固相反应法制备纳米ZnO及其晶粒生长动力学

以乙酸锌和草酸为原料,采用低热固相化学反应法制备纳米氧化锌的前体,通过微波和马弗炉两种焙烧方式焙烧制备得到纳米氧化锌,考察了焙烧温度和时间对纳米氧化锌粒径的影响。使用透射电镜、热重-差热、傅里叶变换红外光谱仪和X射线衍射仪对前体和纳米ZnO进行表征;采用晶粒生长动力学唯象理论计算得出纳米氧化锌在这两种焙烧方式下的晶粒生长动力学规律。结果表明,前体为ZnC2O4?2H2O,随着焙烧温度的提高,纳米氧化锌晶粒迅速长大,在相同焙烧温度和时间下,微波焙烧氧化锌的晶粒尺寸要明显大于常规焙烧方式。微波焙烧和常规焙烧下氧化锌的晶粒生长平均动力学指数分别是6.114和6.858,晶粒生长的平均活化能分别为70.67 kJ/mol和52.13 kJ/mol。     

纳米氧化铁的微波制备及其晶粒生长动力学

采用微波焙烧法和常规焙烧方法分别制备了一种新型的无机非金属材料纳米氧化铁,并研究了氧化铁晶粒生长动力学。使用扫描电镜、热重分析仪、傅里叶变换红外光谱仪和X射线衍射仪对前驱体和纳米氧化铁进行表征。结果表明:在相同焙烧温度和时间下,微波焙烧氧化铁的晶粒尺寸要明显大于常规焙烧方式,同时,微波制备的试样颗粒大小更均匀。微波焙烧和常规焙烧下氧化铁的晶粒生长平均动力学指数分别是4.493和5.133,晶粒生长的平均活化能分别为24.30 k J/mol和30.43 k J/mol。表明微波焙烧有利于晶粒生长,晶粒的平均生长速率较高。     

氯化胆碱-草酸低共熔溶剂处理含铁尘泥制备纳米氧化铁及动力学研究

针对钢铁厂含铁尘泥低附加值的问题,以氯化胆碱-二水合草酸（CC-OA）低共熔溶剂（DES）为研究体系,以钢厂含铁粉尘（经水洗处理）为研究对象,提出了运用氯化胆碱-二水合草酸低共熔溶剂处理含铁粉尘固相前驱体热分解法制备纳米氧化铁,并对处理过程中前驱体热分解及纳米氧化铁晶粒生长进行动力学分析。研究表明:处理过程中得到的前驱体为FeC₂O₄·2H₂O,以其热分解第二阶段为热分析动力学的研究目标,根据Ozawa方程法、Kissinger-Akahira-Sunose方程法和Starink方程法3种等转化率法得到的平均反应活化能为220.54 kJ/mol。前驱体焙烧的最佳条件:焙烧温度为673 K、焙烧时间为1 h。根据唯象方程计算出纳米氧化铁的晶粒生长平均激活能为39.06 kJ/mol,并得到了焙烧温度、焙烧时间与粒径的关系,实现特定粒径纳米氧化铁的制备。最佳焙烧条件下得到的纳米氧化铁纯度达99.67%,扫描电镜下观察其颗粒呈现不规则的立方晶体结构,粒径主要分布在10~100 nm。     

超声波和微波联合辐照下铁酸锌的制备

在超声波辐照下共沉淀法得到铁酸锌前驱体,然后在微波辐照下焙烧得到脱硫剂的活性组分铁酸锌。考察了不同焙烧温度和不同焙烧时间对铁酸锌晶相和粒径的影响。实验结果表明,超声波共沉淀法制备铁酸锌是可行的,且在微波辐照下得到的铁酸锌晶相更完整、晶体粒子更为均匀,同时大大缩短了焙烧时间;在700℃下微波焙烧1 h所形成的铁酸锌能较好地满足作为脱硫剂活性组分的要求。     

微波固相法制备铁酸锌脱硫剂的硫化动力学

通过微波与常规固相法制备了铁酸锌高温煤气脱硫剂,使用X射线衍射（XRD）、氮吸附、扫描电子显微镜（SEM）以及X射线光电子能谱（XPS）对两种不同焙烧方式制备的脱硫剂的物相组成、织构形貌和表面元素进行了表征。数据显示微波焙烧制备的脱硫剂具有孔隙结构丰富、表面金属元素含量高、结合能低等优点。使用热天平对铁酸锌脱硫剂硫化行为进行了研究,根据等效粒子模型计算了两种脱硫剂与硫化氢气体反应的动力学参数,得到了硫化反应动力学方程,并在固定床上对其煤气脱硫性能进行了考察。结果表明硫化过程分为化学反应控制区和颗粒内扩散控制区。微波焙烧制备脱硫剂的化学反应活化能和颗粒内扩散活化能较低,说明其在硫化氢气体脱除上具有更高的活性。在模拟煤气气氛下,相比常规焙烧方法制备的脱硫剂,微波制备的脱硫剂的脱硫性能显著提高,具有更高的硫容和更长的精脱硫时间。     

晶种水热法制备α-氧化铝微粉的生长动力学研究

以硝酸铝为原料,氨水为沉淀剂,得到一水软铝石(γ-A lOOH)沉淀。以该一水软铝石为前驱物,纳米α-氧化铝为晶种,采用水热法直接制备出α-氧化铝微粉。在保温时间为8 h、反应温度从380℃增加到460℃时,水热合成的α-氧化铝微粉的粒径从2.1μm生长到3.5μm;在400℃下,保温时间从8 h增加到36 h时,其粒径从2.3μm增加到4.6μm。据此得出α-氧化铝晶粒生长符合动力学方程:Dn=Dn0 k0.t.e(-Ea/RT),其中晶粒生长指数n=2,活化能Ea=47.37 kJ/mol。分析了α-氧化铝晶体生长机理。     

溶胶-凝胶法制备纳米In2O3粉末

以InCl3·4H2O为原料,经水解、胶溶、凝胶、煅烧得到了纳米级In2O3.利用XRD,TEM,TG-DTA等测试手段对纳米级In2O3的晶粒生长过程进行了研究.计算表明:随着煅烧温度的升高,平均晶粒度增大,而平均晶格畸变率则随着平均晶粒度的增大而减少.表明粒子越小,晶格畸变率越大,晶粒发育越不完整.应用相变理论计算得温度低于500℃煅烧1h,晶粒生长活化能为4.75kJ·mol-1,高于600℃时,晶粒生长活化能为66.40kJ·mol-1.TEM分析表明:加入适量形貌控制剂,可使颗粒的粒径和形貌得到很大改善.     

纳米铜锰复合氧化物前驱物晶粒生长动力学研究

通过对低热固一固化学反应法制备的纳米铜锰复合氧化物前驱物晶粒生长动力学的研究,得到其晶粒生长变化的规律,及晶粒生长激活能和动力学指数的平均值,分别是:E≈33.5 kJ/mol,n≈2.80,为其工业化生产提供理论参考依据.     

柠檬酸络合法制备NiTiO_3纳米粉体

以无机镍盐和钛酸四丁酯为起始原料,柠檬酸为络合剂,采用溶胶–凝胶法制备了NiTiO3纳米粉体。通过X射线衍射、扫描电镜和红外光谱研究了柠檬酸加入量对钛酸镍纳米粉体相组成、显微结构以及晶粒生长活化能的影响。结果表明:在制备过程中加入柠檬酸能明显降低其晶粒生长活化能;随柠檬酸加入量从0g增加至柠檬酸与溶液中阳离子(Ni2++Ti4+)的摩尔比为1:1时,纳米NiTiO3的晶粒生长活化能由60.19kJ/mol降低到43.07kJ/mol;制备的粉体为纯净的NiTiO3物相,结晶性较好。700℃煅烧后NiTiO3粉体颗粒形状为六方形片状结构,粉体的粒子尺寸分布均匀,粒径约为20～30nm。     

新型多孔纳米钛酸锶钡的制备及其对Cd~(2+)的吸附性能

采用反相悬浮聚合溶胶-凝胶法制备了多孔纳米钛酸锶钡吸附剂,分别采用Fourier变换红外光谱、扫描电镜和X射线衍射进行表征。将该多孔纳米钛酸锶钡应用于水中镉离子的吸附,考察了吸附、洗脱条件对其吸附性能的影响,探讨了吸附热力学和动力学规律。结果表明:采用反相悬浮聚合溶胶-凝胶法合成的多孔材料,由纳米粒径的钛酸锶钡晶体组成,平均晶粒粒径为17nm。当pH值为4～7时,该吸附剂对水中的镉离子有很强的吸附能力。其吸附动力学符合Langmuir吸附等温模型和准二级动力学方程式,吸附过程的焓变为37.337kJ/mol,各温度下,Gibbs自由能变均为负值,熵变均为正,吸附活化能为32.965kJ/mol,该吸附为吸热的自发的物理过程。吸附后,该吸附剂可用1mol/L硝酸洗脱再生。     

Microwave sintering and grain growth behavior of nano-grained BaTiO3 materials

In this paper, we investigated the effect of microwave sintering parameters on the development of the microstructure of nano-grained BaTiO₃ materials co-doped with Y and Mg species. It is observed that the materials can not only be sintered densely at a lower temperature (1150 °C) and a shorter soaking time (20 min), but also the grain growth can be suppressed by 2.45 GHz microwave heating process. However, the grain growth exhibits a unique tendency in some processing conditions such as microwave sintering for longer intervals (≧60 min) or at higher temperatures (1200 °C). The grain growth behavior after densification was investigated in terms of the phenomenological kinetics, and the activation energy for grain growth using microwave sintering (59.4 kJ/mol) is considerably less than that of the conventionally sintered ones (96.0 kJ/mol), which indicates that microwave sintering process can accelerate the densification rate of the BaTiO₃ materials comparing with the conventional sintering process.     

Microwave Sintering of Alumina at 2.45 GHz

The sintering kinetics and microstructural evolution of alumina tubes (∼17 mm length, ∼9 mm inner diameter, and ∼11 mm outer diameter) were studied by conventional and microwave heating at 2.45 GHz. Temperature during microwave heating was measured with an infrared pyrometer and was calibrated to ±10°C. With no hold at sintering temperature, microwave-sintered samples reached 95% density at 1350°C versus 1600°C for conventionally heated samples. The activation energy for microwave sintering was 85 ± 10 kJ/mol, whereas the activation energy for conventionally sintered samples was 520 ± 14 kJ/mol. Despite the difference in temperature, grains grew from ∼1.0 μm at 86% density to ∼2.6 μm at 98% density for both conventionally sintered and microwave-sintered samples. The grain size/density trajectory was independent of the heating source. It is concluded that the enhanced densification with microwave heating is not a consequence of fast-firing and therefore is not a result in the change in the relative rates of surface and grain boundary diffusion in the presence of microwave energy.     

The impact of microwave-assisted sintering on fabrication of cobalt ferrite nanostructure foams for gas-sensing

This study employed the Pechini-type sol-gel method to synthesize single-phase cobalt ferrite nanoparticles with almost spherical morphology and an average size of ～50 nm. The Pechini sol-gel is based on the polysterification reaction between citric acid and ethylene glycol and the formation of colloidal nanoparticles due to the polymerization of an iron-cobalt complex. Foam samples were prepared from the obtained nanoparticles by using urea as the progenic agent and subsequent conventional or microwave sintering. The average grain size values for the microwave and conventionally sintered foam samples were 90 and 280 nm, respectively. Microwave sintering has successfully hindered grain growth regarding the initial ～50 nm size of the cobalt ferrite nanoparticles. The microwave sintered foam sample showed an approximately two-fold increase in the surface area value compared to its conventionally sintered counterpart. The pore volume for the conventionally and microwave sintered samples was measured at 0.007 and 0.026 cc/g, respectively. Also, the pore diameter values were measured to be less than 2.5 nm in both samples. The pore size distribution within the microwave sintered sample was unimodal, while the conventionally sintered sample showed a bimodal one. The gas-sensing properties of the samples were examined in pure ethanol, acetone, and liquefied petroleum gas (LPG) atmospheres at different temperatures. The results indicated that for all the samples and in all the three atmospheres, the best working temperature is 300 °C. The microwave sintered foam sample showed the highest sensitivity and the shortest response time. This sample was more selective towards ethanol than the other two gases.     

Ce_(0.8)Y_(0.2)O_(1.9)氧化物的烧结及晶粒生长动力学研究

通过对Ce0.8Y0.2O1.9(YDC)素坯烧结行为的考察,得到了试样的密度、晶粒大小随烧结温度(1000~1500℃)的变化规律。利用扫描电子显微镜对烧结体的晶粒尺寸分布进行统计分析表明:Ce0.8Y0.2O1.9晶粒生长在两个烧结温度区域内分别遵循不同的速率方程,在1000~1300℃较低的温度范围内,晶粒成长的活化能较小(171.1 kJ/mol),即烧结温度对晶粒成长的影响较小;在1300~1500℃较高的温度范围,晶粒生长的活化能较大(479.8 kJ/mol),即晶粒成长对烧结温度的高低表现为非常敏感,并且晶粒尺寸分布显著宽化。烧结体的密度在1000~1400℃范围内随温度的升高几乎直线上升,在1400℃时相对密度达98.5%,1400℃以上则提高的幅度变得很小。     

Demonstration of the cold sintering process study for the densification and grain growth of ZnO ceramics

With the cold sintering process (CSP), it was found that adding acetic acid to an aqueous solution dramatically changed both the densities and the grain microstructures of the ZnO ceramics. Bulk densities >90% theoretical were realized below 100°C, and the average conductivity of CSP samples at around 300°C was similar to samples conventionally sintered at 1400°C. Frequently, ZnO is also used as a model ceramic system for fundamental studies for sintering. By the same procedure as the grain growth of the conventional sintering, the kinetic grain growth exponent of the CSP samples was determined as N=3, and the calculated activated energy of grain growth was 43 kJ/mol, which is much lower than that reported using conventional sintering. The evidence for grain growth under the CSP is important as it indicates that there is a genuine sintering process being activated at these low temperatures and it is beyond a pressurized densification process.     

High Reactive MgO‐Y2O3 Nanopowders via Microwave Combustion Method and Sintering Behavior

To decrease the sintering temperature of MgO‐Y₂O₃ composites to avoid undesired grain coarsening, high reactive MgO‐Y₂O₃ nanopowders were synthesized via microwave combustion method. The degree of combustion was enhanced effectively by adding an extra oxidant ammonium nitrate. The as‐synthesized MgO‐Y₂O₃ nanopowders, ~18 nm in size, showed high specific surface area of 64.55 m²/g and low agglomeration. Relative density of 98% was obtained when sintered at a low sintering temperature of 1350°C. The high reactivity can be attributed to the lower activation energy Q (131.13 kJ/mol), compared with samples without extra oxidant (192.97 kJ/mol).     

Sintering behavior of bimodal iron nanopowder agglomerates

The most important issue in the processing of nanoscale metal powders is whether the metal nanopowder can be fully consolidated into ultra-fine- or nano-grained powder metallurgy parts by pressureless sintering. This paper focuses on the sintering behavior of bimodal iron (Fe) nanopowder agglomerates by considering their microstructure and densification kinetics. During the sintering, bimodal Fe nanopowder compacts underwent discontinuous shrinkage behavior until they neared full density. Three contributions to the sintering mechanisms, asymmetric sintering, densification enhancement, and grain growth inhibition, are presented in relation to the effect of bimodal nanopowder structure. Smaller nanoparticles in the bimodal nanopowders, which are predominantly present at the boundaries and interstitial spaces of larger nanoparticles, are responsible for the three mechanisms stated above. This result is strongly supported by the apparent activation energy values ranging from 48.2 to 90.6 kJ/mol, which correspond to the energy for grain-boundary diffusion in Fe. The experimental results of this study show that bimodal nanopowder agglomerates can be used to produce full density nano-grained powder metallurgical parts by pressureless sintering.     

Induced electromagnetic pressure during microwave sintering of ZnO in magnetic field

This paper presents a unique technological approach for producing a tailored and controlled microstructure in pure zinc oxide using two different sintering methods. A microstructural comparative study between conventional and 2.45 GHz microwave sintered pure ZnO ceramics has been established. Data on the sintering behavior and grain growth as a function of the nature of the heating cycle are collected. The use of two step sintering cycles showed that high density can be achieved with almost complete suppression of grain growth. Compared to conventional sintering, microwave heated samples revealed a denser structure, as two step heated samples presented highest final densities for shorter sintering times. As a semiconductor, the material showed greater heating behavior in H-field which is traduced by higher energy absorption (higher ramp) at the beginning of the heating cycle. H-field sintered pellets showed higher densities and grain size uniformity than the ones sintered in E-field for identical heating cycles. This is likely due to an electromagnetic pressure induced by the combined effect of current loops submitted to a MW–H field.     

Kinetic Analysis of Solution-Precipitation During Liquid-Phase Sintering of Alumina

Densification controlled by solution-precipitation during liquid-phase sintering was analyzed for the aluminamagnesium aluminosilicate glass system. As a model system for liquid-phase sintering, narrowly sized alumina powders and up to 20 vol% magnesium aluminosilicate glass samples were isothermally sintered at 1550° to 1650°C. Densification rate increases with increasing liquid content and sintering temperature but decreases with increasing density. For samples with >15% grain growth, the densification rate during the solution-precipitation stage of sintering was proportional to (particle size)⁻² and thus interface reaction-controlled. Activation energies ranged from 270 to 500 kJ/mol over the relative density range of 66% to 96%, respectively. The low activation energy is attributed to densification by particle rearrangement, whereas the higher activation energy is due to densification controlled by interface-reaction-controlled solution-precipitation. Intermediate activation energies are attributed to simultaneous densification by the two mechanisms.     

Analysis of sintering behavior of alumina green bodies molded under a strong magnetic field based on master sintering curve theory

Understanding and controlling the anisotropic sintering shrinkage behavior of the green body in the strong magnetic field molding technique bring out the superior functions of ceramics. This study aimed to elucidate the sintering behavior of green bodies molded under a strong magnetic field using the master sintering curve (MSC) theory. Green bodies were prepared to obtain MSCs in the directions perpendicular and parallel to the applied magnetic field. A unique MSC of the alumina green bodies molded with and without a magnetic field was obtained using sintering shrinkage ratio estimated by various heating rates. The apparent activation energy of sintering in the direction perpendicular and parallel to the applied magnetic field was 663 kJ/mol, independent of the measured direction, which is higher than that without an applied magnetic field (562 kJ/mol). The (0001) planes of the sintered body obtained from the green body molded in the magnetic field were oriented perpendicular to the magnetic field, whereas the samples without a magnetic field were randomly oriented. Consequently, we found that the grain boundaries with high consistency in the sample applied to a magnetic field should increase the apparent activation energy because of its grain orientation.