2010年何去何从?

2009年对有色行业来说注定是多事之年。全球爆发的金融危机迅速演变成资金链断裂的企业陷入经营困境的一场噩梦。同时,也给企业带来了新的机会,于是就出现了2009年中国有色海内外并购的热潮。     

Fe-15Ce合金在H2-CO2、H2-H2S及H2-H2S-CO2气氛下的腐蚀

研究了600℃时Fe-15Ce合金在H2-CO2、H2-H2S及H2-H2S-CO2 3种气氛中的腐蚀行为，Fe-15Ce合金腐蚀后发生了Ce的内氧化或形成了复杂的腐蚀产物膜，而未出现Ce的选择性氧化或硫化，这主要是合金中存在着两相及Ce在Fe中极低的溶解度的结果。Fe-15Ce合金在本实验条件下的氧化-硫化腐蚀速度低于相同温度、压力下的纯硫化。     

VQ2(Q=H, D, T)热力学氢同位素效应的理论研究

基于量子力学第一性原理,采用赝势平面波函数与密度泛函结合的方法,计算并研究V、VH2、VD2、VT2体系的晶格动力学特征及热力学函数,采用热力学方法分析钒吸氢生成VQ2(Q=H,D,T)的热力学同位素效应。晶格动力学性质研究表明,VQ2的热力学同位素效应主要是氢同位素在钒晶格中的振动频率不同导致的。VQ2生成反应在10～1000K的温度范围内标准吉布斯自由能变由-50kJ·mol-1近似线性上升至140kJ·mol-1。平衡压力与温度关系表明,在高于常温的条件下,平衡压力随温度急剧升高;钒吸附氢同位素生成二氢化钒在整个温度范围内均表现为负同位素效应。     

Hydrothermal conversion of Ti-containing minerals in system of Na<Subscript>2</Subscript>O–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>–CaO–TiO<Subscript>2</Subscript>–H<Subscript>2</Subscript>O

Titanium has a great effect on the digestion of bauxite in the Bayer process because it reacts readily at high temperatures in alkaline sodium aluminate solution. Under this consideration, the hydrothermal conversion of Ti-containing minerals in the system of Na₂O–Al₂O₃–SiO₂–CaO–TiO₂–H₂O with increased temperatures was studied based on the thermodynamic analysis and systematic experiments. The results show that anatase converts to Al₄Ti₂SiO₁₂ at low temperatures (60–120 °C), which is similar to anatase in crystal structure. As the temperature continues to rise, Al₄Ti₂SiO₁₂ decomposes gradually and converts to Ca₃TiSi₂(Al₂Si_0.5Ti_0.5)O₁₄ at 200 °C. When the temperature reaches 260 °C, CaTiO₃ forms as the most stable titanate species for its hexagonal closest packing with O^2? and Ca²⁺. The findings enhance the understanding of titanate scaling in the Bayer process and clarify the mechanism of how additive lime improves the digestion of diaspore.     

H2S应力腐蚀试验用H2S气通设计

在满足H2S应力腐蚀试验的试验条件下,设计了H2S应力腐蚀实验室中H2S气体的通气装置.设计方案切实易行,安全可靠;实现了出口H2S气体的吸收再利用,减少了对环境的污染.     

H2S分压对油管钢CO2/H2S腐蚀的影响

1974-）,男,硕士研究生,研究方向为腐蚀与防护.〖ZK)〗 Tel：0379-4231846〓E-mail：FQ)〗〖HT〗〖HJ〗〖HT5”SS〗 〖JZ(〗〖HT2H〗〖STHZ〗〖WTHZ〗 采用高温高压釜,辅以失重法和扫描电镜,对不同H2S分压下(1.4 kPa,20 kPa,60 kPa,120 kPa)油管钢N80、P110的CO2/H2S腐蚀进行了研究.结果表明,在试验H2S分压范围内,随着H2S分压的升高,两种钢的腐蚀速率先增后降,且都在H2S分压为20 kPa时取得最大值.      

Synthesis and crystal structure of an organic-inorganic complex [Cu（DMF）3（H2O）2]2[SiMo12O40]·2H2O

The synthesis and crystal smacture of an polyoxometalate-based organic-inorganic complex [Cu（DMF）3（H2O）212[SiMo12O40].2H2O （DMF = N, N-dimethyl formamide） is described in this article. It was characterized using elemental analysis, thermal analysis, infrared, ultraviolet, and electron spin resonance spectroscopic studies. The X-ray crystallography analysis showed that the copper centers are pentacoordinated to show the square pyramidal geometry, and the polyanion [SiMo12O40]4- which is semi-coordinated to the copper（I/） centers prevents the existence of a sixth ligand. In addition, the intracationic hydrogen interaction enhanced the stability of the copper coordination cation.     

Sulfidation—oxidation behavior of alloy 800H in SO2-O2 and H2-H2S-CO-CO2 atmospheres

The high-temperature-corrosion behavior of alloy 800H has been studied in an oxidizing (SO₂–O₂, =0.23 atm, =1.9×10^–29 atm) and a reducing (H₂–H₂S–CO–CO₂–N₂, =1.5×10^–18 atm =4.3×10^–8 atm, a_c=0.03) sulfidizing environment, at 750°C and 850°C, respectively. When corroded in SO₂–O₂, the protective chromia scale which developed on the alloy in the early stages cracked and spalled in quite a short time period. This led to the growth of iron and nickel sulfides beneath the chromia layer, causing more chromia spallation. When correded in H₂–H₂S–CO–CO₂–N₂, the alloy exhibited breakaway corrosion in about 35hr, at which stage liquid nodules formed on the sample surface. The nodules were studied in detail and were found to consist of three layers. The growth mechanism of such nodules is proposed.     

310不锈钢在H2S／H2／CO2混合气氛中的高温腐蚀

３１０不锈钢在０．４％Ｈ２Ｓ／Ｈ２／７％ＣＯ２的混合气氛中于６００℃发生硫化腐蚀，前５０ｈ的腐蚀遵抛物线规律，延长至２５０ｈ的腐蚀其增重低于抛物线增长，这一转变对应于内层铬硫化物由分散的颗粒态生长成为连续层。     

PHASE DIAGRAMS OF THE BINARY SYSTEMS TbCl_3-MCl_n(M=Li,Mg,Ca,Pb;n=1 or 2)

The phase diagrams of the binary systems RECl_3-MCl_n(M=Li,Mg,Ca,Pb;n=1 or 2)were investigated bymeans of DTA and X-ray diffraction analysis.It was found that they are of simple eutectic type with eutectic points50.1 Mol.-% TBCl_3(445℃),67.5Mol.-% TbCl_3(589℃),65.9Mol.-% TbCl_(563℃)and 35.6 Mol.-%TbCl_3(445℃)respectively.Unstable compounds,formed in the solid slate,are MgTbCl_7,CaTb_2Cl_8,LiTb_2Cl_7 andPbTbCl_5.Their decomposition temperatures are 388℃ with a phase transition at 352,500 and 521℃ with a phasetransition at 483 and 405℃ respectively.Some rules of the phase diagrams were explored.     

Densification Kinetics of CeO<Subscript>2</Subscript> Reinforced 8 Mol.% Y<Subscript>2</Subscript>O<Subscript>3</Subscript> Stabilized ZrO<Subscript>2</Subscript> Ceramics

The grain growth kinetics of 8YSZ ceramics processed using spark plasma sintering (SPS) has been investigated in the temperature ranging from 1100°C to 1500°C. The activation energy during SPS densification was obtained as 332 kJ/mol with grain boundary diffusion as a dominant mechanism. Further, the effect of CeO₂ on the densification kinetics of 8YSZ ceramic processed via SPS and conventional sintering (CS) has been delineated. The lower grain boundary mobility of CS-processed composites (an order of magnitude lower than SPS) is attributed to the solute drag and lattice distortion mechanism. However, no significant change in the grain boundary mobility was observed with CeO₂ addition (~?14.7–43.9?×?10^?18 m³/N/s for CS and 107.2–116.7?×?10^?18 m³/N/s for SPS) revealing that the defect concentration is nearly constant in 8YSZ. The study highlights the effect of sintering techniques (SPS and CS) and reinforcement (CeO₂) on engineering the desired microstructure of 8YSZ ceramic.     

ZrB₂含量对Nb-Mo-ZrB₂复合材料氧化行为的影响

利用热压烧结法,在2400℃烧结温度下,制备了NbMo固溶体（此后记作(Nb,Mo)ss）基陶瓷颗粒增强复合材料。其中,ZrB2陶瓷增强相的体积分数分别为15%,30%,45%和60%。本文研究了在800℃,1000℃和1200℃下,ZrB2含量对复合材料抗氧化性和氧化产物演变的作用。试验结果表明,氧化温度和ZrB2含量均对复合材料的氧化行为有影响。从氧化速率常数角度讲,ZrB2-(Nb,Mo)ss复合材料的抗氧化性随ZrB2含量的增加而提高,随氧化温度的提高而降低。800℃-1000℃的氧化产物中含有膜状Nb2Zr6O17相,能作为屏障阻止氧气向基体扩散,因此在800℃-1000℃时,复合材料氧化速率较低。然而,在1200℃氧化时未发现Nb2Zr6O17相,MoO3的剧烈挥发和ZrO2的体积效应破坏了Nb2Zr6O17保护层,导致了氧化层严重剥落,材料的抗氧化性极差。综上,本文结合观察到的氧化产物形貌,详细阐述了不同ZrB2含量的复合材料在不同温度下的抗氧化机制。     

The Corrosion of Titanium Aluminides in H2/H2S/H2O Atmospheres at 800–1000°C

The corrosion behavior of three Ti–Al intermetallics containing 20, 30, and 40 wt.% Al was studied over the temperature range 800–1000°C in a H₂/H₂S/H₂O gas mixture. Ti–20Al and Ti–40Al alloys had the single-phase structure of Ti₃Al and TiAl, respectively, while Ti–30Al was a two-phase mixture of Ti₃Al+TiAl. The corrosion kinetics followed the parabolic rate law in all cases, regardless of temperature and alloy composition. The parabolic rate constants increased with increasing temperature, but decreased with increasing Al content. The Ti–40Al alloy exhibited the best corrosion resistance among all alloys studied. The scales formed on Ti–Al intermetallics were heterophasic and duplex, consisting of an outer-scale layer of pure -TiO₂ and an inner layer of -TiO₂ with minor amounts of -Al₂O₃ and Ti_l-xS. The amount of -Al₂O₃, which increased with increasing Al content, is responsible for the reduction of the corrosion rates as compared with those of pure Ti oxides.     

Impact of supporting electrolytes on the stability of TiO<Subscript>2</Subscript>–Ti counter electrode during H<Subscript>2</Subscript>O<Subscript>2</Subscript> electrogeneration

This work focuses on the role of common supporting electrolytes (SEs) in the electro-chemical inertness of Ti-based materials employed for the anodic (direct) oxidation coupled with H₂O₂ electro-generation at the graphite cathode for the concurrent decomposition of organic contaminants. SEs are added to boost up the ionic conductivity of solution but a question always remains on the effect of SEs on the stability of anode materials. The use of ClO ₄ ^? is encouraged in the electro-Fenton process as it does not form complexes with Fe²⁺/Fe³⁺; however, it is found that ClO ₄ ^? corroded the TiO₂ coated Ti (TiO₂–Ti) anode very fast (>60 min) and, Ti⁴⁺ ions formed a yellow color complex (λ_max = 380 nm) with H₂O₂. The influence of Cl^–, NO ₃ ^? and SO ₄ ^2? was insignificant on the stability of TiO₂–Ti. The cell current efficiency of H₂O₂ formation dropped sharply with in the case of TiO₂–Ti anode. The TiO₂–Ti corrosion also reduced the mass transfer co-efficient of DO transport from bulk to the cathode surface because of Ti⁴⁺ adsorption on graphite.     

The corrosion behavior of Fe-Al alloys in H2/H2S/H2O atmospheres at 700–900°C

The corrosion behavior of five Fe-Al binary alloys containing up to 40 at. % Al was studied over the temperature range of 700–900°C in a H₂/H₂S/H₂O mixture with varying sulfur partial pressures of 10^–7–10^–5 atm. and oxygen partial pressures of 10^–24–10^–2° atm. The corrosion kinetics followed the parabolic rate law in all cases, regardless of temperature and alloy composition. The parabolic rate constants decreased with increasing Al content. The scales formed on Fe-5 and –10 at.% Al were duplex, consisting of an outer layer of iron sulfide (FeS or Fe_1–xS) and an inner complex scale of FeAl₂S₄ and FeS. Alloys having intermediate Al contents (Fe-18 and –28 at.% Al) formed scales that consisted of mostly iron sulfide and Al₂O₃ as well as minor a amount of FeAl₂S₄. The amount of Al₂O₃ increased with increasing Al content. The Fe 40 at.% Al formed only Al₂O₃ at 700°C, while most Al₂O₃ and some FeS were detected at T800°C. The formation of Al₂O₃ was responsible for the reduction of the corrosion rates.     

H2S腐蚀的控制

本文总结了H2 S腐蚀控制的常用方法 (包括耐蚀材料的应用、腐蚀介质的处理、保护性覆盖层的使用等 ) ,对从事H2 S腐蚀控制的工作者有一定的参考作用     

MAl2B2O7:Re(M=Ca,Sr,Ba;Re=Eu3+,Tb3+)在VUV激发下的发光性能

采用高温固相法合成了MAl2B2O7:Re(M=Sr,Ba,Ca;Re=Eu3+,Tb3+)系列样品.BaAl2B2O7:Eu3+在130～170 nm和200～250 nm区域有两个很强的吸收带;130～170 nm的宽带是硼氧和铝氧基团的吸收,位于200～250 nm附近的吸收带主要是Eu3+-O2-电荷转移态的吸收;MAl2B2O7:Eu3+(M=Sr,Ba)中Eu3+占据更多的是非对称格位,以5D0→7F2跃迁为主,对应613 nm处的发射强度最大.MAl2B2O7:Re(M=Sr,Ba;Re=Tb3+)在120～200 nm和200～300 nm光谱区有两个较强的吸收带.位于120～200 nm的宽谱带对应于基质吸收.这包括硼氧和铝氧基团在真空紫外的吸收,基质吸收主要是硼酸根的吸收;而位于160～270 nm左右的一组谱峰对应于Tb3+的4f8-4f5d跃迁;在172 nm的激发下,发射峰由492nm,546nm,592 nm和624 nm组成,分别对应Tb3+的5D4→7FJ(J=6,5,4,3)跃迁发射,其中546 nm是主发峰.