Cracking behaviour and mechanism at grain boundary of gibbsite during calcination

Limiting the cracking of gibbsites during calcination can reduce the content of ultrafine particles in the smelter grade alumina product and increase the quality of products. However, the investigation on the cracking behaviour and mechanism of gibbsites during calcination remains a challenge. In this study, we focus on the cracking behaviour and mechanism of gibbsite grain boundary during calcination. We first observe the cracking behaviour of the gibbsite grain boundary during calcination and propose a cracking mechanism. Based on the observed crack evolution at the gibbsite grain boundary, we found that the cracking of gibbsite grain boundary is initiated on the surface of particles, and then the cracks grow into the inner side of particles with the calcination. We also investigate the impact of the crystallite size and the c-axis angle between crystallites on gibbsite grain boundary. As a result, the increased crystallite size and the c-axis angle between crystallites can result in increased crack size at the gibbsite grain boundary.     

Effect of calcination temperature on friction and wear behavior of α–alumina (α-Al2O3) for biomedical applications

In this study, structural evolution, sliding friction, and wear behavior of the nano-sized alpha-alumina (α-Al₂O₃), synthesized by calcination of gibbsite (Al₂(OH)₆) at different temperatures (273-1473 K) are reported using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Scanning electron microscopy (SEM), and ball-on-disk wear tests. The effect of calcination temperature and the correlation between grain size, mechanical properties, and tribological behavior of the compounds are investigated. After calcination at 1473 K, the crystallite size of calcined and sintered alumina (α-Al₂O₃) compacts is as small as 10 nm. Also, it is observed that the average particle and grain size significantly affect the tribological properties of the compounds. At all the applied loads of 2, 8, and 16 N, respectively, the sliding wear rate and coefficient of friction were lower in the alumina compacts calcined at 1473 K. The improved tribological properties are attributed to the finer microstructure resulting in enhanced hardness of the sintered compacts calcined at 1473 K.     

Influence of Dynamic Calcination on Crystallite Growth of Submicron Rare-Earth Oxides

The crystallite growth of rare-earth oxide powders with particle sizes of 10 to 30 Å obtained by the hydrolytic decomposition of alkoxides was investigated. These powders were compared with commercially available powders with average particle sizes from 1000 Å to 10 μm. Static and dynamic atmosphere tests were made, the latter by continuous tumbling during calcination. Dynamic calcination controlled crystallite growth effectively while maintaining uniform particle size. Typical arithmetic mean particle sizes were 250 Å for powders calcined at 800°C for 24 h with tumbling and ∼400 Å for powders calcined under identical conditions without tumbling. TGA, X-ray diffraction, and emission spectrographic analyses were used to characterize the powders. Electron microscopy and BET surface area measurements demonstrated the importance of the dynamic calcination method in the growth of primary crystallites into larger particles during the presintering stage of the processing of these powders.     

Synthesis of morphology-controlled mesoporous transition aluminas derived from the decomposition of alumina hydrates

Aluminum hydroxides were synthesized through the acidification of sodium aluminate solution using single organic diester or diacid as pH adjustor and aluminum chelating agent. The obtained alumina hydrates are investigated by XRD, SEM, IR and TG. Bayerite firstly formed at room temperature, and its morphology greatly varied with the pH adjustors used, which probably attributes to different kinetics of the acidification. The bayerite can evolve to gibbsite and boehmite after the hydrothermal treatment at 100 °C and 145 °C, respectively, where these alumina hydrates show diverse morphologies. After the calcination, these alumina hydrates of bayerite, gibbsite and boehmite could pseudomorphically transform to the corresponding η-, χ- and γ-aluminas, respectively, exhibiting different structural and textural properties. Interestingly, the transition aluminas derived from the aluminum tri-hydroxides, bayerite and gibbsite, both display locally organized mesopores, while no such meso-structure can be observed in γ-alumina obtained from the aluminum mono-hydroxide, boehmite. The changes of bayerite during calcination are investigated detailed. The dehydration of non-porous bayerite accompanied with the formation of meso-structured transition aluminas, where the meso-structure becomes more and more clearly defined and pore size expands with the calcination temperature increasing.     

拜耳法制备高纯氧化铝过程中水热深度脱钠

用拜耳法制备高纯氧化铝,将种分得到的高纯三水铝石在不同条件下水热处理脱钠,并对水热产物进行煅烧得高纯氧化铝,分析了水热条件对产物形貌和脱钠效果的影响. 结果表明,水热处理温度约为180℃时,三水铝石[Al(OH)3]转变为一水软铝石(AlOOH),三水铝石晶间的Na2O返溶于水,且转变过程缓慢,升高温度、降低pH值、延长反应时间均能促进转变过程进行.一水软铝石形貌与三水铝石差异巨大,呈玻璃渣状的四方长条晶型堆叠,更疏松无序. 水热产物于1200℃煅烧后,Na2O含量大幅下降,pH为1时煅烧前Na2O含量为0.0163wt%,煅烧后Na2O含量为0.0187wt%.     

氢氧化铝活化对水热法制备勃姆石的影响

采用氢氧化铝粉体为原料,活化后通过水热法制备勃姆石。研究了氢氧化铝活化对勃姆石颗粒尺寸的影响,并讨论了相关机理。研究结果表明:未活化氢氧化铝水热反应所得产物颗粒粒径为2 μm,经过加热（160~220 ℃）活化的氢氧化铝,水热反应所得产物的颗粒粒径在0.3~2 μm变化。对活化氢氧化铝和水热反应中间产物进行表征,由结构分析推测作用机制:氢氧化铝加热活化过程中生成少量勃姆石,这些勃姆石在氢氧化铝水热反应转化为勃姆石（AlOOH）的过程中成为晶种,活化温度升高和活化时间延长,勃姆石晶种数量增加,氢氧化铝水热反应所得产物的颗粒粒径减小,并且加快了水热反应速率。该工作有望提供一种氢氧化铝水热法制备勃姆石的新途径和相关基础理论。     

A 1-D non-isothermal dynamic model for the thermal decomposition of a gibbsite particle

A 1-D mathematical model describing the thermal decomposition, or calcination, of a single gibbsite particle to alumina has been developed and validated against literature data. A dynamic, spatially distributed, mass and energy balance model enables the prediction of the evolution of chemical composition and temperature as a function of radial position inside a particle. In the thermal decomposition of gibbsite, water vapour is formed and the internal water vapour pressure plays a significant role in determining the rate of gibbsite dehydration. A thermal decomposition rate equation, developed by closely matching experimental data reported previously in the literature, assumes a reaction order of 1 with respect to gibbsite concentration, and an order of −1 with respect to water vapour pressure. Estimated values of the transformation kinetic parameters were k₀ = 2.5 × 10¹³ mol/(m³ s) for the pre-exponential factor, and E_a = 131 kJ/mol for the activation energy. Using these kinetic parameters, the gibbsite particle model is solved numerically to predict the evolution of the internal water vapour pressure, temperature and gibbsite concentration. The model prediction was shown to be very sensitive to the values of heat transfer coefficient, effective diffusivity, particle size and external pressure, but relatively less sensitive to the mass transfer coefficient and particle thermal conductivity. The predicted profile of the water vapour pressure inside the particle helps explain some phenomena observed in practice, including particle breakage and formation of a boehmite phase.     

少量石灰石煅烧生成氧化钙的活性分析

采用静态方法模拟悬浮态反应过程,对少量小粒径的石灰石样品进行煅烧,分析了不同的煅烧温度、煅烧时间、物料质量及粒径对氧化钙的活性影响。结果表明：少量的小粒径石灰石煅烧时,随着煅烧温度和煅烧时间变化,氧化钙活性变化较大;在900 ℃煅烧温度下,随着物料质量减少,物料以稀散状态分布,碳酸钙分解迅速加快,需要的煅烧时间大幅缩短,氧化钙的活性大小逼近悬浮态实际情况。     

Synthesis and Characterization of Ce3+:YAG Phosphors by Heterogeneous Precipitation Using Different Alumina Sources

Ce³⁺-doped yttrium aluminum garnet (Ce:YAG) phosphor powders were synthesized by heterogeneous precipitation process using three different aluminum sources: α-phase, θ-phase, and boehmite (AlOOH). Mixtures of yttrium and cerium nitrate solutions containing various aluminum sources were precipitated by ammonia solution in normal and reverse strike methods. The influence of pH was studied in the normal strike method by maintaining the solutions at pH 7, 9, and 11 during precipitation. Dried precipitates were double calcined at 1300°C/16 h and 1300–1500°C/24 h, at a ramping rate of 10°C/min, with an intermittent wet ball milling in water. Structural evolution of the resultant phosphors was studied by powder XRD. In the normal strike method, a highly pure YAG phase was formed by α- alumina (pH 7, 11) and θ-alumina (pH 11) while boehmite source ended up with mixed phases of YAlO₃ (YAP) and Y₄Al₂O₉ (YAM) along with YAG phase at all pH values of precipitation. However, in the reverse strike process, the θ-phase of alumina gave an extremely pure Ce:YAG phase at a relatively lower calcination temperature (1400°C/24 h) compared with the α-phase and also showed more intense emission of yellowish-green light under blue (λ=469 nm) excitation. Scanning electron microscopy revealed 1–2 μm sized particles with least agglomeration in the reverse strike method.     

Hydrothermal synthesis of submicrometer crystals of boehmite

The effect of solvents, mechanically ground gibbsites and amorphous hydrated alumina gels on the formation of well-crystallized and submicrometer-sized crystals of boehmite was studied. Nearly monodispersed boehmite particles of 0.2–0.3 μm with a parallelogram shape were hydrothermally synthesized from ball-milled gibbsite in water at 200°C for 6 h. The 100 nm-sized crystals of boehmite were prepared from amorphous hydrated alumina gels at 255°C for 24 h.     

Alumina nanofibers obtained from poly(vinyl alcohol)/boehmite nanocomposites

Poly(vinyl alcohol) (PVA)/boehmite nanocomposite (precursor) nanofibers were formed by electrospinning using a PVA aqueous solution of dispersed boehmite nanoparticles as the spinning solution. The alumina nanofibers were obtained by calcination of the precursor nanofibers between 500 and 1200°C. The specific surface area of the precursor nanofibers was around 6 m²/g, and that of the γ‐alumina nanofibers calcined at 500°C was around 300 m²/g. The specific surface areas and the fiber diameters were not affected by the alumina contents in the precursors. Also, the diameter of the alumina nanofibers was not affected by the calcination temperature of the precursor nanofibers. The pore characteristics of the alumina nanofibers decreased with increased calcination temperature due to the sintering, and nonporous α‐alumina nanofibers were obtained by calcination of the precursor nanofibers at 1200°C. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Processing and Properties of Sol–Gel-Derived Alumina/Silicon Carbide Nanocomposites

Dense alumina/5 vol% SiC nanocomposites were prepared by sol–gel processing using nanosized (180 nm) precoated SiC powders and a commercial boehmite sol. The SiC powder was precoated with boehmite by a controlled heterogeneous precipitation from an aluminum nitrate solution. The coated SiC powder was then dispersed in a boehmite sol, gelled, calcined, and densified by gas pressure sintering under argon atmosphere at 7–8 MPa pressure. The dependence of the calcination conditions on densification, the effect of seeding on the microstructural development, as well as the mechanical behavior of the sintered specimens, are presented and discussed.     

Mechanical-Activation-Triggered Gibbsite-to-Boehmite Transition and Activation-Derived Alumina Powders

Mechanical activation of monoclinic gibbsite (Al(OH)₃) in nitrogen led to the formation of nanocrystalline orthorhombic boehmite (AlOOH) at room temperature. The boehmite phase formed after merely 3 h of mechanical activation and developed steadily as the mechanical-activation time increased. Forty hours of mechanical activation resulted in essentially single-phase boehmite, together with α-alumina (α-Al₂O₃) nanocrystallites 2–3 nm in size. The sequence of phase transitions in the activation-derived boehmite was as follows: boehmite to γ-Al₂O₃ and then to α-Al₂O₃ when flash-calcined at a heating rate of 10°C/min in air. γ-Al₂O₃ formed at 520°C, and flash calcination to 1100°C led to the formation of an α-Al₂O₃ phase, which exhibited a refined particle size in the range of 100–200 nm. In contrast, the gibbsite-to-boehmite transition in the unactivated gibbsite occurred over the temperature range of 220°–330°C. A flash-calcination temperature of 1400°C was required to complete the conversion to α-Al₂O₃ phase, with both δ-Al₂O₃ and θ-Al₂O₃ as the transitional phases. The resulting alumina powder consisted of irregularly shaped particles 0.4–0.8 μm in size, together with an extensive degree of particle agglomeration.     

Thermal Reaction of Aluminum Alkoxide in Glycols

Thermal reaction of aluminum isopropoxide in glycols at 300°C yielded the glycol derivatives of boehmite. The physical properties of the products and the aluminas obtained by calcination strongly depended on the crystallite size of the boehmite derivatives, which seems to be controlled by the heterolytic cleavage of the C-O bond of HO(CH₂) _n OAI = formed by alkoxide exchange between aluminum alkoxide and glycol. The product had a unique honeycomb texture, which was preserved on calcination to form a transition alumina.     

Influence of Viscous Deformation at the Contact Point of Primary Particles on Compaction of Alkoxide-Derived Fine SiO2 Granules under Ultrahigh Isostatic Pressure

Viscous deformation and the adhesion force at the contact point between amorphous silica particles under ultrahigh isostatic pressure (up to 1 GPa) are important in the densification of powder compacts. The amount of viscous deformation and the strength of adhesion force have been changed in the present study by altering the calcination temperature and particle diameter, and the new values have been determined successfully using a diametral compression test. The diameter of spherical and monosized alkoxide-derived silica powders has been controlled within the range of 10–400 nm. Close-packed granules of these powders have been produced by spray drying. Because of viscous deformation, as-spray-dried ultrafine silica powders without calcination could be consolidated into highly dense compacts (>74% of theoretical density) by applying ultrahigh isostatic pressure (1 GPa). Relatively high temperature in the calcined particles (400°C) causes viscous deformation at the contact point to disappear almost completely and clearly increases the adhesion force, because of neck growth that has resulted from viscous sintering. At temperatures >200°C, the green density of the calcined powders decreases to 65% of theoretical density, even under 1 Gpa pressure. The relationship between green density and viscous deformation in silica particles at the point of contact has been analyzed quantitatively by the Hertz and Rumpf model. On the other hand, if relatively low isostatic pressure ( P c < 100 MPa) is applied, the green density and intergranular pore volume depend on the strength of the spray-dried granules. The relationship between granule strength and neck growth at the contact point with calcination has been estimated quantitatively.     

Sintering Behavior of Pt Metal Particles Supported on Silica-Coated Alumina Surface

The sintering behavior of Pt metal particles was studied by supporting them on silica-coated alumina. Silica coating was found to be effective for the retention of a large surface area of alumina even after calcination at elevated temperatures. Before sintering, the size of Pt metal particles on all the silica-coated aluminas, including the uncoated alumina, was identical, while the particle size was larger on silica than on alumina. After sintering the Pt catalyst at 1073 K, the particle size increased on uncoated alumina as well as on alumina coated with thicker silica layers, especially on the supports previously calcined at >1473 K. On the other hand, the size of Pt metal particles did not increase much on alumina coated with monolayer silica. The observed suppression of sintering of Pt metal particles resulted from the retention of a large surface area of alumina with a thinner silica layer. In the case of a thicker silica layer, although a large surface area was maintained after calcination at elevated temperatures, the existence of a bulk silica-like property of the support did not favor the suppression of sintering of Pt metal particles.     

Development of technology for the production of microspherical alumina support for the alkane dehydrogenation catalyst: II. The influence of hydrothermal treatment conditions on the operational characteristics of microspherical alumina support and chromium oxide/alumina catalyst for the dehydrogenation of iso-butane

For the purpose of improving the mechanical strength and reducing the abrasive activity of micro-spherical chromium oxide/alumina catalysts for the processes of alkane dehydrogenation in fluidized bed, we have developed technology for the production of new highly durable boehmite support with the use of technical aluminum trihydrate as an initial raw material. The technology includes two consecutive stages: the dehydration of aluminum trihydrate and the subsequent hydrothermal treatment of dehydration product into boehmite. Part II covers the results on the influence of conditions for the hydrothermal treatment of aluminum trihydrate dehydration products in an industrial autoclave of special construction on the phase composition, physicomechanical and structural characteristics of boehmite support, the acidic properties of its respective oxide form and chromium oxide/alumina catalyst based on this support and also on the catalytic properties of this catalyst in the reaction of iso-butane dehydrogenation into iso-butylene. It has been shown that differently sized boehmite crystallites and also gibbsite are formed in the volume of microgranule under hydrothermal conditions of χ-Al₂O₃ dehydration depending on a chosen regime (temperature, time). For the production of iso-butane dehydrogenation selective chromium oxide/alumina catalyst with the minimal content of strong acidic sites, catalyzing the cracking reactions, it is necessary to provide such hydration conditions, under which large (43–47 nm) boehmite crystals are formed. The appearance of strong acidic sites is caused by small boehmite crystals and the presence of nonhydrated χ-Al₂O₃ phase. In the absence of the impurity gibbsite phase, the highly durable microgranules of boehmite support and catalyst are formed. The conditions, providing the complete χ-Al₂O₃ hydration into macrocrystalline boehmite, have been defined. The application of the developed two-stage technology gives the iso-butylene yield of 45–49%, the selectivity of 88–90%, and the abrasivity of 0.10 g/(m² h). The given technology for the production of catalyst is realized in an industrial unit with the capacity of 100 t per month at OAO Karpov Mendeleevsk Chemical Plant (Mendeleevsk). Industrial catalyst lots are currently under operation at the Synthetic Isoprene Rubber Plant of OAO Nizhnekamskneftekhim.     

络合溶胶-凝胶法制备Al_2O_3纳米晶及其表征(英文)

以异丙醇铝为原料,用聚乙二醇(PEG1000)络合溶胶-凝胶法合成了Al2O3纳米晶,并采用差热-热重分析、X射线衍射、透射电子显微镜等对络合前驱体及粉体进行表征;探讨了PEG1000及煅烧温度对纳米Al2O3相结构、粒子尺寸、形貌及分散性的影响规律.结果表明:PEG1000增强了纳米Al2O3粒子的分散性.干凝胶在600～900℃煅烧后得到γ-Al2O3相;在600℃煅烧条件下,得到γ-Al2O3粒子形貌为针状结构,长度约为50～60nm.随着煅烧温度的升高,γ-Al2O3针状粒子长度逐渐减小,在750℃煅烧后,得到γ-Al2O3粒子长度为20～30nm;在900℃煅烧条件下,γ-Al2O3粒子形貌为颗粒状,平均粒径尺寸为10nm;当干凝胶在1 000℃煅烧后得到θ-Al2O3和α-Al2O3的混合相,所得粒子平均粒径尺寸为20 nm;当干凝胶在1 200℃煅烧后,得到的Al2O3全部转化α-Al2O3相,制得的纳米Al2O3粒子尺寸均一且分散性良好.     

直链烷烃脱氢催化剂载体制备新工艺

研究了以Na Al O2-Al2(SO4)3为原料制备直链烷烃脱氢催化剂载体的工艺,考察p H交替变化对直链烷烃脱氢催化剂载体孔结构的影响,采用XRD、TEM、DTG、DTA、氮吸附-脱附仪和压汞仪等对载体的晶相、粒子形态、结晶水含量、比表面积及孔分布进行表征。结果表明,p H交替变化使拟薄水铝石晶粒尺寸增加,结晶水含量降低,制备出孔容≥1.2 m L·g-1、比表面积≤150 m2·g-1和堆积密度≤0.32 g·m L-1的具有双孔分布的直链烷烃脱氢催化剂载体γ型氧化铝。酸性条件下,大量细小无定形氧化铝迅速溶解,有利于更多细小拟薄水铝石颗粒形成;碱性条件下,这些迅速溶解的无定型氧化铝附着在拟薄水铝石颗粒上,使拟薄水铝石一次粒子逐步长大,结晶度增加。     

Decomposition of Two Aluminum Sulfates and Characterization of the Resultant Aluminas

Two special types of anhydrous aluminum sulfate with extreme grain shapes were prepared; one, obtained by precipitation from concentrated sulfuric acid solution, is rhombohedral near cubic single-crystal grains and the other, from acetic acid solution, consists of very thin flaky particles. The morphology of sulfate and calcined alumina, the sulfate decomposition, the η-α alumina transformation, and the crystallite growth of α alumina were studied and compared with those processes for reagent-grade sulfate. The morphology of anhydrous sulfate was shown to greatly affect the heat-treatment characteristics of alumina and the sulfate decomposition behavior.