紫金山东南矿段成矿期次、阶段浅析

通过对紫金山东南矿段铜钼(金)矿床地质矿化特征分析,指出铜钼矿化带主要赋存于花岗闪长斑岩的内外接触带,处于似斑状花岗闪长斑岩的上部,金矿化带赋存在表生氧化带的英安玢岩、隐爆角砾岩中。经过对矿石的组构特征、矿物生成顺序等特征分析,将矿床的成矿演化过程分为斑岩热液期、高硫化浅成低温热液期、表生氧化期三个主要矿化期次,进一步将斑岩热液期分为黑云母-钾长石化阶段、石英-绢云母化阶段、碳酸盐化阶段三个阶段;高硫化浅成低温热液期分为地开石化阶段、明矾石化阶段、硅化阶段三个阶段。研究结果为进一步研究矿床成因提供了依据。     

Instability of zeolite Y supported cobalt sulfide hydrotreating catalysts in the absence of H2S

Ion exchanged CoNaY was sulfided at 473 and 673 K and subsequently heated in He at 673 and 773 K. The resulting samples were characterized by means of overall sulfur analysis, temperature programmed Ar treatment and Fourier transform infrared spectroscopy. It was shown that during He flushing at sufficiently high temperature a protolysis reaction occurs resulting in the decomposition of Co sulfide into Co²⁺ ions and H₂S.     

High-temperature sulfidation of Fe-Nb alloys

The sulfidation behavior of Fe-Nb alloys containing up to 30 w/o Nb was studied over the range of 600–900°C in 0.01 aim. S₂ vapor. All alloys were two-phase, consisting of an Fe-rich solid solution and Fe₂Nb, and followed the parabolic rate law at all temperatures. Scales consisted of two layers-an outer layer of FeS and an inner, complex layer which contained some FeS, FeNb₂S₄ (possibly some FeNb₃S₆), NbS₂, and intermetallic particles which were either completely or only partially sulfidized. Platinum markers were located always at the interface between the two layers, which corresponded to the original metal surface. Activation energies were 18±3 kcal/mol in close agreement with the 19.8 reported for pure iron. The sulfidation rate decreased markedly with increasing Nb content of the alloys. The decrease is attributed to increasing amounts of Fe₂Nb with increasing Nb, the net effect being that the diffusion path for outward iron diffusion through the inner layer is reduced as the Nb content increases. An analysis of the structure of NbS₂ reveals that it is easily intercalated with Fe between loosely bonded layers of S-Nb-S. The S-Nb-S layers are covalently bonded which results in very low diffusivities of either S or Nb in pure NbS₂. Although intercalated Fe tends to change the Van der Waal's type bonding between layers to more ionic or covalent, Fe diffuses readily between the layers in NbS₂. Intercalation of Fe also increases the concentration of sulfur defects in NbS₂, which in turn increases the diffusivity of sulfur. Nb was observed to be immobile. Thus, it is thought that either outward iron diffusion or inward sulfur diffusion in the inner layer is the rate-controlling step, in spite of the close agreement of activation energies with that of the sulfidation of pure iron.     

High-temperature sulfidation of Fe-30Mo alloys containing ternary additions of Al

Fe-30Mo alloys containing up to 9.1 wt% Al were sulfidized at 0.01 atm sulfur vapor over the temperature range of 700–900°C. The sulfidation kinetics followed the parabolic rate law for all alloys at all temperatures. For alloys containing small and intermediate amounts of Al (<4.8 wt.%), a duplex sulfide scale formed. The outer layers of the scales were found to be relatively compact FeS in all cases; whereas the inner layers were composed of the layered compound MoS ₂ (intercalated with iron), the Chevrel compound Fe _x Mo ₆ S ₈,a spinel double sulfide Al _x Mo ₂ S ₄,depending on the Al content of the alloy and the sulfidation temperature. Extremely thin scales were found on the alloys with higher Al contents. Accordingly, extremely slow sulfidation rates were observed—even slower than the sulfidation rate of pure Mo. The transition of the sulfidation kinetics from a high-rate active mode to a low-rate passive mode requires both a critical Al content in the alloy and a critical Mo content. Because of the two-phase nature of the alloys, the latter requirement implies a critical volume fraction of the intermetallic second-phase in the alloy, which has been known as the multiphase effect. Interestingly, the multiphase effect in these alloys was also a function of the Al content in the alloys.     

High-Temperature Corrosion Resistance of Al–Re and Re Coatings

The oxidation behavior in air at 1473 K, and sulfidation behavior in a H2S–H2 gas mixture with a sulfur partial pressure of 10^–2 Pa at 973 K of Al–Re coated CMSX-4 were studied. Investigation on the sulfidation behavior of the Re-coated CMSX-4 was carried out in a H2S–H2 gas mixture with a sulfur partial pressure of 10^–2 Pa at 973 K. The experimental results show that a Re-rich alloy layer was formed between an -Al₂O₃ layer and the inner concentration zone of Ta and Ti for the CMSX-4 single crystal alloy with an Al–Re coating after oxidation. The Re-rich alloy layer containing Cr, W, Ni, Co, and Mo effectively inhibited the outward diffusion of alloying elements and the inward diffusion of Al. The Al/Re-coated CMSX-4 single crystal alloy had excellent sulfidation resistance; the Re-rich alloy layer, containing W, Ti, Ta, and Mo, which formed during the sulfidation process and located between the alumina scale and the CMSX-4 base alloy, plays a role in inhibiting the outward diffusion of alloying elements. The sulfidation resistance of CMSX-4 single-crystal alloy is greatly improved by a Re coating on the CMSX-4 alloy surface; this is attributed to a Re–Cr–W alloy layer that retarded the outward diffusion of cations and the oxide layer containing Ta, Ti, and Al, which inhibited the inward penetration of sulfur.     

The Sulfidation/Oxidation Resistance of Two Ni-Cr-Al-Y Alloys at 700℃

The high temperature corrosion resistance of Ni-25.9Cr-13.5Al-1.2Y-0.6Si and Ni-10.2Co-12.4Cr-16.0Al-0.5Y-0.2Hf alloys was assessed in sulfidation/oxidation environments.In the environment with a sulfur partial pressure of 1Pa. and an oxygen partial pressure of 10^-19Pα,both these alloys exhibited three distinct stages in the weight gain-time curve when tested at 700℃.In the initial stage, selective sulfidation of Cr suppressed the formation of the other metal sulfides,resulting in lower weight gains.In the transient stage, breakdown and cracking of Cr sulfides and insufficient concentration of Cr at the outer zone led to the rapid formation of Ni sulfides and a rapid increase in weight.In the steady-state stage, corrosion was controlled by the diffusion of anions and/or cations, which led to a parabolic rate law.     

The high-temperature corrosion behavior of Co-Nb alloys in mixed-gas atmospheres

The corrosion of Co-Nb alloys containing up to 30 wt.% Nb in H₂-H₂S-H₂O gas mixtures was studied over the temperature range of 600–800°C. The gas composition falls in the stability region of cobalt sulfide and Nb₂O₅ in the phase diagrams of the Co-O-S and Nb-O-S systems at all temperatures studied. Duplex scales, consisting of an outer layer of cobalt sulfide and a complex, heterophasic inner layer, were formed at all temperatures studied. In addition to cobalt sulfide and CoNb₃S₆, a small amount of NbO₂ was found in the inner layer. The reason for the formation of NbO₂ over that of Nb₂O₅ in the scale is that the outer sulfide scale lowers the oxygen activity within the scale into the NbO₂-stability region. Two-stage kinetics were observed for all alloys, including an initial irregular stage usually followed by a steady-state parabolic stage. The steady-state parabolic rate constants decreased with increasing amounts of Nb, except for Co-20Nb corroded at 700°C. Nearly identical kinetics were observed for Co-20Nb corroded at 600°C and 700°C. The presence of NbO₂ particles leads only to a limited decrease of the available cross-section area for the outward-diffusing metal ions. The activation energies for all alloys are similar and are in agreement with those obtained in a study of the sulfidation of the same alloys. The primary corrosion mechanism involves an outward Co transport.     

Oxidation-sulfidation behavior of Ni aluminide in oxygen-sulfur mixed-gas atmospheres

Oxidation-sulfidation studies were conducted on sheet samples of nickel aluminide, containing 23.5 at. % Al, 0.5 at. % Hf, and 0.2 at. % B in an annealed condition and after preoxidation treatments. Continuous weight-change measurements were made by a thermogravimetric technique in exposure atmospheres of air, a low- gas mixture, and low- gas mixtures with several levels of sulfur. Detailed scanning electron microscopy (SEM), X-ray, and electron microprobe analyses of the corrosion product scale layers were performed. The air-exposed specimens developed predominantly nickel oxide; the specimen exposed to a low- .     

Microcrack generation and its healing in the oxide scale formed on Fe-Cr alloys

Fe -base alloys containing 5, 10, and 20 wt. % Cr were oxidized in a stream of O₂ at 750 and 900°C up to 264 hr. A sulfur decoration method was applied to detect the cracks generated in the scale during oxidation. This method revealed frequent crack generation and its healing in the scale. In the case of low-Cr alloys, the cracks are filled up with newly formed Fe-rich oxide but may be regenerated during further oxidation. Cracks are generated in the scale on an Fe-20Cr alloy also, although this alloy is not so severely attacked because of rapid healing.