The reduction/oxidation behaviour of MnAPO-5 as studied by ESR spectroscopy

It is shown by ESR spectroscopy that Mn²⁺ ions in MnAPO-5 are oxidized to Mn³⁺ during calcination atT475 K. Mn²⁺ occupies variously distorted tetrahedral positions within the framework and in extra-lattice sites. Octahedrally coordinated Mn²⁺ presumably located in the channels becomes detectable after adsorption of water. The ESR spectra of reduced MnAPO-5 show line-narrowing due to spin exchange interactions. The material behaves reversible in redox cycles at temperatures near 500 K.     

Catalytic dehydrogenation of isopropanol on La2−xSrxNiO4±y

The series of compounds La_2–xSr_xNiO_4±y (0.0 x 1.0) crystallising in tetragonal K₂NiF₄ structure were prepared and catalytic activity have been investigated using isopropanol decomposition as model reaction. All the catalyst compositions catalyse only the dehydrogenation of isopropanol reaction. The composition La_1.5Sr_0.5NiO₄ showed high activity compared to other compositions in the series. The composition is unique not only in catalytic property but also in other physical properties like structural characteristics, electrical resistivity and metal to semiconductor transition.     

2-（4-氯苯氨基）甲基苯酚降解的动力学研究

采用高效液相色谱技术,开展了Fenton试剂对2-（4-氯苯氨基）甲基苯酚（CMP）的氧化降解动力学的研究。考察了初始双氧水摩尔浓度、亚铁离子摩尔浓度和温度等因素对CMP降解速率的影响,结果表明,当双氧水摩尔浓度、亚铁离子摩尔浓度增大和温度升高时,CMP的氧化速率明显加快。在30~45℃的温度范围内,其氧化降解符合假一级反应动力学模型,反应的表观活化能Ea为102.90kJ/mol。     

Immobilizing chromium in stainless steel slags with MnO addition

This work investigates the stabilizing impact of MnO on the leaching behavior of hazardous Cr-containing CaO-SiO₂-Al₂O₃-Cr₂O₃-MnO stainless steel slags after equilibrating at various elevated temperatures and evaluates the potential immobilization of Cr into a MnCr₂O₄ spinel phase from the existing Cr₂O₃ phase. The MnCr₂O₄ spinel phase was found to be an excellent Cr-stabilizer in stainless steel slags, where the leaching tendency of potentially hazardous Cr-related ions decreased with higher MnO content and lower equilibration temperatures within the range of 0 to 15 mass pct. and 1500 to 1300°C, respectively. Thermodynamic calculations by conducting the phase stability diagram also showed that the MnCr₂O₄ spinel phase was relatively stable and the Ca₃Si₂O₇ (Ca_3-xMn_xSi₂O₇) phase was relatively unstable compared with other crystal phases in acid extractant with pH value of 3.2. Combined with the scanning electron microscopy and X-ray powder diffraction results along with the thermodynamic calculations, the leached Cr-related ions was predominantly originating from the unstable amorphous glass phase.     

Infrared heat treatment of Ti-6Al-4V with electroplated Cu

The objective of this study is to investigate an innovative infrared (IR) technique to enhance adhesion of electroplated copper (Cu) on Ti-6Al-4V without dichromate dipping. The ultimate goal is to develop a Cu coating process on Ti-6Al-4V without hazardous hexavalent chromium (Cr) solution treatments. Cu coatings of around 50 μm were electroplated on Ti-6Al-4V specimens at a current density of 0.03 A/cm² in an acidic Cu solution. To improve adhesion of coatings, IR heat treatments were performed on the Cu-coated samples at different temperatures and durations: 860 °C for 600 s and 875 °C for 20–120 s. This process was accomplished in an attempt to replace the use of dichromate dipping before electroplating. For samples heat treated at 860 °C, no bonding existed, even after 600 s. It is believed that solid-state diffusion prevailed at 860 °C and that 600 s was not enough for sufficient diffusion to occur. Adhesion was poor when samples were heat treated at 875 °C for 20 s. Excellent adhesion was observed when the heat treatment holding time was increased to 40 s. For 90 s, the surface appearance of coatings partially changed from Cu-colored to a grayish color. There was no Cu left on the surface after a 120 s heat treatment. From optical microscopic observations on sample cross sections, an interlayer between the Cu and Ti-6Al-4V formed when heat treated at 875 °C for 40 s and longer. The interlayer thickness increased as the holding time increased, until depletion of Cu. The sheet resistivity of coated specimens was on the order of pure Cu for samples heat treated at 875 °C and less than 90 s. During the 875 °C heat treatment, the following occurred: solid-state diffusion of Cu in Ti-6Al-4V, formation of eutectic solutions, dissolution of Cu and Ti-6Al-4V into the liquid phase, and the formation of intermetallic compounds. The lowest eutectic temperature of 875 °C played a key role in this innovative process of Cu coating on Ti-6Al-4V. This paper was presented at the 2nd International Surface Engineering Congress sponsored by ASM International, on September 15–17, 2003, in Indianapolis, Indiana and appears on pp. 403–10 of the Proceedings.     

Ni-Cr-Fe-Si-B合金涂层及铝青铜基体熔合区组织的研究

采用钨极氩弧焊方法在铝青铜基体上施焊了Ni—Cr-Fe-Si—B合金涂层，并运用金相显微镜、扫描电子显微镜及能谱分析了喷涂层、熔合区及热影响区的组织形貌和成分分布。结果表明，喷焊时，在涂层与基体界面两侧各组元均发生了明显的扩散，Cu、Ni组元间可相互取代，基体融合区组织的基本组成仍为α (α γ2)，但同时也形成了Cu2FeAl7、NiAl3等新相，且融合区组织细小，涂层与基体间为冶金态结合。     

含Cl^-溶液中SO4^2-对316不锈钢临界点蚀温度的影响

采用外加恒电位下腐蚀电流-温度扫描方法研究了在0．5％Cl^-溶液中，SO4^2-浓度对316不锈钢点腐蚀行为的影响．结果表明，随着SO4^2-浓度的增加，钝化电流增加，开路电位降低．当SO4^2-浓度低于0．42％时，316不锈钢的临界点蚀温度比不存在SO4^2-时的临界点蚀温度低；当SO4^2-浓度大于0．42％时，临界点蚀温度比不存在SO4^2-时的临界点蚀温度高．从离子竞争吸附的角度进行分析，对SO4^2-加速与抑制点蚀两种作用规律的形成原因进行了解释．     

(Short communication) Degradation of corrosion resistance of Zircaloy-4 in LiOH aqueous solution

To investigate the degradation of corrosion resistance of Zircaloy-4 in LiOH aqueous solution, SIMS (secondary ion mass spectrometry) analysis was performed to examine the profiles of Li~ , K~ , and OH~- in oxide layers formed in the same concentration (0.1 mol/L) LiOH and KOH solutions. Even though the oxide layers have an equal thickness, the penetration depth of K~ is shallower than that of Li~ , and the penetration depth of OH~- corroded in KOH solution is also shallower than that corroded in LiOH solution. It shows that the diffusion of OH~- into oxide layer is accompanied by the corresponding cation. The difference of degradation effect of LiOH and KOH solutions on the corrosion resistance of Zircaloy-4 was discussed.     

Anti-oxidation mechanism of SiC-B4C-C composites

Mixture of green petroleum coke, B4 C and SiC together with short carbon fiber were employed as starting materials, the mixture was press formed without any binder after grinding, dense and homogeneous binderless SiC-B4 C-C（carbon/ceramic） composites were then obtained after sintering. Composites thus prepared possess excellent anti-oxidation property, that is, mass loss less than IG within the temperature range from 900 to 1 100 ℃ for 10 h. Anti-oxidation mechanism was also discussed from the viewpoint of thermodynamics, excellent anti-oxidation property of materials thus prepared can be discribed to 1） solid SiO2 formed from SiC, which restrains the filtering of oxygen and simultaneously, its volume expansion brought about by the reaction takes roles both walling up the original pores and making the material more compact; 2） liquid B2O3 from the reaction of B4C not only makes the combination with C, B4 C and SiC tighter through forming solid solution, but also effect of reaction SiC（s）＋2CO（g） =SiO2 （s）＋3C（s） is an expansive process, which improves the microstructure of the material.     

ZTC4筒形件温成形扩口数值模拟

对铸造Ti-6Al-4V筒形件温成形扩口成形工艺进行了数值模拟分析,得出了优化的工艺参数,并对凸模锥角进行了优化模拟,得出了合适的锥角。