沉淀法合成纳米CeO2的晶粒生长动力学

以Ce(NO3)3·6HzO为铈源,(NH4)2CO3·H2O为沉淀剂,并加入一定量表面活性剂PEG4000,采用液相沉淀法制备前驱体Ce2(CO3)3·H2O,前驱体经热处理合成纳米CeO2.根据XRD线宽法研究了纳米CeO2热处理过程的晶粒生长动力学,结果表明随焙烧温度升高,CeO2晶粒尺寸显著增大;300℃下焙烧时间对CeO2晶粒尺寸影响不明显,700℃下CeO2晶粒随焙烧时间延长而长大,且焙烧初期粒径增长较快,超过180 min后增长速率变慢;700℃时CeO2晶粒生长指数为5,即符合5次方动力学方程,晶粒生长速率常数为1.986 5×104 nm5/min;由于纳米尺寸效应,使得CeO2晶粒生长活化能在低温区和高温区不同,低于400℃时为25.64 kJ/mol,高于400℃时为87.64 kJ/mol;认为热处理过程CeO2的晶粒生长为扩散生长机制.     

纳米级氧化铟锡复合粉体的制备及其性能

采用化学共沉淀法制备纳米级氧化铟锡复合粉体前驱物,煅烧得到纳米级氧化铟锡(ITO)复合粉体,用TG-DTA,XRD,TEM,ICP-AES,XRF和BET研究了纳米级ITO复合粉体的性能.前驱物铟锡氢氧化物的分解温度为291.5℃,300℃下烧结即可得到立方结构的ITO结晶粉体,Sn嵌入到In2O3晶格中,形成单相的ITO固溶体颗粒.随着温度的升高,ITO固溶体颗粒结晶更完全,晶粒长大.前驱物铟锡氢氧化物分别在600℃,800℃和900℃煅烧4 h得到粒度均匀、分散性好、粒径为20 nm～30 nm的类球形ITO复合粉体.600℃煅烧得到的ITO复合粉体的纯度为99.995%,配比为In2O3:90.045%,SnO2:9.955%,比表面积为50.88 m2/g.该粉体烧结活性高,将该粉体用简单的烧结工艺在1000℃烧制的ITO靶材相对理论密度达到99.25%.     

热处理温度对YAG粉体及其多孔陶瓷合成的影响

采用共沉淀法合成的钇铝石榴石(YAG)粉体真空烧结制备多孔陶瓷,通过分析讨论表明,YAG前驱体中绝大部分吸附水蒸发以及绝大部分Al(OH)3和Y(OH)3的分解分别转变成Al2O3和Y2O3失去离子水而产生的失重出现在600℃以下完成。YAG前驱体在1100℃下煅烧后,大量YAG晶相已经形成,而且具有完整的晶型。升高煅烧温度对晶粒尺寸和晶粒形貌的影响显著,也说明YAG粉体颗粒粒径和形貌对最终煅烧温度非常敏感。采用真空烧结技术,成功制备了孔结构均匀规整,大部分微孔径处于5μm左右,且外形保持良好的YAG多孔陶瓷,综合考虑性价比,确定YAG多孔陶瓷的烧结温度为1500℃较为适宜。     

Pr掺杂量对Ce1-xPrxO2晶体结构的影响

通过改变Pr掺杂量,即Ce1-xPrxO2中的x值(0.01≤x≤0.50),以Ce(NO3)3·6H2O,Pr6O11为主要原料,用低温燃烧合成法在247℃～291℃点火,合成了具有纳米晶粒的粉体,其晶粒尺寸在12nm～41nm之间.采用DSC,XRD,SEM测试分析手段,研究了Pr掺杂量对其结构的影响.结果表明所合成粉体为萤石型Ce1-xPrxO2固溶体,不同的x值对反应物着火温度、产物晶型结构及形貌和晶粒尺寸均有影响.改变x值对反应物点火温度影响不大,产物晶型结构均未发生变化,为均一的萤石型结构.掺杂后Ce1-xPrxO2粉体的晶胞参数与未掺杂的CeO2相比有不同程度的减小,说明Pr进入CeO2晶格形成Ce1-xPrxO2置换固溶体.改变Pr掺杂量,颜料晶粒粒度随x值的增大而减小.     

纳米CeO2在热处理过程中的结构和性能变化

采用XRD方法结合粉体相对密度测定研究了热处理条件对沉淀法合成纳米CeO2的结构和性能的影响. 结果表明: 随焙烧温度升高, CeO2晶粒尺寸显著增大, 晶粒发育趋于完整导致晶格畸变度明显降低, 结构致密程度增加使得晶格常数减小, 粉体烧结程度增大, 相应粉体相对密度随之增加; 较低温度(如300.℃)下, 焙烧时间对CeO2晶粒尺寸无明显影响, 相应晶格畸变度、晶格常数和粉体相对密度变化不大; 较高温度(如700.℃)下, CeO2晶粒尺寸随焙烧时间延长而增大, 且焙烧初期粒子增长较快, 此过程伴随着CeO2晶格畸变度进一步下降, 晶格常数却有所增加, 粉体相对密度略有下降; 认为热处理过程CeO2晶粒生长为扩散生长机制是造成不同焙烧温度下焙烧时间对纳米CeO2结构和性能的影响行为不同的主要原因.     

Sm2O3对放电等离子烧结AlN陶瓷致密化和导热性能的影响

针对AlN陶瓷难以烧结致密的特点,采用放电等离子烧结(Spark Plasma Sintering,SPS)技术,利用SPS过程中脉冲电流产生局部高温来加强扩散作用,促进颗粒间颈部接触点形成,并通过添加适量烧结助剂Sm2O3,在短时间内实现了AlN陶瓷的烧结致密化.重点研究了烧结助剂Sm2O3的加入量、烧结温度等工艺参数对AlN陶瓷致密化钩毯统潭鹊挠跋?研究发现Sm2O3的加入使AlN致密化过程提前,烧结温度降低;SPS制备的AlN陶瓷晶粒尺寸均匀一致,晶粒发育良好烧结过程中Sm2O3与AlN粉体表面的Al2O3膜层在晶界处形成Sm-Al-O化合物,该反应有效促进了AlN颗粒间的相互扩散和烧结体的致密,对于AlN晶格完整性的保留非常有利,使AlN烧结体获得了良好的导热性能,其热导率达到150W/(m·K).     

固相合成Co3O4纳米晶及晶化动力学研究

以Co(NO3)2·6H2O和NH4HCO3为原料,利用固相反应合成无定形前驱体,再经焙烧合成Co3O4纳米晶.用X射线衍射(XRD)分析了不同焙烧温度对合成Co3O4晶粒尺寸的影响.研究结果表明按Scherrer公式估算合成Co3O4纳米晶的晶粒尺寸在10～40nm,焙烧温度越高,晶粒尺寸越大;根据前驱体不同升温速率下的差热(DTA)曲线,用Kissinger和Ozawa法计算合成Co3O4纳米晶的活化能分别为132.77kJ/mol和141.17kJ/mol,差别不大;根据晶粒生长动力学理论计算Co3O4晶粒长大的活化能为15.44kJ/mol,表明热处理过程Co3O4纳米晶粒的长大主要以界面扩散为主.     

BaHfO3:Ce闪烁陶瓷的制备及发光性能

通过掺杂摩尔分数为0.3%的稀土Ce3+,制备了BaHfO3:Ce闪烁陶瓷,用XRD,TG-DSC,SEM及TEM表征了BaHfO3:Ce物相及形貌,研究了不同烧结工艺下BaHfO3:Ce的致密化及显微组织.结果表明:前驱体的晶化转变存在三个阶段,在900℃煅烧2 h合成出BaHfO3:Ce纳米粒子,形貌为近球状,粒径尺寸约为15 nm.经真空烧结与常压烧结的样品致密化和显微组织存在明显差异:前者在1750℃真空烧结保温1.5 h,样品基本致密化,晶粒尺寸在40-50 μm范围内;而后者晶粒尺寸分布离散性较大.真空烧结后的闪烁陶瓷和同组分粉体样品在530 nm波长的激发光谱中分别存在380-420 nm紫色和420-450 nm蓝色的发光谱带,在391,398和445 nm波长处均出现较强峰值,对应着Ce3+4f→5d能级跃迁的吸收,这表明该闪烁陶瓷的发光强度高于同组分粉体样品.     

掺钕钇铝石榴石透明激光陶瓷的制备及其显微结构

以Al（NO3）3·9H2O、Y（NO3）3·6H2O和Nd2O3为原料，采用硝酸盐热分解法在1000℃左右合成了单相Nd：YAG陶瓷超细粉体。采用XRD及SEM等测试手段对Nd：YAG陶瓷材料进行了表征。结果表明，当焙烧温度为1000℃时，前驱粉体可以直接得到YAG立方晶相。没有YAM和YAP等中间相生成，煅烧所得的粉末颗粒细小均匀，呈椭球状，分散性较好，粒径在150-200nm之间。使用0．5％（质量分数，下同）的正硅酸乙酯作为烧结添加剂，前驱粉体经1700℃真空热压烧结5h后得到具有一定透明度的Nd：YAG多晶陶瓷，晶粒大多在3～4μm之间，晶界间还分布着少量的气孔。     

纳米SrCe0.95Y0.05O3-x陶瓷粉的制备与烧结

采用基于Pechini法的低温燃烧工艺制备了SrCe0.95Y0.05O3-x(SCY)前驱物.前驱物在900℃经0.5 h的煅烧处理即可得到纯的粒度在7～25 nm范围内的SrCe0.95Y0.05O3-x固体电解质纳米粉.将煅烧的粉体在18 MPa压力下压成片状的素坯,在900～1 500℃的温度范围内于空气中烧结索坯10 h.用X射线衍射(XRD)表征煅烧粉体的晶体结构,用扫描电镜(SEM)和透射电镜(TEM)表征了煅烧粉体和烧结体的形貌和粒度,采用阿基米德法测量了烧结体的密度.结果表明:温度达到1 000℃时,烧结体的径向收缩率和密度随着温度的升高而显著增加;温度达1 300℃时烧结体的径向收缩率和密度趋于恒定,得到相对密度高于96%、平均粒径约为3.68 μm的SrCe095Y0.05O3-x固体电解质陶瓷体.     

Influence of rare-earth ions on structural and magnetic properties of CdFe<Subscript>2</Subscript>O<Subscript>4</Subscript> ferrites

Nano-sized powders of rare-earth ions added CdFe2O4 ferrites were synthesized by oxalate co-precipitation method.The influence of R ions(R = Sm3+, Y3+, and La3+) on the microstructure and magnetic properties of CdFe2O4 ferrites was studied.XRD, SEM, FTIR, and magnetic hysteresis loops were used for analyzing the samples.The addition of R ions alters the structure of the powders and decreases the crystalline size, lattice constant, and grain size.The magnetic properties such as saturation magnetization, rema...     

Influence of rare-earth ions on structural and magnetic properties of CdFe_2O_4 ferrites

Nano-sized powders of rare-earth ions added CdFe2O4 ferrites were synthesized by oxalate co-precipitation method.The influence of R ions(R = Sm3+, Y3+, and La3+) on the microstructure and magnetic properties of CdFe2O4 ferrites was studied.XRD, SEM, FTIR, and magnetic hysteresis loops were used for analyzing the samples.The addition of R ions alters the structure of the powders and decreases the crystalline size, lattice constant, and grain size.The magnetic properties such as saturation magnetization, remanent magnetization, and magnetic moment increased due to addition of rare-earth ions in CdFe2O4 ferrite.The formation of secondary phase on the grain boundaries supports the abnormal growth.FTIR spectra show two absorption bands.Results suggest that the magnetic properties depend on the particular method of preparation and additives.     

复合稀土氧化物掺杂W-20Cu复合材料的制备及组织性能研究

以偏钨酸铵和硝酸铜为原料,采用EDTA-柠檬酸法制备了含有0~0.8wt.%稀土氧化物( Ce_0.8Sm_0.2O_1.9, SDC)的W-20Cu复合粉体,所制备的复合粉体经压制成型、1250°C烧结2h后获得SDC/W-20Cu复合材料烧结体。对所制备复合粉体进行物相、形貌的表征;研究稀土氧化物的添加对SDC/W-20Cu烧结体的密度、组织结构和物理力学性能的影响。实验结果表明：所制备的W-Cu复合粉体平均粒度为100~200nm;同时,SDC的添加对烧结体的密度和电导率会有轻微的影响,但能够抑制晶粒的长大并明显改善烧结体的力学性能。经1250°C烧结后,SDC/W-20Cu烧结体的相对密度均高于97%;当SDC的添加量为0.6%时,具有最大的抗弯强度和显微硬度,分别是1128MPa和258HV;此外,在室温和600°C的测试条件下,其最大的抗拉强度可以达到580MPa和258MPa。     

Sm2Ce2O7-Gd2Zr2O7复合材料制备及热导率

目的探讨了Gd_2Zr_2O_7的颗粒度和含量对(Sm_2Ce_2O_7)1-x(Gd_2Zr_2O_7)x复合材料热导率的影响。方法用纳米级和微米级粉体制备了两个系列的(Sm_2Ce_2O_7)1-x(Gd_2Zr_2O_7)x复合材料。用X射线衍射技术分析了材料的相组成,用扫描电镜观察了复合材料的显微形貌,用纽曼科普定律计算了复合材料的比热,用激光脉冲法测试了材料的热扩散系数。根据比热、密度和热扩散系数计算了复合材料的热导率,并根据最终热导率结果,分析了Gd_2Zr_2O_7颗粒度和含量对复合材料热导率的影响。结果所合成的粉体均具有单一的萤石晶体结构,纳米级Gd_2Zr_2O_7粉体最大比表面积为15.413 m~2/g,微米级Sm_2Ce_2O_7粉体最小比表面积为0.226 m~2/g。所制备的两个系列的(Sm_2Ce_2O_7)1-x(Gd_2Zr_2O_7)x复合材料也表现出单一的萤石晶体结构,但晶粒大小不均匀。结论当x=0.5时,纳米粉体制备的复合材料存在明显的纳米晶。微米级Gd_2Zr_2O_7对复合材料声子热导率抑制不明显,但可以抑制高温光子热导率;纳米级Gd_2Zr_2O_7的引入可明显降低复合材料的声子热导率,但对高温光子热导率抑制不明显。两个系列复合材料的热导率均低于YSZ。     

Study on rare earth/alkaline earth oxide-doped CeO2 solid electrolyte

Five types of rare earth/alkaline earth oxide-doped CeO2 superfine-powders were synthesized by a low-temperature combustion technique. The relevant solid electrolyte materials were also sintered by pressureless sintering at different temperatures. The results of X-ray diffraction and transmission electron microscopy showed that the grain size of the powders was approximately 20-30 nm, and rare earth/alkaline earth oxides were completely dissolved into ceria-based solid solution with fluorite structure. The electrical conductivities of the SmzO3-CeO2 system were measured by the ac impedance technique in air at temperatures ranging from 513-900℃. The results indicated that the ionic conductivities of Srno.2oCe0.8Ol.875 solid electrolyte increase with increasing sintering temperature, and the relationship between the conductivities and measuring temperature obeys the An＇henius equation. Then the SmzO3-CeO2 material was further doped with other rare earth/alkaline earth oxide, and the conductivities improve with the effective index.     

Synthesis and characterization of nanocrystalline Ni produced by cryomilling in liquid nitrogen

NanocrystaUine Ni powders were successfully fabricated by mechanically milling at cryogenic temperature （cryomilling） with 1 wt.%Y2O3 particles. The experimental results have shown that the Ni grain size is reduced to 25 nm after 2 h of cryomilling in the presence of the Y2O3 particles. The cryomiUed Ni/Y2O3 powders can maintain their nanocrystalline structure up to 900℃, or 62% of the melting point of Ni. A bulk nanocrystalline Ni/Y2O3 material with a thermally stable grain size of approximately 100 nm was produced by cryomilling, cold isostatic pressing, followed by hot isostatic pressing. The microhardness of bulk nanocrystalline Ni/1wt.%Y2O3 is 315 DPH, which is two times as high as that of conventional Ni.     

碳化镧锰水解氧化法制备La0.978Mn0.946O3氧化物

碳化镧锰合金在室温常压下进行水解氧化反应,洗涤并在50～80℃烘干得到La(OH)3和Mn3O4纳米粉。探讨了反应温度、反应时间、悬浮液浓度和碳化镧锰颗粒大小对晶粒尺寸的影响。优化工艺条件为:反应温度35℃,反应时间18 h,悬浮液浓度0.1 g/ml,碳化镧锰颗粒小于0.15 mm,得到比表面积为122.6 m2/g的La(OH)3和Mn3O4纳米粉。将该纳米粉分别在400、600、800℃和1 000℃煅烧2 h,最终得到晶化程度较好的La0.978Mn0.946O3氧化物。     

溶胶-凝胶法制备稀土锆酸盐陶瓷的结构及介电性能

采用溶胶-凝胶(Sol-Gel)法分别合成一元及多元稀土锆酸盐Sm2Zr2O7和(Gd0.4Sm0.5Yb0.1)2Zr2O7陶瓷粉体,在1600℃无压烧结10h合成致密的陶瓷块体。利用X射线衍射(XRD)仪及场发射扫描电镜(SEM)对各粉体和块体的微观结构进行表征,采用阻抗分析仪测试2种材料的介电性能。结果表明,一元及多元稀土锆酸盐均具有单一的焦绿石结构,中等的介电常数以及低的介电损耗,二者的介电常数均随频率的增加而下降;(Gd0.4Sm0.5Yb0.1)2Zr2O7陶瓷的介电常数低于Sm2Zr2O7,但二者的介电损耗值相差不多。该研究为进一步研究材料介电常数与热导率之间的关系奠定了基础。     

Sm掺杂对Ca_(0.4)Sr_(0.6)Bi_4Ti_4O_(15)铁电薄膜性能的影响

利用溶胶凝胶工艺在Pt/TiO_2 /SiO_2 /Si衬底上制备了Ca_0.4Sr_0.6Sm_xBi_4-xTi_4O_(15)铁电薄膜.研究了不同钐掺量对薄膜的显微结构、晶粒取向及铁电性能的影响.结果表明:钐掺杂对钙锶铋钛铁电薄膜既有抑制氧空位所导致的畴钉扎作用,也有抑制晶粒生长发育的作用.当钐掺量x=0.05时薄膜样品晶粒发育较良好,沿a轴择优取向,I_((200))/I_((119))=0.869;样品铁电性能优良,剩余极化强度P_r=10.2 μC/cm~2,矫顽场强度E_c=120 kV/cm.     

Electrochemical performance of La1-xSrxCuO3-δ-Sm0.15Ce0.85O1.925 composite cathodes in IT-SOFCs

The cathode material La1-xSrxCuO3-δ( x =0.15, 0.2, 0.3, 0.4) was synthesized by a sol-gel method. X-ray diffraction reveals that a single phase of perovskite is formed. The investigation of the electrical properties suggests that La0.7Sr0.3CuO3-δ has the highest electrical conductivity. La0.7Sr0.3CuO3-δ powder was mixed with different amount SDC (Sm0.15Ce 0.85O1.925) powder (5wt.%-30wt.%) as composite cathodes. Electrochemical properties of the composite cathodes were researched further. Investigation suggests that the addition of appropriate amount SDC to La0.7Sr0.3CuO3-δ can improve the electrochemical properties and obtain better cathodic performance. Using La0.7Sr0.3CuO3-δ-SDC composite materials as a cathode based on SDC electrolyte, higher current density and power density at intermediate temperatures can be obtained.