取向硅钢脱碳过程的数值模拟分析

通过对硅钢钢带表面的脱碳反应动力学和碳在钢带内部扩散机理的研究,建立取向硅钢脱碳过程的数学模型,模拟分析脱碳气氛、退火温度、钢带的初始碳含量和厚度等因素对脱碳过程的影响,并与试验结果进行对比分析。结果表明,所建模型是可靠的;气氛中的水氢比过高会引起钢带表面过氧化而阻碍脱碳;钢带初始碳含量只在脱碳初期对脱碳过程有所影响;钢带中心部位的碳向外表面的扩散是影响脱碳过程的重要环节;提高退火温度并适当降低露点有利于加快取向硅钢钢带脱碳过程的进行。     

Effect of decarburization annealing temperature and time on the carbon content,microstructure, and texture of grain-oriented pure iron

In this study, the effect of decarburization annealing temperature and time on the carbon content, microstructure, and texture of grain-oriented pure iron was investigated by optical microscopy and scanning electron microscopy with electron-backscatter diffraction. The results showed that the efficiency of decarburization dramatically increased with increasing decarburization temperature. However, when the annealing temperature was increased to 825℃ and 850℃, the steel's carbon content remained essentially unchanged at 0.002%. With increasing decarburization time, the steel's carbon content generally decreased. When both the decarburization temperature and time were increased further, the average grain size dramatically increased and the number of fine grains decreased; meanwhile, some relatively larger grains developed. The main texture types of the decarburized sheets were approximately the same:{001}<110> and {112~115}<110>, with a γ-fiber texture. Furthermore, little change was observed in the texture. Compared with the experimental sheets, the texture of the cold-rolled sheet was very scattered. The best average magnetic induction (B₈₀₀) among the final products was 1.946 T.     

Decarburization rate of RH refining for ultra low carbon steel

The decarburization behaviors of ultra low carbon steel in a 210-t RH vacuum degasser were investigated under practical operating conditions. According to the apparent decarburization rate constant (K_C) calculated by the carbon content in the samples taken from the hot melt in a ladle at an interval of 1–2 min, it is observed that the total decarburization reaction period in RH can be divided into the quick decarburization period and the stagnant decarburization period, which is quite different from the traditional one with three stages. In this study, the average apparent decarburization rate constant during the quick decarburization period is 0.306 min-1, and that of the stagnant period is 0.072 min-1. Increasing the initial carbon content and enhancing the exhausting capacity can increase the apparent decarburization rate constant in the quick decarburization period. The decarburization reaction comes into the stagnant decarburization period when the carbon content in molten steel is less than 14×10-6 after 10 min of decarburization.     

热镀55% Al-Zn时化合物层生长动力学研究

针对用钝化法在Q235钢板上热镀55％Al-Zn，进行了热镀时化合物层的生长动力学分析，建立了化合物层动力学数学模型并提出了其数学处理方法。通过试验数据曲线拟合，获得了不同热镀温度下化合物层的生长动力学关系式及其反应扩散激活能，探讨了硅对化合物层形成和生长的影响。     

A process model for BOF process based on bath mixing degree

The process model for BOF process can be applied to predict the liquid steel composition and bath temperature during the whole steelmaking process. On the basis of the traditional three-stage decarburization theory, the concept of mixing degree was put forward, which was used to indicate the effect of oxygen jet on decarburization. Furthermore, a more practical process model for BOF steelmaking was developed by analyzing the effect of silicon, manganese, oxygen injection rate, oxygen lance height, and bath temperature on decarburization. Process verification and end-point verification for the process model have been carried out, and the verification results show that the prediction accuracy of carbon content reaches 82.6% (the range of carbon content at the end-point is less than 0.1wt%) and 85.7% (the range of carbon content at end-point is 0.1wt%–0.7wt%) when the absolute error is less than 0.02wt% and 0.05wt%, respectively.     

侧底复吹RH真空精炼脱碳过程研究

基于RH内流场,结合冶金反应热力学及动力学,通过建立数学模型研究了侧底复吹RH真空脱碳过程.数值结果表明计算结果与试验结果符合良好.在总吹气量相同条件下,侧底复吹RH前20 min的脱碳速率高于传统RH的脱碳速率.对于传统RH脱碳,前3 s以熔池内CO本体脱碳为主,3~1 000 s以氩气泡表面脱碳为主;对于侧底复吹RH脱碳,前1 000s以氩气泡表面脱碳为主,并且氩气泡表面脱碳速率约为熔池内CO本体脱碳速率的两倍;提高RH处理后期的脱碳速率可提高超低碳钢生产效率.     

Microstructure and mechanical properties of twin-wire arc sprayed Ni-Al composite coatings on 6061-T6 aluminum alloy sheet

We have systematically studied the microstructure and mechanical properties of Ni-5wt%Al and Ni-20wt%Al composite coatings fabricated on 6061-T6 aluminum alloy sheet by twin-wire arc spraying under different experimental conditions. The abrasive wear behavior and interface diffusion behavior of the composite coatings were evaluated by dry/wet rubber wheel abrasive wear tests and heat treatment, respectively. Experimental results indicate that the composite coatings exhibit features of adhesive wear. Besides, the Vickers microhardness of NiAl and Ni₃Al intermetallic compounds is relatively larger than that of the substrate, which is beneficial for enhancing the wear resistance. With the increase of annealing temperature and time, the interface diffusion area between the Ni-Al coating and the substrate gradually expands with the formation of NiAl₃ and Ni₂Al₃ phases, and is controlled by diffusion of aluminum atoms. The grain growth exponent n of diffusion kinetics of the Ni-Al coating, calculated via a high-temperature diffusion model at 400, 480, and 550℃, is between 0.28 and 0.38. This satisfies the cubic law, which is consistent with the general theoretical relationship of high-temperature diffusion.     

对45号钢冷轧薄钢板脱碳层超标的改进措施

简述了优质碳素结构钢的脱碳机理,以及影响钢脱碳的主要因素——加热温度、加热时间、炉内气氛,分析了实际生产中造成脱碳的原因,提出在现有的条件下,解决45号钢脱碳问题最经济、简单、实用的方法是在退火炉内适当增设木炭或木块,以调节和控制炉内气氛。     

Fabrication of Fe–TiC–Al2O3 composites on the surface of steel using a TiO2–Al–C–Fe combustion reaction induced by gas tungsten arc cladding

The aim of the present study was to fabricate Fe–TiC–Al₂O₃ composites on the surface of medium carbon steel. For this purpose, TiO₂–3C and 3TiO₂–4Al–3C–xFe (0 ≤ x ≤ 4.6 by mole) mixtures were pre-placed on the surface of a medium carbon steel plate. The mixtures and substrate were then melted using a gas tungsten arc cladding process. The results show that the martensite forms in the layer produced by the TiO₂–3C mixture. However, ferrite–Fe₃C–TiC phases are the main phases in the microstructure of the clad layer produced by the 3TiO₂–4Al–3C mixture. The addition of Fe to the TiO₂–4Al–3C reactants with the content from 0 to 20wt% increases the volume fraction of particles, and a composite containing approximately 9vol% TiC and Al₂O₃ particles forms. This composite substantially improves the substrate hardness. The mechanism by which Fe particles enhance the TiC + Al₂O₃ volume fraction in the composite is determined.     

Kinetics and mechanism of titanium hydride powder and aluminum melt reaction

Based on the measurement of the released hydrogen gas pressure (P_H2), the reaction kinetics between TiH₂ powder and pure aluminum melt was studied at various temperatures. After cooling the samples, the interface of TiH₂ powder and aluminum melt was studied. The results show that the 2 H P_H2-time curves have three regions; in the first and second regions, the rate of reaction conforms zero and one order, respectively; in the third region, the hydrogen gas pressure remains constant and the rate of reaction reaches zero. The main factors that control the rate of reaction in the first and second regions are the penetration of hydrogen atoms in the titanium lattice and the chemical reaction between molten aluminum and titanium, respectively. According to the main factors that control the rate of reaction, three temperature ranges are considered for the reaction mechanism:(a) 700-750℃, (b) 750-800℃, and (c) 800-1000℃. In the first temperature range, the reaction is mostly under the control of chemical reaction; at the temperature range of 750 to 800℃, the reaction is controlled by the diffusion and chemical reaction; at the third temperature range (800-1000℃), the dominant controlling mechanism is diffusion.     

球团矿还原的动力学模型分析

基于还原炉控温还原实验,通过分析CO和H2还原球团矿过程中的反应速率模型,提出两种气体混合后还原球团矿的反应动力学模型,得到还原过程中阻力和反应速率随温度及还原度的变化规律,得出结论:CO还原球团矿时,内扩散阻力所占比例随着温度及还原度增加而变大;H2还原球团矿时,内扩散属于速率控制环节;混合气还原球团矿时,反应速率随温度升高而增大,温度低于500℃时,CO浓度增加,反应速率降低,而温度超过500℃后,反应速率则随着CO浓度的增加而增大;混合气反应速率模型的计算值与实验结果一致。     

Simulation experiments on the reaction system of CH4-MgSO4-H2O

H2S-rich gas in carbonate reservoirs is usually attributed to thermochemical sulfate reduction （TSR）. In this paper, thermal simulation experiments on the reaction system of CH4-MgSO4-H2O were carried out using autoclave at 425℃--525℃. The threshold temperature for initiating TSR is much lower than our previous studies （550℃）. Properties of the reaction products were analyzed by microcoulometry, gas-chromatography （GC）, Fourier transform-infrared spectrometry （FT-IR） and X-ray diffraction （XRD） methods. Thermodynamics and reaction kinetics of TSR processes were investigated on the basis of the experimental data. The results show that thermochemical reduction of magnesium sulfate with methane can proceed spontaneously to produce magnesium oxide, hydrogen sulfur, and carbon dioxide as the main products, and high temperature is thermodynamically favorable to the reaction. Ac- cording to the reaction model, the calculated activation energy of TSR is 101.894 kJ/mol, which is lower than that by most previous studies. Mg^2＋ may have played a role of catalytic action in the process of TSR. The elementary steps of TSR and reaction mechanism were discussed tentatively. The study can provide important information on the explanation of geochemical depth limit for natural gas and on the generation of high H2S gas in deep carbonates reservoirs.     

Insight into the covalent grafting of organic films onto carbon steel surfaces for protection

The novel use of p-nitrophenyldiazonium tetrafluoroborate salt(GG salt)as a protectant that is electrochemically grafted onto carbon steel has been investigated in0.05 mol L-1H2SO4and 5 wt%NaCl solutions using various corrosion monitoring techniques,such as electrochemical impedance spectroscopy,potentiodynamic polarisation,infrared spectra and scanning electron microscopy measurements.The electrochemical study reveals that this compound is a mixed inhibitor that predominantly controls the cathodic reaction.The surface-grafted film decreases the double-layer capacitance and obviously increases the charge transfer resistance relative to a bare carbon electrode.The values of inhibition effect remain nearly unchanged with an increase in temperature range of 298–318 K.The aryl diazonium is covalently bonded on the steel surface,causing a slight decrease in the apparent activation energy.Overall,the surface-grafted films exhibit excellent inhibition performance in acid and saline solutions within the studied temperature range.     

Gas-based reduction of vanadium titano-magnetite concentrate: behavior and mechanisms

The reduction of vanadium titano-magnetite pellets by H₂-CO at temperatures from 850 to 1050℃ was investigated in this paper. The influences of pre-oxidation treatment, reduction temperature, and V_H2/(V_H2 + V_CO) on the metallization degree were studied. The results showed that pre-oxidation played a substantial role in the reduction of vanadium titano-magnetite pellets. During the reduction process, the metallization degree increased with increasing temperature and increasing V_H2/(V_H2 + V_CO). The phase transformation of pre-oxidized vanadium titano-magnetite pellets during the reduction process under an H₂ atmosphere and a CO atmosphere was discussed, and the reduced samples were analyzed by scanning electron microscopy (SEM) in conjunction with back scatter electron (BSE) imaging. The results show that the difference in thermodynamic reducing ability between H₂ and CO is not the only factor that leads to differences in the reduction results obtained using different atmospheres. Some of Fe_3-xTi_xO₄ cannot be reduced under a CO atmosphere because of the densification of particles' structure and because of the enrichment of Mg in unreacted cores. By contrast, a loose structure of particles was obtained when the pellets were reduced under an H₂ atmosphere and this structure decreased the resistance to gas diffusion. Moreover, the phenomenon of Mg enrichment in unreacted cores disappeared during H₂ reduction. Both the lower resistance to gas diffusion and the lack of Mg enrichment facilitated the reduction of vanadium titano-magnetite.     

300M钢的脱碳行为演化及防护研究

300M钢是重要的飞机主承力结构用材. 然而, 该材料在模锻热处理过程中会出现不同程度的表面氧化和脱碳, 严重影响锻件成品率. 本文对300M钢在不同热处理条件下的脱碳行为进行了系统研究, 利用扫描电镜(SEM)、X射线能谱分析(EDS)等手段表征分析了热处理后试样表层组织形貌, 并采用硬度法统计了脱碳层深度的变化情况, 阐明了300M钢在不同热处理条件下的脱碳行为演化规律, 厘清了防氧化涂层对脱碳层深度的影响. 结果表明, 300M钢在热处理过程中近表面处生成的致密氧化层对碳和氧元素的扩散具有明显的抑制作用; 碳的扩散速度与表层氧化速度在不同温度下都会有一个平衡点, 而表面防氧化剂涂层的施加则会破坏原有平衡. 微观组织分析结果显示, 300M钢表层全脱碳区为珠光体或铁素体, 半脱碳区为马氏体及析出碳化物. 本文还阐明了300M钢表层微观组织随保温时间的演化规律. 最后本文从热力学角度揭示了300M钢表层脱碳-氧化耦合机制. 本文的研究成果有望为300M钢的模锻优化工艺和热处理防护技术提供重要的数据和理论支撑.     

Coordinated control of carbon and oxygen for ultra-low-carbon interstitial-free steel in a smelting process

Low residual-free-oxygen before final de-oxidation was beneficial to improving the cleanness of ultra-low-carbon steel. For ul-tra-low-carbon steel production, the coordinated control of carbon and oxygen is a precondition for achieving low residual oxygen during the Ruhrstahl Heraeus (RH) decarburization process. In this work, we studied the coordinated control of carbon and oxygen for ultra-low-carbon steel during the basic oxygen furnace (BOF) endpoint and RH process using data statistics, multiple linear regressions, and thermodynamics computations. The results showed that the aluminum yield decreased linearly with increasing residual oxygen in liquid steel. When the mass ratio of free oxygen and carbon ([O]/[C]) in liquid steel before RH decarburization was maintained between 1.5 and 2.0 and the carbon range was from 0.030wt%to 0.040wt%, the residual oxygen after RH natural decarburization was low and easily controlled. To satisfy the re-quirement for RH decarburization, the carbon and free oxygen at the BOF endpoint should be controlled to be between 297 × 10?6 and 400 × 10?6 and between 574 × 10?6 and 775 × 10?6, respectively, with a temperature of 1695 to 1715°C and a furnace campaign of 1000 to 5000 heats.     

Element distribution and diffusion behavior in Q&P steel during partitioning

Carbon, manganese, and silicon distribution in quenching and partitioning （Q＆P） steel during partitioning process was investigated to reveal the diffusion behavior. The microstructure and chemical composition were analyzed by means of scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, and three-dimensional atom probe. It is shown that the studied Q＆P steel consisted of martensite laths and thin, film-like retained austenite showing extraordinary phase transformation stability. Carbon atoms mostly diffused to the retained austenite from martensite at a higher partitioning temperature. In the experimental steel partitioned at 400℃ for 10-60 s, carbides or cementite formed through carbon segregation along martensite boundaries or within the martensite matrix. As a result of carbon atom diffusion from martensite to austenite, the carbon content in martensite could be ignored. When the partitioning process completed, the constrained carbon equilibrium （CCE） could be simplified. Results calculated by the simplified CCE model were similar to those of CCE, and the difference between the two optimum quenching temperatures, where the maximum volume fraction of the retained austenite can be obtained by the Q＆P process, was little.     

The genesis of H2S in the Weiyuan Gas Field, Sichuan Basin and its evidence

The Sinian Dengying Formation gas pool in Weiyuan is the oldest large-scale sulfur-bearing gas field in China, which has a H2S content ranging from 0.8% to 1.4%. The Cambrian Xixiangchi Formation gas pool discovered recently above the Dengying Formation contains gas geochemical behaviors similar to those of Dengying Formation but different in sulfur isotopes of H2S. Investigations show that though these two Sinian and Cambrian gas pools are separate ones, they share the same Cambrian source rock. The higher dry coefficient, heavier carbon isotopes, sulfur isotopes of sulfide, lower filling of gas pools, formation water characteristics, reservoir properties and H2S distribution, indicate that H2S in both the Sinian and Cambrian gas pools originates from TSR. The sulfur isotopes of sulfates have shown that H2S was formed in respective pools, namely hydrocarbons charged into the pools reacted with the Dengying Formation and the Xixiangchi Formation gypsum （TSR）, respectively, to form H2S. Compared with sulfur isotopes of sulfates in each pool, δ^34S values of H2S are 8‰ lighter for the Dengying Formation pool and 12‰ lighter for the Xixiangchi Formation pool, respectively, which is attributed to the difference in temperatures of TSR occurrence. The reservoir temperature of the Xixiangchi Formation pool is about 40℃ lower than that of the Dengying Formation pool. Temperature plays a controlling role in both the sulfur isotopic fractionation and amounts of H2S generation during TSR.     

关于国内硅钢薄板高温退火工艺的建议

本文利用对比试验,指出了国内硅钢薄板高温退火工艺未能使硅钢获得足够磁感问题的关键,即在于高温退火所用氢气氛含有杂质。并对如何改善工业生产提出了建议。     

含H2S天然气井溢流过程动态模拟

考虑H₂S在井筒中的相态变化,建立了含H₂S气井井筒动态溢流模型,同时采用有限差分法对模型进行求解,结合四川某含H₂S天然气井现场数据模拟含H₂S天然气井溢流过程,并将模拟结果与不含H₂S气井进行对比分析。研究结果表明：随着温度和压力的降低,H₂S在上部地层井段发生相变并直接引起气体体积的膨胀。含气率的突增使钻井液池增量迅速增加,且在相同的溢流时间内,关井时刻钻井液池增量增加更明显。含H₂S气井井筒内气体膨胀更迅速,导致环空压力下降更快,环空流型转化更加迅速。此外,井底压力下降更快,关井套压迅速增加,进一步加剧了溢流程度。因此,含H₂S气井井喷预警时间急剧缩短,井控难度和井喷危险大大增加。