The thermal behavior of mechanically activated galena by thermogravimetry analysis

The thermal decompositions of mechanically activated and nonactivated galenas were studied by thermogravimetry analysis (TGA) at the heating rate of 10 K min⁻¹ in argon. Results indicate that the initial temperature of thermal decomposition (abbreviated as T _di) in the TGA curves for different galenas decreases gradually with increased grinding time. The specific granulometric surface area (S _G), the structural disorder, and the content of elemental sulfur of mechanically activated galenas were analyzed by an X-ray diffraction (XRD) laser particle-size analyzer, XRD analysis, and the gravimetric method, respectively, which shows that the specific granulometric surface area of mechanically activated galenas remains almost constant after a certain grinding time, but the lattice distortions (ε) rise, the crystallite sizes (D) decrease, and the elemental sulfur contents of mechanically activated galenas increase with increased grinding time. The results imply that the decrease of the initial temperature of thermal decomposition in the TGA curves for mechanically activated galenas is mainly caused by the increase of lattice distortions, and the formation of new dangling bonds resulted from the production of elemental sulfur of mechanically activated galenas with increased grinding time. Finally, the differences in the thermal-decomposition reactivity between nonactivated and mechanically activated galenas were also discussed.     

Influence of solid state properties on ferric chloride leaching of mechanically activated galena

The reaction of mechanically activated galena with ferric chloride solution was investigated in the concentration range [Fe³⁺] =0.01–0.6 M at temperatures between 303 and 338 K. The mechanical activation lasting 5–30 min was carried out in a planetary mill. It has been found that this reaction is sensitive to the microstrains produced in the structure of galena during grinding as well as to the concentration of Fe³⁺ in the solution. The influence of Fe³⁺ concentration is in operation practically only in the region [Fe³⁺] < 0.2 M.     

The oxidation behavior of unactivated and mechanically activated sphalerite

The oxidation behaviors of unactivated and mechanically activated sphalerites were investigated using the thermogravimetry method (TG) in flowing highly pure oxygen at the heating rate of 10 K min⁻¹. It is found that the remaining mass between 400 and 873 K in the TG curves of mechanically activated sphalerites rises with increasing grinding time. The difference in oxidation reactivity of unactivated and mechanically activated sphalerites was also discussed. The specific granulometric surface area (S _G), the structural disorder, and the content of elemental sulfur of unactivated and mechanically activated sphalerites were determined by X-ray diffraction (XRD) laser particle size analysis, X-ray diffraction, and the gravimetric method, respectively. The results show that the specific granulometric surface areas of mechanically activated sphalerites remain almost constant after a certain grinding period. The elemental sulfur contents of unactivated and mechanically activated sphalerites were determined to be 0.5 mg/g, and the lattice distortions (ɛ) increase but the crystallite sizes (D) decrease with increasing grinding time. All the results imply that the mass increase between 400 and 873 K in the TG curves of mechanically activated sphalerites depends mainly on the increase of lattice distortions (ɛ) and the decrease of the crystallite sizes (D) with increasing grinding time. It was concluded that TG is a useful method for characterizing mechanically activated sphalerites.     

Oxidative acid leaching of mechanically activated sphalerite

The pressure leaching kinetics of mechanically activated sphalerite was investigated in this work. X-ray diffraction and scanning electron microscopy were used to characterise the influences of crystalline structure and morphology, respectively. A laser particle size analyser and specific surface area tester were used to determine the particle size and specific surface area, respectively. Compared to the non-activated sample, the activated samples demonstrated distinct physicochemical properties with higher reaction efficiencies and increased Zn recovery ratios. The activation energy of sphalerite decreased from 69.96 to 45.91, 45.11, and 44.44?kJ?mol^?1 as the activation time increased from 0 to 30, 60, and 120?min, respectively. The reaction orders for the H₂SO₄ solutions of the sphalerite samples activated for 0, 30, 60, and 120?min were 1.832, 1.247, 1.214, and 1.085, respectively, which indicated that the dependency of the sphalerite leaching process on H₂SO₄ could be reduced by means of mechanical activation.     

Sintering of mechanically activated Zno-TiO2 powders

Zinc oxide and titanium dioxide powders mixed in an equimolar ratio are mechanically activated in a planetary ball mill and sintered under nonisothermal and isothermal conditions. Nonisothermal sintering is studied using dilatometry and SEM. The activation energy of sintering is determined using the method based on different heating rates and Dorn’s method as well. The phase composition of the isothermally sintered samples is determined using x-ray powder diffraction. Published in Poroshkovaya Metallurgiya, Vol. 47, No. 1–2 (459), pp. 55–62, 2008.     

机械活化W-Cu粉末的压力烧结

为了改善工艺与提高W-Cu合金的密度及性能，在对原料粉末进行机械活化处理后进行压力烧结，包括加压烧结与气压烧结，制备出W-Cu合金，考察其烧结合金的组织与性能。结果表明，机械活化能有效的促进烧结。加压烧结与气压烧结都能够有效地促进合金的致密化。加压烧结时，在加压方向上有明显的收缩，但在与加压垂直的方向上却略有膨胀。而气压烧结则可以使合金在各个方向上收缩。烧结组织细密、均匀．相对密度达98％以上。压力烧结是提高W-Cu合金密度的有效手段。     

Hydration of mechanically activated granulated blast furnace slag

Ground granulated blast furnace slag (GGBFS) is known to possess latent hydraulic activity, i.e., it shows cementitious properties when in contact with water over a long period of time. Results are presented in this article to show that, in sharp contrast to published literature on the hydration of neat GGBFS, the complete hydration of slag is possible in a short time (days), even without a chemical activator. This is achieved if the slag used for hydration is mechanically activated, using an attrition mill. The nature of the hydration product of the mechanically activated slag depends not only on the initial specific surface area (SSA) of the slag but also on the surface activation, as manifested by the change in the zeta potential (ξ) of the slag during the milling process. Depending upon the SSA and the ξ, the hydration product changed from nonreacted slag with high porosity (slag SSA < 0.3 m²/g, ξ>−29 mV) to hydrated slag with a compact structure (SSA=0.3 to 0.4 m²/g, ξ=−29 to −31 mV), and, finally, to fully hydrated slag with high porosity (SSA>0.4 m²/g, ξ ∼ 26 mV). Unlike the poorly crystalline hydration product formed by the nonactivated slag, even after prolonged hydration for years, the hydration product of mechanically activated slag was crystalline in nature. The crystallinity of the product improved as the duration of the mechanical activation increased. The calcium-silicate-hydrate (C-S-H) phases present in the slag hydration product, characterized by a Ca/Si ratio of 0.7 to 1.5, were similar to those found for the hydraulic cement binder, except for the presence of Mg and Al as impurities. In addition, the presence of a di-calcium-silicate-hydrate phase (α-C₂SH), which normally forms under hydrothermal conditions, and a Ca-deficient and Si-Al-rich phase (average Ca/Si mole ratio < 0.1 and Si/Al ∼ 3) is indicated, especially in the hydration product of slag that was activated for a longer time.     

Preparation of synthetic rutile by hydrochloric acid leaching of mechanically activated Panzhihua ilmenite

Dissolution of mechanically activated Panzhihua ilmenite in hydrochloric acid for the preparation of synthetic rutile was investigated. Both the dissolution and its coupled titanium hydrolysis were greatly enhanced by the mechanical pretreatment. Increases in the lattice strain and surface area of ilmenite induced by energetic ball milling were responsible for the enhanced dissolution. The rapid hydrolysis led to formation of quantities of the nanosized primary particles, giving rise to a solid/liquid separation problem. The 15 min milled ilmenite, however, yielded an easy-to-filter hydrolysate due to formation of porous, micron-sized, secondary particles during the dissolution. The crystallization and aggregation behaviour of the primary particles were probably related to both the surface property of the un-reacted solid and the ferric ion concentration in solution. The technology for preparation of synthetic rutile was systematically investigated. The optimum milling and dissolution conditions were as follows: milling in air for 15 min, hydrochloric acid concentration 20%, initial reaction temperature 100 °C, ilmenite/20% acid mass ratio 1 g:5.5 g, reaction time ≥ 6 h. The synthetic rutile prepared under the optimum conditions contained 92% TiO₂ and 2.1% Fe₂O₃ as well as combined CaO and MgO of 0.28%. The results demonstrate that the mechanical pretreatment can take the place of the traditional high temperature pretreatment of ilmenite and avoid the dissolution being conducted under pressurized condition.     

Production of tungsten-based composite materials from mechanically activated powders

The effects of the composition and metal additives on the compressibility of mechanically activated tungsten-based powder mixtures, the volume changes upon sintering, and the structure and strength of high-temperature composite materials are studied.     

基于非等温热重法的氟化石墨热分解动力学研究

针对氟化石墨热分解动力学机理不确定和动力学预测信息不足的问题,通过测量多组非等温热重曲线,并利用无模型动力学方法分析（CF）_n热分解反应动力学机理.热重曲线显示（CF）_n热分解经历一步失重,产生的平均气相成分为CF_2.95.动力学分析结果表明机理函数随转化率依次变化:α < 0.1,机理函数为JMA方程f（α）=1.5（1-α）[-ln（1-α）]1/3;0.15 < α < 0.3,机理函数为二维Avrami-Erofeyev方程f（α）=2（1-α）[-ln（1-α）]1/2;0.3 < α < 0.8,机理函数为?esták-Berggren方程f（α）=7.5α1.2·（1-α）2;0.85 < α,机理函数为一维Avrami-Erofeyev方程f（α）=（1-α）.推荐的动力学预测参量活化能为264.23±7.82 kJ/mol,指前因子为（8.70±0.21）×1014/s.另外,动力学机理反映出（CF）_n分解过程存在碳核的链生长以及与分支链的相互作用的特征,这可能是反应产物形成非晶态结构碳的重要因素.      

机械活化-放电等离子烧结制备Y3Al5O12陶瓷

以高纯Y2O3和Al2O3粉体为原料,通过机械活化和放电等离子烧结制备Y3Al5O12(YAG)陶瓷.研究结果表明:机械活化Y2O3和Al2O3粉体,不但细化了Al2O3颗粒,而且使Y2O3发生了晶态转变,由立方晶转变为斜方晶,并最终非晶化;机械活化过程最终还合成了过渡产物YAlO3(YAP),但球磨5h后,继续延长球磨时间,会引入大量ZrO2杂质;球磨处理的Y2O3和Al2O3粉体具有很高的活性,能促进在较低温度下通过放电等离子烧结合成YAG.对球磨5h的粉体在不同温度进行放电等离子烧结的研究表明,在1000℃可获得纯YAG陶瓷,在1 400℃可得到相对密度为99.4%、晶粒大小为1～2μm的YAG陶瓷.     

小波变换方法消除热重实验噪音信号

由于受实验条件的影响,在用等温热重法进行稀土氧化物脱除烟气中SO₂的动力学实验过程中有噪音信号的干扰,因而采用Daubechies(N=3)小波函数和Matlab软件讨论了小波变换方法消除热重实验噪音信号的影响因素.研究发现阀值的选取规则和软硬阀值处理方式对消除噪音信号的影响不大,分解层数则对消除噪音信号的影响较大.当信噪比变化平缓时所对应的分解层数是最佳分解层数.经Daubechies(N=3)小波函数消噪后得到的信号能够比较真实地反映等温热重实验的动力学过程.     

Tensile deformation behavior of mechanically stabilized Fe-Mn austenite

The tensile deformation behavior of mechanically-stabilized austenite is investigated in Fe-Mn binary alloys. A 30 pct thickness reduction by rolling at 673 K (above the A_f temperature) largely suppresses the austenite (γ) to hcp epsilon martensite (ε) transformation in 17Mn and 25Mn steels. However, the deformation behavior of the mechanically stabilized austenite in the two alloys differs significantly. In 25Mn steel, the onset of plastic deformation is due to the stress-induced γ→ ε transformation and results in a positive temperature dependence of the yield strength. The uniform elongation is enhanced by the γ → ε transformation during deformation. In 17Mn steel, bccα′ martensite is deformation-induced along with e and a plateau region similar to Lüders band deformation appears at the beginning of the stress-strain curve. The mechanical stabilization of austenite also suppresses the intergranular fracture of 17Mn steel at low temperatures. M. STRUM, formerly Candidate for Ph.D. at the University of California at Berkeley     

机械活化强化铌钽矿碱性水热体系浸出

针对现行铌钽矿HF酸处理工艺氟污染严重的问题,提出以KOH溶液替代高毒性HF介质的铌钽矿碱性水热体系浸出新方法,研究了铌钽矿在KOH碱性水热体系浸出规律.结果表明,在KOH质量分数50%范围内,KOH质量分数和反应温度的提高会促进铌钽矿分解生成可溶性六铌(钽)酸钾,但过高的KOH质量分数和反应温度会使可溶性六铌(钽)酸钾向不溶性偏铌(钽)酸钾转化,造成铌、钽浸出率的下降.在KOH质量分数35%、反应温度200℃、碱矿质量比4:1以及反应时间2 h的最佳浸出条件下,铌和钽浸出率仅为18.73%和9.4%;通过机械活化对铌钽矿进行预处理后,铌和钽浸出率可大幅度提高至95%和60%,说明机械活化可显著强化铌钽矿碱性水热浸出过程.铌钽矿经机械活化后,矿物粒度减小,比表面积增加,晶格畸变增大,无定形化程度增加,内部缺陷程度增加,矿物的反应活性大大增加,铌钽矿的浸出率显著提高.     

The dissolution of galena in ferric chloride media

The dissolution of galena (PbS) in ferric chloride-hydrochloric acid media has been investigated over the temperature range 28 to 95 °C and for alkali chloride concentrations from 0 to 4.0 M. Rapid parabolic kinetics were observed under all conditions, together with predominantly (>95 pet) elemental sulfur formation. The leaching rate decreased slightly with increasing FeCl₃ concentrations in the range 0.1 to 2.0 M, and was essentially independent of the concentration of the FeCl₂ reaction product. The rate was relatively insensitive to HCl concentrations <3.0 M, but increased systematically with increasing concentrations of alkali or alkaline earth chlorides. Most significantly, the leaching rate decreased sharply and linearly with increasing initial concentrations of PbCl₂ in the ferric chloride leaching media containing either 0.0 or 3.0 M NaCl. Although the apparent activation energy was in the range 40 to 45 kJ/mol (∼10 kcal/mol), this value was reduced to 16 kJ/mol (3.5 kcal/mol) when the influence of the solubility of lead chloride on the reaction rate was taken into consideration. The experimental results are consistent with rate control by the outward diffusion of the PbCl₂ reaction product through the solution trapped in pores in the constantly thickening elemental sulfur layer formed on the surface of the galena.     

The kinetics of leaching galena with ferric nitrate

The kinetics of leaching galena with ferric nitrate as oxidant has been studied. Experimental results indicate that the rate of galena dissolution is controlled by surface chemical reaction. Rate is proportional to the square root of the concentration of ferric ion. The addition of more than one mole/liter sodium nitrate decreases reaction rate. With nitrate additions below this concentration, rate either remains constant or is slightly enhanced. An activation energy of 47 kJ/mol was measured, and rate is proportional to the inverse of the initial size of galena particles. These results are explained in terms of mixed electrochemical control. The anodic reaction involves the oxidation of galena to lead ion and elemental sulfur, and the cathodic reaction involves the reduction of ferric ion to ferrous ion.     

The leaching of galena in ferric sulfate media

The leaching of galena (PbS) in ferric sulfate media was investigated over the temperature range 55 °C to 95 °C and for various Fe(SO₄)_1.5, H₂SO₄, FeSO₄, and MgSO₄ concentrations. Relatively slow kinetics were consistently observed; in most instances, the 1-2/3α-(1−α)^2/3 vs time relationship, indicative of a diffusion-controlled reaction, was closely obeyed. The diffusion-controlled kinetics were attributed to the formation of a tenacious layer of PbSO₄ and S⁰ on the surface of the galena. The generation and morphology of the reaction products were systematically determined by scanning electron microscopy, and complex growth mechanisms were illustrated. The leaching rate increased rapidly with increasing temperature, and the apparent activation energy is 61.2 kJ/mol. The rate increases as the 0.5 power of the ferric ion concentration but is nearly independent of the concentration of the FeSO₄ reaction product. The rate is insensitive to H₂SO₄ concentrations <0.1 M but increases at higher acid levels. The presence of neutral sulfates, such as MgSO₄, decreases the leaching rate to a modest extent.