO₂ film (Vs = −50 V) was 5.69×10⁻⁴ A/cm², and this value was much lower than the 1.21×10⁻⁴ A/cm² for the ZrO₂ film (Vs = 0 V). It was found that the two-step process by subsequent oxidation after film deposition using a negative substrate bias voltage is useful for obtaining high-quality dielectric layers.     

Effect of electrolysis voltage on electrochemical reduction of titanium oxide to titanium in molten calcium chloride

The electrochemical reduction of solid TiO2 directly to solid metal is a ptomising alternative to the current Kroll process. The present work is aimed at studying the effect of electrolysis voltage on the rate of electrochemical reduction. The products of electrochemical reduction of TiO2 and Ti2O were examined using the scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques. The results show that Ti2O was reduced to low valent titanium oxide at 1.5 -1.7 V, which was the result of ionization of oxygen. TiO2 and Ti2O were reduced to titanium metal at 2.1-3.1 V, which was the co-action of ionization of oxygen and calciothermic reduction. The oxygen content decreased rapidly with voltage increasing from 2.1 to 2.6 V, while it changed little from 2.6 to 3.1 V. The optimized cell voltage was 2.6-3.1 V.     

Anomalous photoconductivity of ferrocene

Photoconductivity behaviour of ferrocene, a very useful metallo-organic sandwich compound, has been investigated at different constant temperatures using powdery material in a sandwich type of cell configuration and with the exposure of a polychromatic light source (mercury lamp of 125 W). Measurements with a constant d.c. bias voltage (27 V) across the sample cell and a fixed intensity of the exciting light source have shown a drastic change in the photocurrent versus time profile with the increase in temperature. Anomalous changes have been observed in the plot of the photocurrent versus reciprocal of temperature. Such changes are completely absent in the corresponding dark current behaviour. The photoinduced changes have been observed to be almost reversible in the entire temperature range. In a particular temperature range the reversibility of photocurrent is accompanied by fluctuations in equilibrium current obtained after switching off the light source. The observed anomalous changes in photocurrent have been explained by photoinduced phase transition in ferrocene. The possible origin and implications of this photoinduced phase transition are discussed.     

Mechanical Behaviors of Ti-Si-N Coatings Deposited by Bias Sputtering

Ti-Si-N hard coatings were deposited on steel substrates by reactive unbalanced magnetron sputtering from Ti and Si elemental targets in a mixture of Ar and N2 gases.The influences of negative bias voltage(in the range of-30 to-80 V)on the mechanical properties of the coatings were investigated.In particular,the critical cycle during dynamic impact tests was employed to indicate the bonding strength of the coatings.It was found that the Ti-Si-N coatings prepared at lower constant bias voltages could effectively improve the adhesion and the cyclic impact performance,but their hardness was dropped significantly to 13 GPa at a bias of-30 V.Higher bias voltage values induced greater hardness.A maximum hardness of 47 GPa was obtained at a bias of-60 V.However,the coating adhesion was worse in this case,and the number of impact cycles(～8×10 3)that the coatings could endure was much shorter than that of TiN binary coatings(～2×104).On the other hand,the bias voltage was varied linearly from-40 to-60 V during Ti-Si-N deposition.Under this circumstance,the hardness of the coatings deposited with the bias-graded configuration remained very high(42 GPa),and the adhesion strength was improved substantially.Also,the critical impact cycle could reach as high as 1.8×104.Therefore,bias-graded deposition can provide an effective processing route to prepare Ti-Si-N superhard coatings with high adhesion strength and impact resistance.     

草酸中阳极氧化铝纳米孔洞形成的稳定性(英文)

研究在金属铝阳极氧化过程中外加电压对于纳米阳极氧化铝孔洞形成稳定性的影响。恒定外加电压下的金属铝阳极氧化是制备纳米孔洞阳极氧化铝材料的常用方法。金属铝阳极氧化的实验结果分析主要基于THAMIDA模型和SINGH模型。经分析发现:在pH=0.96的草酸溶液中进行阳极氧化,纳米氧化铝的孔间距与外加电压之间呈线性关系(2.24 nm/V)。此实验规律与THAMIDA模型的预测完全符合。另一方面,氧化铝纳米孔在60V电压以上不稳定形成。SINGH模型能预测此失稳区域的存在。此外,在低电压下(≤30V)阳极氧化铝孔洞亦呈现不稳定形成。但是,现有理论没有预测这类失稳区域的存在。     

Stability of nanopore formation in aluminum anodization in oxalic acid

The effect of applied voltage on nanopore formation stability of porous anodized alumina (PAA) in oxalic acid electrolyte was investigated. The Al anodization at a constant applied voltage is a popular electrochemical method to synthesize PAA templates. The experimental observations of Al anodization are used to compare the predictions of the THAMIDA model for interpore distance and the stability criterion of the SINGH model. It is found that, in the electrolyte of pH = 0.96, the interpore distance—applied voltage has a linear dependence coefficient of 2.24 nm/V, which agrees well with the THAMIDA model. It has also been confirmed that pore formation is instable at above 60 V which can be predicted by SINGH model. A second unstable growth regime below 30 V is also observed, which is not predicted by any of the models.     

直接电解金属氧化物制备CeCo_5合金

在CaCl2熔盐中,以Co3O4和CeO2混合氧化物为原料,采用熔盐电脱氧法制备CeCo5合金。研究电解电压、烧结温度等对电脱氧过程的影响。采用SEM和XRD对不同条件下制备的产物微观形貌和相组成进行表征,并结合动电位极化法,研究电脱氧机理。采用循环伏安法研究材料的电化学性能。结果表明：随着电解电压的升高和烧结温度的降低,电脱氧速度逐渐加快。在850°C下烧结的混合氧化物试样,在3.1V电压下电解,可制备出纯相的CeCo5合金。在电脱氧过程中,Co3O4还原成单质Co,CeO2还原成CeOCl,CeOCl在单质Co表面还原而形成CeCo5合金。所制备的合金表现出良好的电化学循环稳定性。     

薄板高速熔化极脉冲气体保护焊控制及实现

高速焊接条件下容易产生咬边等缺陷,实现大电流低电压的稳定焊接是解决问题的关键,设计一种新型单周期弧压反馈闭环控制系统,在每一个周期内保证电弧电压的平均值相同,可以实现快速稳定的弧长调节.对偶然发生的短路,采用相应的波形控制方式.对脉冲参数进行优化,有效的减小了熔滴尺寸,缩短了弧长.试验表明,该系统具有很强的电弧自身调节能力,相对于传统控制方式,在相同送丝速度条件下工作电压可以降低1～5V.在焊接速度1.3m/min时,仍可以有效地避免产生缺陷,焊缝成形美观,背面熔透均匀,几乎没有飞溅.     

The improvement of high-temperature oxidation of Ti–50Al by anodic coating in the phosphoric acid

The high temperature cyclic oxidation resistance of Ti–50Al can be improved by anodic coating in phosphoric acid aqueous solution (4 wt% H₃PO₄) at 18°C. Sparking occurs sporadically on the surface as the voltage is over 300 V and the instantaneous current density after 45 min of anodization increases with increasing voltage. The anodic films are amorphous and contain substantial amount of phosphorus. Cyclic oxidation test indicates that the anodization can remarkably reduce the oxidation in air at 800°C and the improvement increases with increasing anodizing voltage up to 400 V, at which the parabolic oxidation rate constant can be reduced to about 1/600 of that for as-homogenized Ti–50Al. Raman spectra show that the anodic film can slow down the formation of rutile and α-Al₂O₃ during oxidation. The doping effect of phosphorus ions in titanium oxide accounts for the improvement of high temperature oxidation of Ti–50Al.     

Dielectric characteristics and nonlinear properties of ZnO–polypyrrole composites

The nonlinear properties and frequency characteristics of ZnO–polypyrrole composites were investigated at 200 Hz–5 MHz frequency interval with different zinc oxide contents. Samples were prepared using hot press method at 130 °C. Results show an optimum point for breakdown voltage at ZnO content of 70%. Breakdown voltage decreases from 590 to 380 V and after that tends to increase from 450 to 740 V due to the absence of polypyrrole at grain boundaries. No matter how breakdown voltage behaves, nonlinear coefficient increases from 4.2 to 9 by increasing ZnO content because of the increase in acceptor-like states at grain boundaries by increasing ZnO content. The electrical parameters such as dielectric constant, dielectric loss and series resistance of samples show a strong dependence on frequency especially below 1 kHz. These parameters fall off by increasing frequency up to 1 kHz, which is related to charge transportation through the Schottky barrier at grain boundaries. The high dielectric constant of samples below 1kHz is related to the Maxwell–Wagner polarization at grain boundaries. The presence of different anomalies at different frequency intervals is related to interfacial polarization because of different structures of grains and intergranular layer with a huge difference in conductivity.     

Corrosion Resistance and Color Properties of Anodized Ti-6Al-4V

In this research, color anodizing of Ti-6Al-4V alloy was performed in phosphoric acid solution of 0.4 M concentration and within 30 s in different voltages (10-120 V) of a DC power supply. The effect of anodizing voltages on the color and thickness of anodized layers on Ti-6Al-4V alloy surface was surveyed. Thickness and refractive index of layers were measured by spectrophotometery and reflectance curves. According to the results, thickness of layers increased with increasing anodizing voltage and was in the range of 38-167 nm. Also the refractive index of anodic film was approximately constant at about 2 and increased inconsiderably with increasing anodizing voltage. Corrosion resistance of the anodized samples in 20 and 50 V was surveyed in physiological solutions of Ringer’s solution, Artificial Saliva solution, and Ringer’s + 150 mM H₂O₂ solution at the temperature of 37 °C by potentiodynamic polarization method. The anodized sample in 50 V indicated lower corrosion rate than the non-anodized sample as well as the sample which was anodized in 20 V in all solutions. The non-anodized sample indicated the highest corrosion rate of about 0.25 μA cm⁻².     

不同电压下镁合金的微弧氧化行为

为了解电压在镁合金微弧氧化中的作用,本工作在双极性脉冲电源的恒流加载方式下,通过考察电压对氧化时间、膜层厚度及表面形貌的影响,研究电压对微弧氧化机理的影响。结果发现,当负电压为零,占空比20%和30%时,电压低于380V时所需的氧化时间要短于电压高于380V时的氧化时间。当占空比30%,负电压为零和40V时,电压低于340V的氧化时间和膜层增长速率都小于电压高于340V的;电压低于340V时的膜层表面形貌优于340V以上膜层。可见,微弧氧化过程中存在一个临界电压,微弧氧化过程分成两种情况,两种情况的微弧氧化机理不尽相同。     

梯度基体负偏压真空多弧离子镀沉积TiN涂层及其力学性能

目的通过梯度基体负偏压沉积工艺,获得综合性能优良的Ti N涂层。方法采用多弧离子镀工艺,在0~-180 V连续变化的梯度基体负偏压参数下沉积梯度Ti N涂层。通过X射线衍射仪和扫描电子显微镜对涂层的物相结构和形貌进行分析,通过纳米压痕和纳米划痕对涂层的力学性能进行系统研究。结果与无梯度沉积的涂层相比,梯度基体负偏压沉积Ti N涂层的(111)晶面衍射峰减小,厚度增加,表明涂层的沉积速率增大。经测试,梯度涂层的断裂临界载荷L_(c2)=215.21 m N,硬度值H=31.2GPa,弹性模量E=498 GPa,塑性变形临界载荷L_y=81.65 m N;无梯度沉积涂层的L_(c2)=248.63 m N,H=29.6 GPa,E=452 GPa,L_y=23.39 m N。二者相比之下,梯度涂层虽然断裂临界载荷有所减小,但硬度值和弹性模量均有所增大,并且塑性增大,塑性变形临界载荷大幅增加,综合力学性能提高。结论梯度基体负偏压沉积工艺改变了常规的单一参数设置,在沉积过程中,基体负偏压对涂层生长的影响不断改变,获得的涂层具有结构上的梯度变化,从而力学性能得到了改善。     

恒电位对TiN涂层在人工海水环境中腐蚀磨损的影响

目的研究不同恒电位对TiN涂层在人工海水环境中腐蚀磨损行为的影响。方法用多弧离子镀系统在316不锈钢上沉积TiN涂层。通过XRD测试、纳米压痕硬度测试、膜基结合力测试、电化学工作站测试、不同恒电位下磨蚀实验和涂层的磨痕截面轮廓测试,分别评价TiN涂层的相结构、硬度、结合力、电化学性能、摩擦系数、磨损率,并通过扫描电子显微镜对涂层表面形貌、截面形貌和磨痕形貌进行分析。结果在摩擦条件下,TiN涂层的开路电位随着滑动摩擦时间的增加而逐渐降低。TiN涂层在不同恒电位(-1V、-0.5 V、OCP、0 V)下滑动摩擦,平均摩擦系数分别为0.392,0.416、0.324、0.348。磨损率分别为1.8117×10-6、3.1123×10-6、4.5958×10-6、7.7724×10-6 mm3/(N·m)。在0.5 V下,涂层被磨穿。TiN涂层在人工海水环境中的主要腐蚀磨损破坏机制为磨粒磨损和疲劳点蚀。结论提高加载电位,涂层的磨损量和磨损率同步增大。在-1、-0.5 V,OCP下,由腐蚀促进磨损的损失量占TiN涂层损失总量的比重逐渐增大,依次为0%、41.78%、61.77%。在0 V时,TiN涂层产生了由磨损促进腐蚀的损失量,占TiN涂层损失总量的比例为6.1%。     

Charge transport properties of an organic solar cell

The electronic properties of ITO/PEDOT-PSS/P3HT-PCBM/LiF/Al organic solar cell have been investigated using current-voltage and capacitance-voltage techniques. The electrical parameters like ideality factor n, series resistance R_s and barrier height ?_b, have been extracted using current-voltage and capacitance-voltage techniques. The photovoltaic parameters such as open circuit voltage V_oc, short circuit current I_sc and fill factor FF were determined from current-voltage characteristics of the solar cell under illumination. The ideal value than unity for the organic solar cell indicates the presence of non-ideal behaviour. The barrier height of the solar cell is found to be dependent both temperature and applied voltage and the model of Gaussian distribution of the barrier height was presented for explaining their anomalous behaviour. The standard deviation of the barrier height distribution σ_o indicates the presence of interface inhomogeneities. The ideality factor n, open circuit voltage V_oc, short circuit current density J_sc, fill factor FF and Richardson constant A* values for the organic solar cell were found to be 2.29, 0.58 V, 5.84 mA/cm², 0.31 and 10.41 A/cm² K², respectively.     

Influence of vibration on micro-tool fabrication by electrochemical machining

Recent trend in societies is to have micro products in limited space. Efficient micromachining technologies are essential to fabricate micro products which in turn will be helpful in saving material, energy and enhancing functionality. For micromachining, micro tool is very much essential. This paper is aimed at finding the most suitable and quickest method of micro tool fabrication by electrochemical machining. Tungsten micro tools were fabricated at different machining conditions to know the influences of voltage, frequency of tool vibration, amplitude of vibration of tungsten tool, concentrations of electrolyte and dipping length of tool inside the electrolyte. Fabrication of uniform diameter of micro tool is possible at each applied voltage starting at 2 V to higher volt utilizing vibration with appropriate amplitude. Good quality micro tools with different shapes can be fabricated by controlling a proper diffusion layer thickness within a very short time introducing the vibrations of micro tool. Finally, the fabricated micro tools were applied for machining precise micro holes and micro channel using electrochemical micromachining (EMM).