Characterization of mechanothermally processed nanostructured ZnO

In this paper, the Taguchi method with an L₉(34) orthogonal array was used as experimental design to determine the optimum conditions for preparing ZnO nanoparticles via a mechanothermal route. ZnSO₄·H₂O and Na₂CO₃ were used as starting materials. The effects of milling time, Na₂CO₃/ZnSO₄·H₂O molar ratio, and ball-to-powder mass ratio (BPR) on the bandgap (E_g) of ZnO nanoparticles were investigated. The ranges of the investigated experimental conditions were 5–15 h for the milling time (t), 1.0–1.2 for the Na₂CO₃/ZnSO₄·H₂O molar ratio (M), and 10–30 for BPR. The milling time and BPR exhibited significant effects; an increase in milling time reduced the bandgap. The optimum conditions from this study were t₃ = 15 h, M₁ = 1, and BPR₂ = 20. Only two significant factors (t₃, 15 h; BPR₂, 20) were used to estimate the performance at the optimum conditions. The calculated bandgap was 3.12 eV, in reasonable agreement with the experimental results obtained under the optimized conditions.     

Large-scale synthesis of nickel sulfide micro/nanorods via a hydrothermal process

Rhombohedral-phase NiS micro/nanorods were synthesized on a large scale through a hydrothermal method using NiCl₂·6H₂O and thiourea crystals as starting precursors. Recrystallized thiourea was observed to play an important role in the formation of micro/nanosized rods and flower-like structures. The molar ratio and reaction temperature of the precursors influenced the morphology and phase of NiS products. Pure rhombohedral NiS micro/nanorods were obtained on a large scale when the molar ratio between NiCl₂·6H₂O and thiourea crystals was fixed at 2:1, and the mixture was heated at 250℃ for 5 h. Flower-like NiS nanostructures were formed when the molar ratio between NiCl₂·6H₂O and thiourea crystals was maintained at 1:1. The Raman and Fourier-transform infrared (FTIR) spectra of the as-prepared rhombohedral NiS micro/nanorods were collected, and their magnetic properties were investigated. The results showed that the FTIR absorption peaks of the as-prepared product are located at 634 cm-1 and their Raman peaks are located at 216 and 289 cm-1; the as-prepared NiS micro/nanorods exhibited weak ferromagnetic behavior due to the size effect.     

Reaction condition optimization and kinetic investigation of roasting zinc oxide ore using (NH<Subscript>4</Subscript>)<Subscript>2</Subscript>SO<Subscript>4</Subscript>

An orthogonal test was used to optimize the reaction conditions of roasting zinc oxide ore using (NH₄)₂SO₄. The optimized reaction conditions are defined as an (NH₄)₂SO₄/zinc molar ratio of 1.4:1, a roasting temperature of 440°C, and a thermostatic time of 60 min. The molar ratio of (NH₄)₂SO₄/zinc is the most predominant factor and the roasting temperature is the second significant factor that governs the zinc extraction. Thermogravimetric–differential thermal analysis was used for (NH₄)₂SO₄ and zinc mixed in a molar ratio of 1.4:1 at the heating rates of 5, 10, 15, and 20 K·min-1. Two strong endothermic peaks indicate that the complex chemical reactions occur at approximately 290°C and 400°C. XRD analysis was employed to examine the transformations of mineral phases during roasting process. Kinetic parameters, including reaction apparent activation energy, reaction order, and frequency factor, were calculated by the Doyle–Ozawa and Kissinger methods. Corresponding to the two endothermic peaks, the kinetic equations were obtained.     

Reaction zone characterization of counter-flow diffusion flame with diluted and preheated reactants

Reaction zone characteristics were studied using hydroxy radical planar laser-induced fluorescence (OH-PLIF) technique for a counter-flow preheated (CH₄+N₂)/(Air+N₂) diluted diffusion flames. The effects of preheat temperature and dilute ratio on the reaction zone characteristics were investigated by demonstrating the OH intensity distribution and reaction zone thickness from OH-PLIF images. Under the experimental conditions of constant cold flow velocity, the results show that the OH intensity and reaction zone thickness decrease with the increase of dilute ratio at constant preheat temperature and increase with preheat temperature at fixed dilute ratio. The OH maximum intensity shifts towards the "lean" side of counter flow at constant preheat temperature, and it shifts towards the fuel side with the increase of dilute ratio of fuel stream and towards the oxidizer side with the increase of dilute ratio of oxidizer stream respectively. The feasibility of OH as a reaction zone marker in this diluted combustion is verified further. The variation of diffusion and chemical reaction rate of reactants due to preheat and dilution contributes to the reaction zone characteristics simultaneously. The effect of strain on the flame reaction zone should be included in the future work.     

Optimization of operation conditions for extracting lithium ions from calcium chloride-type oil field brine

Al(OH)3 was prepared to extract lithium ions from calcium chloride-type oil field brine. The influences of four factors, namely temperature, Al3+/Li+ molar ratio, OH-/Al3+ molar ratio, and contact time between Al(OH)₃ and the brine, on the yield of lithium ions were investigated. It is found that their optimal values are 35℃, 4.5, 2.6, and 6 h, respectively. In the course of the experiment, the apparent pH value was observed. The results reveal that the apparent pH value has no remarkable influence on the yield of lithium ions. Meanwhile, the effects of the concentrations of calcium ions and magnesium ions in the brine on lithium recovery were studied. The results indicate that calcium ions have minor negative influence on the yield of lithium ions under optimal conditions, and magnesium ions slightly influence the yield of lithium ions.     

Removal of zirconium from hydrous titanium dioxide

A method was proposed for removing zirconium (Zr) from hydrous titanium dioxide (HTD) by the NaF solution. The effects of main parameters, i.e. pH values, NaF dosage, temperature and retention time, on the removal of zirconium were studied. The optimal conditions were found as the following: pH value, <5.5; molar ratio of NaF to TiO₂, 0.6; retention time, 80 min; and temperature, 80℃. The removal rate of Zr under the optimized conditions was above 87.7%. The adsorption energy of the preferential absorption of hydrofluoric acid for Zr(OH)₂SO₄(OH₂) on the (001) crystal surface of HTD was determined by theoretical calculation. The possible mechanism of the removal process was also discussed.     

Preparation of sol-gel derived microcrystalline corundum abrasives with hexagonal platelets

The effects of different additives on the mechanical properties, microstructures, and wear behavior of corundum abrasives were investigated. When the number of additive phases increases, the sintering temperature and wear rate decrease, while the densification and mechanical properties increase. The additive SiO₂ is responsible for the development of equiaxed grains, whereas both CaO and MgO promote the development of platelike grains. By controlling the molar ratio of additives, it is possible to obtain different microstructures. With SiO₂-MgO-CaO (molar ratio, 2:1:1) as the additives and nano α-Al₂O₃ powders as the seed, microcrystalline corundum abrasives with hexagonal platelets were obtained using sol-gel process by sintering at 1300℃ for 0.5 h. The average diameter and thickness of hexagonal platelets are 1.38 μm and 360 nm respectively, the single-particle compressive strength is 26.44 N, and the wear rate is (3.06±0.21)×10?7 mm3/(N·m).     

New pyrometallurgical process of EAF dust treatment with CaO addition

The non-carbothermic zinc pyrometallurgical processing of electric arc furnace (EAF) dust was investigated on a laboratory scale. The main objective of this process was to convert highly stable zinc ferrite (ZnFe₂O₄), which accounts for more than half of total zinc in the EAF dust, into ZnO and Ca₂Fe₂O₅ by CaO addition. The EAF dust was mixed with CaO powder in various ratios, pressed into pellets, and heated in a muffle furnace in air at temperatures ranging from 700 to 1100℃ for a predetermined holding time. All ZnFe₂O₄ was transformed into ZnO and Ca₂Fe₂O₅ at a minimum temperature of 900℃ within 1 h when sufficient CaO to achieve a Ca/Fe molar ratio of 1.1 was added. However, at higher temperatures, excess CaO beyond the stoichiometric ratio was required because it was consumed by reactions leading to the formation of compounds other than ZnFe₂O₄. The evaporation of halides and heavy metals in the EAF dust was also studied. These components could be preferentially volatilized into the gas phase at 1100℃ when CaO was added.     

Thermodynamics and phase transformations in the recovery of zinc from willemite

Willemite is a common component of zinc and lead metallurgical slags that, in the absence of effective utilization methods, cause serious environmental problems. To solve this problem and increase zinc recovery, we proposed a novel extraction method of zinc from willemite by calcified roasting followed by leaching in NH₄Cl-NH₃·H₂O solution. The thermodynamics and phase conversion of Zn₂SiO₄ to zinc oxide (ZnO) during calcified roasting with CaO were investigated. The mechanism of mineralogical phase conversion and the effects of the CaO-to-Zn₂SiO₄ mole ratio (n(CaO)/n(Zn₂SiO₄)), roasting temperature, and the roasting time on zinc-bearing phase conversion were experimentally investigated. The results show that Zn₂SiO₄ was first converted to Ca₂ZnSi₂O₇ and then to ZnO. The critical step in extracting zinc from willemite is the conversion of Zn₂SiO₄ to ZnO. The zinc percent leached in the ammonia leaching system rapidly increased because of the gradual complete phase conversion from willemite to ZnO via the calcified roasting process.     

(NH4)2SO4焙烧?浸出法从氧化锌矿石中提取锌

An improved method of (NH₄)₂SO₄ roasting followed by water leaching to utilize zinc oxidized ores was studied. The operating parameters were obtained by investigating the effects of the molar ratio of (NH₄)₂SO₄ to zinc, roasting temperature, and holding time on zinc extraction. The roasting process followed the chemical reaction control mechanism with the apparent activation energy value of 41.74 kJ·mol?1. The transformation of mineral phases in roasting was identified by X-ray diffraction analysis combined with thermogravimetry–differential thermal analysis curves. The water leaching conditions, including the leaching temperature, leaching time, stirring velocity, and liquid-to-solid ratio, were discussed, and the leaching kinetics was studied. The reaction rate was obtained under outer diffusion without product layer control; the values of the apparent activation energy for two stages were 4.12 and 8.19 kJ·mol?1. The maximum zinc extraction ratio reached 96% while the efficiency of iron extraction was approximately 32% under appropriate conditions. This work offers an effective method for the comprehensive use of zinc oxidized ores.     

采用聚氨酯模板法制备花形纳米氧化锌

以乙酸锌(Zn(CH3COO)2)为锌源,尿素(CO(NH2)2)为碱源,非离子型聚氨酯(PU)为模板,采用水热法制备碱式碳酸锌(Zn5(CO3)2(OH)6)前驱体.在400 ℃进一步煅烧前驱体2 h,即获得氧化锌粉末.用粉末X射线衍射和扫描电镜研究产物的形貌和结构.结果表明:以PU为模板制备的氧化锌可以获得由纳米片状结构组成的花状形貌,PU的加入可以有效减小氧化锌的晶粒尺寸.进一步研究反应物的组成、反应温度及反应时间对产物结构的影响,发现当体系中碱源(OH-)和锌源(Zn2+)的摩尔比为4,水热反应时间为18 h,反应温度为150 ℃时,前驱体可以获得最完整的花状形貌,并且煅烧后氧化锌的花形形貌不变.     

ZnO纳米片的水热合成及其光催化性能

目的以Zn(CH_3COO)_2·2H_2O和NaOH为原料,制备ZnO纳米粒子,并研究ZnO纳米材料的形貌对其光催化性能的影响。方法采用一步水热法合成ZnO片状纳米粒子,通过X-射线粉末衍射(XRD),场发射扫描电镜(FE-SEM)和拉曼光谱(Raman)等分析手段对合成产物的结构和形貌进行表征,探讨反应物摩尔比、水热温度和水热时间等合成条件对形成的ZnO纳米粒子形貌的影响,以及形貌演变机理。通过光催化分解水实验对所制备的ZnO纳米粒子的光催化性能进行测试。结果 Zn~(2+)/OH~-摩尔比为1∶4时,在100℃反应6h,可制得片状的纳米ZnO,其产氢量为313μmol·h~(-1)·g~(-1)。结论在本文制备的ZnO纳米材料中,ZnO纳米片的光催化性能优于短棒状和纤维状的ZnO粒子。     

树叶状CuO微结构:低温水浴合成、影响因素和光催化降解性能

以CuCl2·2H2O和NaOH为起始反应物,在没有任何表面活性剂或模板的辅助下,于80℃的水浴中恒温60 min,快速合成了树叶状的CuO微结构.利用X-射线粉末衍射仪和场发射的扫描电子显微镜对所得产物的物相和形貌进行了系统的表征,并调查了起始反应物的摩尔比、反应的温度和时间等实验参数对最终产物形貌的影响.实验显示,所得的树叶状的CuO微结构在365nm的紫外光的照射下具有强烈的促进有机小分子降解的能力.这在环境治理与防护领域有潜在的应用.     

基于正交试验设计的十三聚铝[Al13]7+含量多因素优化研究

采用碱中和滴定法合成羟基铝的过程中影响十三聚铝[Al₁₃]₇₊含量的因素较多,本文选取了总铝浓度、碱化度、反应温度和碱化率等4个主要因素进行了综合优化研究,分析各因素的敏感性影响程度,最终确定合成[Al₁₃]₇₊的最佳条件组合。对4个因素分别选取了代表性的3个水平,运用正交试验设计原理建立了9组实验方案,根据确立的方案合成羟基铝溶液并进行₂₇Al-NMR检测,然后以各铝形态的含量为指标进行极差分析。分析结果表明,4个因素中碱化度影响最显著,总铝浓度次之,反应温度和碱化率显著性较弱;合成[Al₁₃]₇₊的最佳因素组合为总铝浓度为0.1 mol/L、反应温度为60 ℃、碱化度为2.5和碱化率为50 ml/min。     

Photoluminescence of ZnO nanorods grown by hydrothermal method on Si substrate

ZnO nanorods were grown on Si substrate by hydrothermal method under various reaction time (12, 24, and 36 h), Zn²⁺ concentrations (0.01, 0.02, and 0.05 mol/L) and reaction temperatures (70–95 °C). Their photoluminescence (PL) tests were taken at room temperature. Nanorods grown under longer reaction times or higher temperatures can emit stronger UV light and depressed green light, suggesting better crystallization of ZnO nanorods. Higher Zn²⁺ concentration results in stronger green band emitting, whereas the UV peak is depressed with the Zn²⁺ concentration over 0.02 mol/L. This indicates that excessive interstitial Zn defects may be introduced into the nanorods in Zn-rich environment.     

复合固体超强酸S2O82-/Fe2O3/ZnO/ZrO2催化合成乙酸异戊酯

采用沉淀、老化、浸渍、干燥、焙烧等方法制备复合固体超强酸催化剂S2O28-/Fe2O3/ZnO/ZrO2,在该固体超强酸的催化作用下,由异戊醇和冰乙酸合成乙酸异戊酯,探讨醇酸摩尔配比、反应温度、反应时间、不同焙烧温度以及催化剂用量等条件对酯化率的影响。结果表明,此催化剂制备的最优条件为:焙烧温度为650℃,(NH4)2S2O8浸渍浓度为0.5 mol/L,焙烧时间为3 h。合成乙酸异戊酯适宜的反应条件是:反应时间50 min,原料异戊醇与冰乙酸的摩尔配比为2:1,用量为1 g,用复合固体超强酸S2O28-/Fe2O3/ZnO/ZrO2催化剂催化合成乙酸异戊酯的产率是88.5%。     

水热合成一维氧化锌及其影响因素

用Zn(NO3)2、NaOH为原料,十六烷基溴化铵(CTAB)为形貌控制剂,采用水热合成技术制备了一维纳米氧化锌.用X射线衍射仪和透射电镜对产物的相组成和微观形态进行了表征和分析.结果表明,合成的一维氧化锌属于六方晶系,纯度很高,长径比较好.研究了[Zn2 ]:[OH-]、碱度、时间、CTAB的浓度对一维氧化锌微观形貌的影响,并探讨了氧化锌纳米棒的生长机理.研究结果表明,增大[Zn2 ]:[OH-]、pH值、CTAB的浓度有利于氧化锌[0001]面的极性生长;反应时间的增加可以提高一维氧化锌的结晶度,氧化锌的直径和长度也随之增大.     

氮修饰ZnO/ZnAl2O4复合光催化剂及其活性

以硝酸锌和硝酸铝为原料,采用共沉淀法制备了纳米异质结ZnO/ZnAl2O4复合光催化剂.用不同氮源经固相混合焙烧对样品进一步修饰,通过 XRD、SEM、HRTEM、TG-DTA和BET等手段对样品进行了表征.结果表明样品是由ZnO与ZnAl2O4两相组成,平均粒径约为15～20 nm,最佳焙烧温度下的比表面为54.81 m2/g.在模拟太阳光照射下,以甲基橙溶液的光催化降解考察样品的光催化活性.研究了Zn/Al物质的量比,氮源和掺氮量,样品焙烧温度等对光催化降解活性的影响.实验表明,当Zn/Al物质的量之比为1：1.5,六次亚甲基四胺（HMT）作为氮源且与ZnO/ZnAl2O4质量比为1：3混合时,所得样品经600℃焙烧后具有最佳光催化活性.当光催化剂用量为0.5 g/L,用模拟太阳光照射60 min后,对浓度为25 mg/L甲基橙溶液的脱色率为91%.     

超声协同作用下亚微米掺铝氧化锌催化降解亚甲基蓝的研究

通过溶液直接沉淀法制备了掺Al3+的亚微米氧化锌Zn(Al)O,利用XRD和SEM确定其晶体结构和形貌大小.采用Fenton/Co2+体系,在掺铝氧化锌存在和超声协同下进行降解亚甲基蓝的实验,研究溶液初始pH、H2O2浓度、反应温度、Zn(Al)O投加量、Co2+浓度、亚甲基蓝(MB)浓度等实验条件对MB降解率的影响,并对4种降解方法的效果进行比较. 结果表明:采用Fenton/Co2++Zn(Al)O+超声体系,在H2O2浓度为100 mmol/L,pH5～9,温度30～50C,Co2+浓度0.1～0.3 mmol/L,Zn(Al)O投加量1.0 g/L的条件下降解初始质量浓度达80 mg/L的MB溶液,自然光下超声1h后降解率高达72%. 对其降解机理进行了初步讨论.对掺铝氧化锌循环使用的研究发现,循环1次后降解率为68%, 2次下降到48%.在自然光下降解,该文合成的Zn(Al)O的降解率是P25（降解率约40%）的1.8倍.     

六方相NaDyF4微纳米晶的水热合成

采用水热法合成六方相NaDyF4微纳米晶,考察反应温度、反应时间、F-和Dy3+的摩尔比等对产物晶型和形貌的影响.采用X线衍射仪(XRD)和扫描电子显微镜(SEM)对试样进行表征.结果表明:在水-乙醇-油酸体系中,固定水、乙醇和油酸的体积分别为10、12、6mL,NaOH为0.5g,调整F-和Dy3+的摩尔比值为4、5、7和10,220℃反应72 h,可以得到片状、短棒状、六棱柱状和长棒状等纯六方相NaDyF4微纳米晶.提出了六方相NaDyF4微纳米晶可能的生长机制.