Simple and novel synthesis of zirconia whiskers from a phosphate flux

High quality zirconia whiskers have been successfully prepared by molten salt method, using zirconium oxychloride (ZrOCl₂·8H₂O) and sodium phosphate tribasic dodecahydrate (Na₃PO₄·12H₂O) as precursor and molten salt, respectively. The effects of types of molten salt and heat treatment temperature on the formation of zirconia whiskers were characterized by XRD, Raman, DTA-TG, FE-SEM, TEM, SAED and HR-TEM. When Na₃PO₄·12H₂O is utilized as molten salt and the heat treatment temperature is 900?°C, the as-prepared zirconia whiskers with length ranging from 4?µm to 8?µm show an average aspect ratio of 25. The obtained ZrO₂ whiskers with monoclinic structure are elongated along [010] direction and exhibit a smooth surface with no distinct defects. The XRD and Raman results reveal that the phase transformation from tetragonal zirconia to monoclinic zirconia occurs with the increased crystal size and the water quenching treatment can significantly reduce the content of sodium zirconium phosphate [Na_9–4×Zr_x(PO₄)₃] in the final product. The growth mechanism of zirconia whiskers is supposed to be a dissolution-precipitation process. Since the sodium zirconium phosphate [Na_9–4×Zr_x(PO₄)₃] effectively promotes the dissolution of zirconia in liquid molten salt, zirconia can grow into zirconia whiskers according to its anisotropy.     

碳化锆陶瓷有机前驱体的热解过程

合成了碳化锆陶瓷有机前驱体，研究了其在热解过程中化学成分和物相组成变化，探讨了从有机高分子向无机陶瓷转化的机理，对碳热还原反应进行了热力学分析。结果表明，前驱体在600℃以下完成了有机结构的断裂、裂解碎片的重排与挥发，600℃以上裂解产物不再具备有机特征；随热解温度升高，无定型碳和单斜相ZrO2逐渐生成，大于1200℃时可检测到立方相ZrC，1400℃时单斜相ZrO2基本消失；1500℃时完成碳热还原反应，在远低于热力学反应温度的条件下生成了高度结晶的纳米尺寸的立方相碳化锆陶瓷。     

退火温度对新型锆合金薄板带材析出相和织构的影响

采用扫描电镜和超高分辨透射电镜,对具有良好冲制性能的新型锆合金薄板成品带材进行含晶粒、第二相粒子等在内的显微组织研究,并探索真空退火处理条件下温度对带材显微组织的影响。结果显示:新型锆合金薄板成品带材晶粒平均尺寸2.17 μm,存在{0001}<1010>和{0001}<1120>两种织构,大部分晶粒<1120>平行带材RD方向,较少晶粒<1010>平行带材RD方向;第二相粒子分布在晶粒内部及晶界,平均尺寸114 nm,尺寸较大的为不规则椭圆形的Zr-Nb-Fe相,尺寸较小的为圆形的β-Nb相;热处理退火温度降低,带材晶粒尺寸减小,第二相粒子细小弥散分布;新型锆合金薄板成品带材良好冲制性能主要源于轧制积累应变诱发再结晶过程进行充分,导致晶粒细小及孪晶发生破碎;相对轧制变形,退火对带材冲制性能影响不显著。     

基于BP神经网络的条带刚凸特征回弹预测

为了研究核燃料组件格架的条带刚凸特征的回弹量与压边力、冲压速度、凸凹模间隙、摩擦系数等冲压工艺参数之间的关系,首先,获取包含50个GA拉丁超立方抽样的数据点以及10个随机抽样的数据点的数据集,前者作为训练集、后者作为测试集。将前者输入到BP神经网络进行训练,后者验证训练模型的精度。最后,通过响应面图研究各因素之间的交互作用以及各因素的敏感程度。结果表明:BP神经网络能够有效预测刚凸回弹量与冲压工艺参数之间的关系,相对于其他因素,压边力对回弹量的影响特别明显,冲压速度对回弹量的影响不明显,但与凸凹模间隙和摩擦系数有明显的交互作用。     

Diffuse reflectance behavior of the printed cotton/nylon blend fabrics treated with zirconium and cerium dioxide and citric acid in near- and short-wave IR radiation spectral ranges

Near- and short-wave IR emission spectra of printed cotton/nylon blend fabrics coated with inorganic compounds in order to tune their diffuse reflectance behavior to the ones with woodland and desert backgrounds are investigated. In this regard, cotton/nylon blend fabrics printed with a four-color digital pattern were used as the substrate, and different concentrations of zirconium and cerium dioxide (ZrO₂ and CeO₂) with and without citric acid as a cross-linker were loaded on these fabrics using the pad-dry-cure method. The diffuse reflectance of the coated fabrics with various concentrations of nanoparticles and a cross-linker was first measured by near-infrared (NIR) diffuse reflectance spectroscopy (DRS). Then, fabrics with an optimum concentration of nanoparticles and appropriate reflectivity profiles similar to woodland and desert were investigated by field emission scanning electron microscopy (FE-SEM), energy-dispersive spectroscopy (EDS), washing, and rubbing fastness properties. In general, NIR and short-wave infrared (SWIR) reflectance of fabrics coated with ZrO₂ and CeO₂ nanoparticles in range of 1% to 1.5% (w/v [%]) was suitable for matching with different environments. According to the findings obtained from the durability test, it was concluded that the washing fastness of the treated fabrics with CeO₂ nanoparticles was excellent in both environments. FE-SEM images of the treated fabrics containing ZrO₂ and CeO₂ indicated that the presence of nanoparticles on the surface of fabrics in woodland patterns was greater than the desert ones. However, the coated fabrics with CeO₂ and citric acid in the woodland pattern have shown better dispersion with a mean particle size of 30 to 60 nm.     

Phase evolution and microstructure of new Sr0.5Zr2(PO4)3-NdPO4 composite ceramics prepared by one-step microwave sintering

Sodium Zirconium Phosphate (NaZr₂(PO₄)₃, hereinafter NZP) and monazite are both potential materials for immobilization of nuclear waste. In this work, novel (1-x)Sr_0.5Zr₂(PO₄)₃-xNdPO₄ composite ceramics (x = 0, 0.2, 0.4, 0.6, 0.8, and 1.0) for simultaneously immobilizing the simulated fission product (FP) Sr and trivalent minor actinide (MA) Nd were prepared by one-step microwave sintering technique, in which Sr and Nd were immobilized into NZP and monazite type structures, respectively. The phase evolution and microstructure of the samples were investigated by X-ray diffraction (XRD), Raman, and backscattering scanning electron microscopy (BSE). The results showed that the expected composite ceramics were successfully obtained by one-step microwave sintering at 1050 °C for 2 h. The as-prepared samples consisted of Sr_0.5Zr₂(PO₄)₃ and NdPO₄ phases, and the content of the two phases varied regularly as x changed, generally conforming to the designed nominal chemical composition. Importantly, the composite ceramics presented the homogenous and dense microstructure. The relative density of the composite ceramics was more than 95%, meanwhile, the Vickers-hardness of the samples was higher than 600 MPa. It was indicated that NZP-monazite type composite ceramics could be a potential matrix for the simultaneous immobilization of actinide and fission product.     

新型合成气甲烷化催化剂La2O3-ZrO2-Ni/Al2O3的制备与性能

针对常规合成气甲烷化催化剂高热结构稳定性差、活性低、适应性差等不足，本文创新地引用稀土金属氧化物La₂O₃复配过渡金属氧化物ZrO₂作为多功能复合助剂，利用反向沉淀法制备了新型合成气甲烷化催化剂La₂O₃-ZrO₂-Ni/Al₂O₃，同时制备催化剂Cr₂O₃-Ni/Al₂O₃作为参照组。采用X射线衍射（XRD）、透射电子显微镜（TEM）表征了催化剂的微观结构，并利用N₂吸附仪（BET）测量催化剂经高温水热处理前后的微孔结构参数，以考察催化剂的高热结构稳定性。结合国内某大型煤制天然气项目工艺特征和运行实践，应用Aspen Plus软件模拟了四段甲烷化工艺理论平衡值。基于自主固定床合成气甲烷化评价实验装置，考察了反应压力、空速和原料气H₂O(g)含量等因素对La₂O₃-ZrO₂-Ni/Al₂O₃催化性能的影响，并开展了1000h长周期寿命评价实验。结果表明，La₂O₃-ZrO₂-Ni/Al₂O₃比Cr₂O₃-Ni/Al₂O₃具有更优的高热结构稳定性；可使CO和CO₂反应达到或接近催化剂床层出口温度下的理论平衡状态，呈现显著的宽温活性；活性组分NiO晶粒尺寸介于7~10nm，分散度较高；对反应压力、空速和原料气H₂O(g)含量的变化不敏感，具有良好的操作弹性；1000h反应后仍能保持较高的活性和稳定性。     

Improvement in hydration resistance of CaO granules by addition of Zr(OH)4 and Al(OH)3

Improving the hydration resistance of CaO aggregates is the key to successful application of lime-based refractories in metallurgical industry. Additive Zr(OH)₄ and Al(OH)₃ were introduced in the preparation of CaO granules using granulation equipment and calcination method in this study. The results showed that the hydration resistance of CaO granules was improved significantly, especially for granules with 0.6 wt.% Zr(OH)₄ and 0.9 wt.% Al(OH)₃, respectively. The shell of CaO granules was relatively dense after calcination and the volume of open pores of CaO granules decreased from 3.56 × 10⁻² to 1.80 × 10⁻² cm³/g when additive was introduced. Zr(OH)₄ and Al(OH)₃ have the opposite effect on the closed porosity of CaO granules, the closed porosity of CaO granules was decreased with Zr(OH)₄ addition, but increased with Al(OH)₃ addition.     

2A12铝合金在两种体系中微弧氧化膜层的磨损性能研究

目的比较两种不同溶液体系中铝合金微弧氧化膜层的摩擦磨损性能。方法以2A12铝合金为研究对象,通过微弧氧化技术,制备了在两种体系中的微弧氧化膜层。利用扫描电子显微镜(SEM)和X射线衍射仪(XRD)、显微硬度计、摩擦磨损机,研究了两种不同溶液体系中的微弧氧化膜层的形貌、厚度、硬度和磨损性能的差异。结果锆盐体系中膜层的生长速率较磷酸盐中的更大。锆盐和磷酸盐体系中膜层的硬度分别为1050HV和1250HV。锆盐体系的膜层主要由α-Al_2O_3、γ-Al_2O_3、c-ZrO_2和少量的t-ZrO_2组成,磷酸盐体系膜层的主要成分是α-Al_2O_3和γ-Al_2O_3。锆盐体系中,450 V电压下膜层的摩擦系数为0.425,500 V电压下膜层的摩擦系数为0.375;磷酸盐体系中,450 V电压下膜层的摩擦系数为0.328,500 V电压下膜层的摩擦系数为0.325。结论锆盐膜层的摩擦系数总体大于磷酸盐膜层。在磨损过程中,被磨掉的GCr15材料填充到膜层的凹坑中。两种溶液体系下,膜层在高电压下表现出更小的摩擦系数。磨损起始阶段为磨粒磨损,稳定阶段为粘着磨损。     

聚合物基杂化阳离子交换膜的制备及性能研究

传统方法制备的异相离子交换膜,在强酸强氧化性溶液体系中使用存在树脂粉脱落和膜性能严重下降的现象,针对这一问题使用流涎法制备出了以聚偏氟乙烯为高分子膜骨架,以聚氯乙烯树脂粉为主要荷电基团,以磷钨酸和磷酸锆颗粒为掺杂荷电基团的聚合物基杂化阳离子交换膜。研究了聚合物基杂化阳离子交换膜的基本性能,测试了膜在强酸强氧化性溶液体系中的电解稳定性,利用扫描电子显微镜(SEM)对膜的表面和截面微观形貌进行了表征。结果表明,相比于传统方法制备的异相阳离子交换膜,流涎法制备的聚合物基杂化阳离子交换膜,膜的选择透过性能和导电性能均有所提高,在强酸强氧化性溶液体系中的电解稳定性也得到了很大的改善,基本上不存在树脂粉脱落和膜性能严重下降的问题。