STUDIES ON THE KINETICS OF Ni DISSOLUTION IN AQUEOUS AMMONIACAL SOLUTION

研究了Ni在氨-碳酸铵溶液中有氧存在下的溶解动力学. 结果表明Ni的溶解过程主要是电化学溶解过程,但尚有Ni的氧化伴生.反应速度为氨控制区或氧控制区,这与氨和氧的浓度之比有关. 在NH_3控制区Ni表面易钝化生成氧化膜,并停止溶解;在氧控制区,Ni的溶解速度为氧在液膜中的扩散所控制,可由氧传递速度方程来表达.     

Use of ferricyanide for gold and silver cyanidation

Low gold and silver leaching kinetics has been commonly observed in traditional gold-silver cyanidation process, especially in heap leaching and in situ leaching operations. The different mineralogy of gold and silver in the ores is suspected to be the main reason, e.g., the occurrence of low solubility acanthite (Ag2S) typically results in low overall silver extraction. Due to the low solubility of oxygen in cyanide solution, the reactivity and availability of oxidant is believed to be the critical limitation for gold and silver dissolution. The use of ferricyanide as the auxiliary oxidant for gold and silver cyanidation has been examined. The rotating disc test results prove the assistant effect of ferricyanide on increasing the dissolution rate of gold and silver. The potential use of ferricyanide in gold/silver cyanidation process is proposed based on the leaching results of actual ores.     

气氛及微量元素对Ag／W润湿性的影响

用座滴法研究了Ag/W在真空,Ar,H_2及3H_2+N_2气氛下的润湿角及其与温度的关系,并进行了表面及界面分析。结果表明,气氛中的氧分压是影响Ag/W润湿角的主要因素。微量的Ni,Cu,Ce元素可以显著提高Ag/W润湿性,使熔点附近的润湿角从69°降低至10°—20°。     

EFFECTS OF ATMOSPHERE AND TRACE ELEMENT ON THE WETTABILITY OF SOLID W BY LIQUID Ag

The contact angle of liquid Ag with solid W and its temperature dependance wereexamined by sessile drop method under various atmospheres,e.g.vacuum,Ar,H_2 andcarcked NH_3.The O_2 partial pressure in the atmosphere is found to be the major factor.An obvious improvement on the wettability may be made by a trace amount of Ni,Cu orCe added to liquid Ag,The contact angle near M.P.is then narrowed from 69 to about10—20 deg.     

Fe—Ni—Cr封接合金的高温氧化及氧化膜,氧化物晶须的结构

试验表明,Fe-Ni-Cr封接合金在高温湿氢气氛中氧化膜的生长受扩散控制,其主要组成为刚玉型的Cr_2O_3与尖晶石型的(Fe,Mn)O·Cr_2O_3。电子衍射及能谱分析证实,氧化过程中生长的晶须为(Fe,Mn)O·Cr_2O_3。     

炮膛残留铜垢清除的研究

应用化学热力学理论对清除铜垢机理进行了论证：铜能被强氧化剂Na2S2O3氧化成铜离子，铜离子又与NH3生成稳定的[Cu(NHs)3]4^2 络离子；缓蚀剂(NaNO2)的存在可以使炮管材料不发生腐蚀。同时进行了实验验证。     

HIGH TEMPERATURE OXIDATION AND STRUCTURE OF SCALE AND WHISKERS FOR Fe-Ni-Cr SEALING ALLOYS

The oxidation rate,the growth,morphology and structure of oxide scale and whiskers forFe-Ni-Cr sealing alloys in H_2-H_2O atmosphere at high temperatures have been studied.The growth rate of scale is controlled by diffusion.The scale is composed of Cr_2O_3 andspinel(Fe,Mn)O·Cr_2O_3 and the oxide whisker,are spinel(Fe,Mn)O·Cr_2O_3.     

硼酸钠浓度对镁合金阳极化的影响

采用电压-时间曲线、全浸腐蚀实验、极化曲线法、X射线衍射法（XRD）、扫描电镜（SEM）、能量色散谱仪（EDS）和X射线光电子能谱法（XPS）等方法研究了AZ91D镁合金在含不同浓度四硼酸钠的阳极化溶液中的阳极氧化行为和膜层的成分、结构.结果表明：在文中给定工艺中,AZ91D镁合金的阳极化过程可分为3个阶段：电火花出现之前的致密层生成阶段;少量小电火花出现的多孔层生成阶段;出现较大电火花的多孔膜层稳定生长阶段.阳极氧化过程中,随着阳极氧化溶液Na2B4O7浓度的升高,出现电火花的时间延长,出现电火花时的电压值升高;膜层厚度增加,膜层上的孔径增大.阳极化膜层中主要含有Mg^2＋、O^2-、Si^4＋和B^3＋,主要相结构为MgO、MgSiO3和Mg3B2O6.四硼酸钠浓度对阳极化膜的耐蚀性影响较大,当四硼酸钠浓度为160 g/L时,膜层耐蚀性能最好.     

A STUDY OF THE STRESS CORROSION CRACKING OF SENSITIZED 1Cr18Ni9Ti STAINLESS STEEL IN HIGH TEMPERATURE HIGH PRESSURE WATER

从环境角度研究了敏化1Cr18Ni9Ti不锈钢在高温水中的腐蚀行为.研究指出,在一定浓度Cl~-和(或)O_2存在情况下,在酸性和中性高温高压水中都会出现应力腐蚀破裂.断口电子金相表明,在氯离子为主的环境中,破裂系晶间型;在氧为主的环境中,破裂系以解理为主的混合型.给出了1Cr18Ni9Ti在高温水中腐蚀的表观和真实动力学曲线,表明腐蚀包含溶解和湿氧化两部分,而以湿氧化为主.借Mossbauer内转换电子谱研究了氧化膜结构与腐蚀的关系,指出在一般腐蚀条件下,膜的主要组分为Fe_3O_4,而在应力腐蚀条件下,膜的主要组分为Fe_2O_3,并且系Fe_2O_3和Fe_3O_4多层重叠结构.当水中添加了一定量的硼,在氧化膜中会局部出现FeBO_3相,既不会引起也不会抑制应力腐蚀.硼的这种“惰性”作用和膜结构中Fe_3O_4相的非化学计量比,膜具有阴离子选择性有关.根据腐蚀电化学,认为应力腐蚀系发生在钝化/过钝化区域,增高Cl~-或O_2含量,从不同角度都会使合金的电位接近过钝化区.Cl~-的作用在于改变阳极极化曲线,O_2的作用在于改变阴极极化曲线.在含Cl~-水中,晶界TiC的迅速溶解是应力腐蚀的主要原因,而在含氧水中,晶粒Fe-Cr-Ni中Cr的选择性溶解是应力腐蚀的主要原因.在分析应力腐蚀的特征后,指出应力既是某些严重腐蚀点形     

Al2O3和Cr过渡层对Ag膜光学性质及其附着力的影响

研究了在玻璃基底上镀制Al2O3和Cr过渡层对Ag膜反射率及附着力的影响.分光光度计测试了Ag膜的反射率,结果表明,与Cr过渡层相比,Al2O3过渡层对Ag膜反射率的降低相对较小;而且,随着Al2O3厚度的增加,Ag膜的反射率先增大后减小.XRD与AES测试表明,引入Al2O3或Cr可明显细化Ag晶粒,减弱Ag膜(111)织构;Al2O3作过渡层时,Al原子向Ag层中扩散显著;而Cr作过渡层时,只有少量Cr原子扩散进入Ag层.因此,Al2O3作过渡层能显著增强薄膜与玻璃基体之间的附着力.     

Comparison Study on the Semiconductive and Dissolution Behaviour of 316L and Alloy 625 in Hydrochloric Acid Solution

The corrosion behaviour of 316 L and Alloy 625 was investigated using cyclic polarization,electrochemical impedance spectroscopy,X-ray photoelectron spectroscopy,Auger electron spectroscopy and induced coupled plasma-optical emis sion spectrometer.The results indicated that Alloy 625 showed better corrosion resistance than 316 L and the prolonging immersion time could enhance corrosion resistance of the two alloys.The passive film formed on the surface of 316 L exhibited an electronic structure of p-p heterojunction,with Fe_3 O_4 and Cr_2 O_3 enriched in the outer and inner layers,respectively.However,Alloy 625 presented the electronic structure of n-p heterojunction dominated by the outer Fe_2 O_3/NiFe_2 O_4 and inner Cr_2 O_3.This resulted in the opposite semiconductive properties of the passive films formed on the two materials.In the acid solutions,Fe and Mo suffered from selective dissolution while Cr and Ni were relatively stable.The corrosion rates were mainly dominated by the dissolution of iron.Alloy 625 presented better corrosion resistance than 316 L due to the obviously lower content of Fe and the higher content of Cr and Ni in the passive film.The continuously selective dissolution of iron resulted in the increase in Cr/Fe ratio in the passive film,which was responsible for the enhancement in corrosion resistance.     

铁锰多金属矿综合利用新工艺

以生物制剂KZSH01作为还原剂与铁锰多金属矿发生氧化还原反应,研究了铁锰矿的细度和还原剂的含量对还原效果的影响,考察了还原过程中温度和物相的变化,探讨了H2SO4用量对Mn和Zn浸出效果的影响.结果表明:生物还原剂KZSH01可使铁锰矿中93.0%MnO2转化为MnO,90.0?2O3转化为Fe3O4;Mn和Zn的浸出率均大于90.0%;Fe的磁选回收率大于85.0%,79.0%Pb和82.5%Ag富集在渣中.     

Valence variation of arsenic in bioleaching process of arsenic-bearing gold ore

The concentration and variational trend of As3+ and As5+, the bacterial resistance for the As3+ and As5+ and converting conditions from As3+ to As5+ were analyzed. The additive was used to prompt the bacterial leaching efficiency by changing valence state of arsenic. The results show that the concentration of As3+ is larger than that of As5+ in the lag phase. The concentration of As3+ decreases in the log phase, and is lower than that of As5+. HQ-0211 typed bacteria express better resistance for As3+ and As5+ and remain growing when the concentrations of As3+ and As5+ are above 6.0 g/L and 12.0 g/L, respectively. It is found that Fe3+ cannot oxidize As3+ singly as strong oxidant in the leaching system, but can cooperate with pyrite or chalcopyrite to do that. The oxidation of As3+ is prompted with addition of H2O2. The bacterial activity is improved in favor of bacterial leaching efficiency. NaClO restrains the bacterial growth to depress leaching efficiency because of the chloric compounds affecting bacterial activity.     

氧化锌贫矿提锌渣中铅和银的氯盐一步浸出

运用X射线衍射、扫描电镜和X射线能谱等分析手段,对山东某地深度氧化锌贫矿提锌后渣进行工艺矿物学特征分析可知,矿物中金属赋存状态复杂,属难选矿物。开发出氯盐一步法浸出铅和银的新工艺,考察反应温度、NaCl浓度、添加剂用量、液固比、HCl加入量和浸出时间对浸出过程的影响。结果表明:加入添加剂对铅的浸出率没有影响,但可以显著提高银的浸出率。条件试验研究得出最佳工艺条件如下:浸出温度90℃、NaCl浓度390 g/L、添加剂用量15 mL、液固比(质量比)7?1、HCl加入量3 mL、浸出时间3 h。在此最佳工艺条件下,铅的浸出率达到95%左右,银的浸出率达到90%左右。     

Determining the partial currents of silver ionization, its oxide formation, and chemical dissolution by multicycle chronoammetry with an RRDE

A multicycle chronoammetry with a rotating disc electrode with a ring (RRDE) enables one to experimentally discriminate between the partial currents of the substrate metal ionization, anodic formation of the oxide, and chemical dissolution of the oxide in the summary polarization current of the disc. The technique is approved by an example of Ag|Ag₂O|OH⁻(H₂O) system. In a range of relatively small anodic potentials of the Ag disc (0.48 to 0.51 V), the active dissolution of silver at the open surface sites and via pores in the surface film dominates; the phase formation current and, accordingly, the current efficiency of the process rapidly drop. At the potentials of the voltammogram maximum (0.52 to 0.53 V) when the silver active dissolution current is suppressed, the phase formation currents prevail and substantially exceed the chemical dissolution rate of the oxide. The thickness of an Ag₂O film rapidly increases under these conditions, and the current efficiency of the oxide formation is close to 100% for the whole polarization period. The rate constant of the chemical dissolution of an Ag(I) oxide is practically independent of the anodic phase-formation potential, but slightly depends on the oxide film thickness, reflecting changes in the film structure and, possibly, in its composition, from AgOH to Ag₂O. Original Russian Text ? D.A. Kudryashov, S.N. Grushevskaya, A.V. Vvedenskii, 2008, published in Zashchita Metallov, 2008, Vol. 44, No. 3, pp. 321–330.     

Ce对Fe-Cr合金高温氧化行为的影响

Fe-15Cr 和 Fe-30Cr 合金在1000至1200℃空气中氧化时,表面富铁氧化伤的发展导致保护性Cr_2O_3层衰退,氧化速率增大。添加 Ce 可延迟衰退过程的发生,从而大幅度减低氧化速率。随氧化温度和合金成份变化,Cr_2O_3层衰退的开始时间和发展特征随之改变,Ce 对氧化行为的影响因而呈现出规律性的变化。研究发现,合金中 Cr 的内氧化使 Cr_2O_3层形成小舌包卷合金并使其氧化成富铁氧化物。这是Cr_2O_3层衰退的原因之一。含 Ce 合金中 Ce 的优先内氧化则降低自氧化层进入合金的氧浓度,抑制Cr 的内氧化。氧浓度降低还能促进 Si 的内氧化物在氧化层/合金界面集聚。     

Dissolution of lateritic nickel ore using ascorbic acid as synergistic reagent in sulphuric acid solution

The dissolution of nickel and cobalt from Caldag lateritic nickel ore using the combination of sulphuric and ascorbic acids was investigated. The use of other organic acids, namely citric, maleic and stearic acids, as synergistic reagents was studied for comparison. The results revealed that the use of ascorbic and citric acids markedly improved the dissolution of cobalt compared to the other two organic acids that only showed slight synergistic effect on the leaching rate. In terms of nickel dissolution, ascorbic acid is the most effective synergist, followed by citric, maleic and stearic acids in descending order. Under the most optimized conditions found in this study, i.e., using 1 mol/L of sulphuric acid with the presence of 4 g/L of ascorbic acid at 80 °C and solid-to-liquid ratio of 1/10, more than 99% and 98% leaching rates of cobalt and nickel, respectively, can be achieved within 4 h of leaching. In addition, the leaching performance is relatively insensitive to the change of ascorbic acid concentration from 2 to 4 g/L which is highly desirable from operational perspective.     

YBa2Cu3O7—x—Ag界面与表面的研究

使用XRD,SEM-EDX和LAS-3000联合谱仪研究了YBCO-Ag界面与表面。结果表明,YBCO体内掺0.4 mol Ag对123结构无影响.Ag偏聚在晶界上使晶粒间变得明显清晰;AES分析指出Ag偏聚在表面上,降低了YBCO-金属导线的接触电阻.实验还证实,不论掺入的原料是单质(Ag粉)还是化合物(Ag_2O,AgNO_3),经高温退火处理,Ag总是以单质形态固溶和偏聚在晶界及表面上,由于Ag的室温电阻率很小,有利于增强超导颗粒间的连通性。     

STUDY OF INTERFACES AND SURFACES OF YBa_2Cu_3O_(7-x)-Ag

Interfaces and surfaces of YBa_2Cu_3O_(7-x)(YBCO)-Ag have been studied by SEM-EDXand AES.No effect of Ag on 123 structure in X-ray diffraction pattern was observedfor 0.4 mol Ag doped YBCO.AES analysis indicated that Ag segregated on surfaceof YBCO and resulted in decrease of YBCO-metal lead resistance.In addition,solutionand segregation of Ag as elemental state were often appeared on interfaces and surfacesof high temperature annealed YBCO,whether elemental Ag or compound Ag_2O andAgNO_3 adopted as doping material.     

FeCl3浸取含Au复杂硫化矿的动力学研究

研究了FeCl_3溶液浸取复杂含金硫化精矿中有价金属Cu,Ag,Pb和Zh的过程,考察了主要过程参量对浸取速率的影响.实验数据用非线性回归方法处理,给出动力学模型,说明精矿中Cu的溶解过程由表面化学反应控制,其速率是Fe~(3+)的0.5级和Cl~(-)的零级反应.实验条件下Cu,Ag,Ph和Zn的最终浸取率分别达到96,95,90和91%,超过90%的Fe进入浸取液,总硫的70%以上转化为元素硫,而Au的浸取率则小于3%表明FeCl_3溶液浸取是含Au复杂硫化精矿预处理并回收有价金属的有潜力的方法