亚微米Al2O3 对重结晶碳化硅的作用机制

使用不同粒径的SiC和亚微米Al₂O₃添加剂制备重结晶烧结碳化硅并表征其物相组成、微观形貌、孔径分布和耐压性能,研究了亚微米Al₂O₃对重结晶碳化硅的作用机制。结果表明,在亚微米Al₂O₃作用下,重结晶碳化硅的烧结过程可分为液相烧结和重结晶烧结两个阶段。在液相烧结过程中高活性的亚微米Al₂O₃促进了液相的形成,使SiC的传质方式由扩散传质演变为粘性流动传质。在重结晶烧结温度SiC的传质以蒸发-凝聚为主,形成含铝气相并与SiC固溶促进了6H-SiC向4H-SiC晶型的转变。引入亚微米Al₂O₃后,重结晶碳化硅材料的孔径分布由单峰分布转变为多峰分布,其中孔径较小的特征峰对应重结晶烧结形成,而较大孔径的特征峰则来源于液相烧结的形成；同时,随着保温时间的延长SiC晶粒生长发育更为完全,由不规则颗粒状转变为较规则六方结构。但是,体积密度的下降、SiC晶粒尺寸不均一以及材料孔径的多峰分布使其耐压强度降低。     

铝酸盐的组成对钡钨阴极性能的影响

采用液相共沉淀法制备了612铝酸盐(n(BaO):n(CaO):n(Al₂O₃)=6:1:2)前驱粉末, 在不同气氛(H₂、CO₂、N₂)、不同温度(1300℃、1400℃、1500℃)焙烧制备铝酸盐, 系统研究了不同工艺制备的铝酸盐对钡钨阴极性能的影响。结果表明: 前驱粉末的最佳焙烧工艺为: H₂气氛、1500℃, 可获得主相为Ba₅CaAl₄O₁₂的铝酸盐, 用其制备的钡钨阴极发射电流密度可达12.2 A/cm², 蒸发速率仅为1.09×10^-8 g/(cm²?s)。     

以YbH2-MgO体系为烧结助剂制备高热导率高强度氮化硅陶瓷

以YbH₂-MgO体系为烧结助剂, 采用两步法烧结制备了高热导率高强度氮化硅陶瓷, 研究了YbH₂-MgO对氮化硅致密化行为、相组成、微观形貌、热导率和抗弯强度的影响。在预烧结阶段, YbH₂在还原SiO₂的同时原位生成了Yb₂O₃, 进而形成“缺氧-富氮”液相。该液相不仅有利于晶粒的生长, 更有利于阻碍晶格氧的生成, 相较于Yb₂O₃-MgO助剂体系, β-Si₃N₄晶粒尺寸更大, 晶格缺陷更少, 低热导晶间相更少, 在1900 ℃保温24 h后, 热导率最优可达131.15 W·m^-1·K^-1, 较Yb₂O₃-MgO体系提升13.7%。用YbH₂代替Yb₂O₃, 在低温条件下烧结制备得到的氮化硅抗弯强度有所改善, 在1800 ℃保温4 h的抗弯强度可达(1008±35) MPa; 但在高温烧结时强度略有下降, 这与微观结构的变化密切相关。研究表明, YbH₂-MgO体系是制备高热导率高强度氮化硅陶瓷的有效烧结助剂。     

钪钨基压制型阴极的制备及性能研究

将活性发射盐与氧化钪掺杂钨粉采用不同混合的方法结合,结合氢气气氛下的高温烧结法制备了氧化钪掺杂钨基扩散阴极。实验结果表明元素混合的均匀性对阴极的发射有着重要的影响。采用高能球磨法混合的粉末,元素分布均匀且颗粒细小,高温烧结过程中有利于发射盐与基体元素钨之间反应充分,形成有利于发射的活性物质。该种方法制备的阴极,发射性能为手工研磨混合的8倍,且为覆Os钡钨阴极的4倍。在激活过程中,活性元素Ba、Sc和O从阴极内部向表面扩散,在表面形成均匀分布的含Ba、Sc和O的活性层,促进了阴极的发射。     

二氧化钛纳米棒的制备及其晶体生长机理分析

采用溶剂热法合成具有高结晶性与单分散性的TiO₂纳米棒. 采用TEM、XRD、HRTEM等对样品的微观结构进行表征, 并考察了TiO₂纳米棒对亚甲基蓝的光催化性能. 通过控制反应时间、反应温度, 研究纳米棒的形貌演变规律.结果表明, 可以通过“奥斯特瓦尔德熟化”和“取向接触”两种晶体生长过程制备出棒状TiO₂纳米晶, 降低纳米晶的表面能是晶体生长与形貌演变的主要驱动力; 高结晶性的TiO₂纳米棒具有高于P25的光催化能力.     

氧化钪掺杂、亚微米结构多孔钨基扩散阴极的研究

为了改进氧化钪的分布均匀性及提高阴极表面氧化钪的扩散补充能力,作者在前期研究的基础上,分别采用液固掺杂和液液掺杂的方法制备了Sc2O3掺杂W粉基材,研究了利用这种W粉制作多孔钨基体的工艺技术和多孔体的微观结构.研究表明在改进压制、烧结技术的基础上,可以获得具有适当孔度的亚微米结构多孔基体.氧化钪在基体中的分布得到进一步改进.在这种基体中铝酸盐的浸渍率可以达到常规浸渍阴极的要求.发射试验结果表明,阴极具有很高的发射水平.研究还证实多孔体的结构越趋细微,越有利于阴极的发射均匀性和耐离子轰击的性能的改善.     

蒸汽相转化涂晶法SAPO-34分子筛膜的制备及表征

采用一种新型涂晶方法即蒸汽相转化涂晶法, 在廉价大孔α-Al₂O₃载体上水热合成制备高质量的SAPO-34分子筛膜。该方法能够有效修复α-Al₂O₃载体的大孔缺陷, 通过制备平整均匀的晶种层, 最终得到了连续并且无明显“针孔”缺陷的SAPO-34膜。实验考察了浆料中添加尺寸分别为2 μm、1 μm、500 nm及100 nm的晶种对形成晶种层及分子筛膜的影响, 并将制备的分子筛膜用于渗透汽化异丙醇脱水实验。在75℃下对90wt%的异丙醇/水混合物具有优良的分离性能, 其通量和分离系数分别为1.396 kg/(m²·h)和973。     

含稀土氧化物难熔盐浸渍W基直热式阴极研究

为了提高磁控管阴极的工作性能, 采用新型La₂O₃/Y₂O₃-Gd₂O₃-ZrO₂难熔盐浸渍W基制备直热式阴极, 并对该阴极的热发射特性和寿命特性等进行了测试。热发射测试结果表明, La₂O₃-Gd₂O₃-ZrO₂浸渍阴极在1600℃可提供超过0.18 A/cm²的空间电荷限制区电流密度。在同等发射电流下, 该浸渍阴极的工作温度比纯W阴极降低至少300℃, 该阴极在1750℃, 0.5 A/cm²直流负载下, 可以连续工作2100 h。当以Y₂O₃代替La₂O₃, 采用相同的配比制备阴极时, 1400℃、1700℃下即可分别提供超过0.6、3.4 A/cm²的空间电荷限制区电流密度。Y₂O₃-Gd₂O₃-ZrO₂浸渍阴极的工作温度比La₂O₃-Gd₂O₃-ZrO₂浸渍阴极降低至少400℃, 该阴极在1600℃, 1.5 A/cm²直流负载下, 可以连续工作2600 h。最后, 对这两种新型含稀土氧化物难熔盐浸渍阴极的热发射机理进行了探讨。     

稀土难熔金属阴极材料的研究进展

介绍了3种阴极,镧钼阴极、稀土钼金属陶瓷阴极及钪钨基扩散阴极的制备方法及发射性能.针对电子管用镧钼阴极发射不稳定的问题,采用原位光电子能谱法研究高温下La2O3(4%,质量分数)-Mo阴极表面La的价态,确定了适合La2O3-Mo阴极的碳化、激活等关键工艺制度,使实用型La2O3-Mo电子管的使用寿命超过了应用要求的水平.为满足大功率磁控管的发展要求,研究了新型稀土钼金属陶瓷阴极.经过高温激活处理后,材料的最大次级发射系数达5.24,实用管型测试结果表明,稀土钼金属陶瓷阴极的性能优于钡钨阴极,显示了良好的应用前景.亚微米结构的钪钨基扩散阴极具有优异的热发射性能,850 ℃下阴极的发射电流密度可达42 A/cm2,激活后Ba,Sc,O等元素形成的活性多层,均匀覆盖在阴极表面,促进了阴极的发射.     

Gd0.2Ce0.8O2包覆LaNi0.6Fe0.4O3-δ阴极材料抗铬污染性能

应用丝网印刷和共烧结制备LaNi_0.6Fe_0.4O_3-δ (LNF)/Sc_0.1Zr_0.9O_1.95(ScSZ)/LaNi_0.6Fe_0.4O_3-δ 对称电池.以硝酸铈和硝酸钆为原料、柠檬酸为燃料,采用燃烧法制备质量分数为21.3%的Gd_0.2Ce_0.8O₂(GDC)包覆的LNF阴极.电化学阻抗谱(EIS)表明:在750 ℃工作温度下,当无Cr基合金接触时,质量分数21.3%的GDC包覆的LNF经过1 200 h的搁置,其极化电阻由0.13 Ω·cm²增加至0.40 Ω·cm²,而纯LNF经过500 h的搁置,极化电阻由0.70 Ω·cm²增加至2.36 Ω·cm²,GDC的包覆加速了气体/阴极/电解质三相界面反应区的扩散过程,降低了阴极极化电阻;当有Cr基合金接触时,相对于质量分数为21.3%的GDC包覆的LNF阴极,LNF/ScSZ界面处沉积出大量Cr₂O₃,减缓了活性粒子在三相界面处的扩散,故其极化电阻远大于相同条件下质量分数为21.3%的GDC包覆的LNF阴极的极化电阻,质量分数为21.3%的GDC包覆的LNF阴极具有较佳的抗铬污染性能.     

CaO对17Ni/(10NiO-NiFe2O4)金属陶瓷的致密化及力学性能的影响

采用冷压-烧结技术制备了CaO掺杂的17Ni/(10NiO-NiFe₂O₄)金属陶瓷惰性阳极。研究了CaO的添加量和烧结温度对17Ni/(10NiO-NiFe₂O₄)金属陶瓷的物相组成、 致密度和力学性能的影响。结果表明, CaO含量在小于5.0wt%范围内, 烧结样品由Ni、 NiO和NiFe₂O₄组成。CaO掺杂对17Ni/(10NiO-NiFe₂O₄)金属陶瓷具有明显的助烧作用。当烧结温度为1250℃时, CaO掺杂量为1.0wt%的样品致密度达到最大值97.87%, 继续增加CaO掺杂量将导致材料致密度的下降。当烧结温度从1250℃提高到1350℃时, 当CaO掺杂量小于0.5wt%时, 样品的致密度随烧结温度的提高而增加; 当CaO掺杂量大于或等于0.5wt%时, 样品的致密度随烧结温度的提高而降低。提高烧结温度和添加CaO均能促进陶瓷相晶粒长大。样品在1250℃烧结时, 其抗弯强度在CaO掺杂量为1.0wt%时达到极大值为150.66MPa。     

Preparation of Gd_2O_2S:Pr Scintillation Ceramics by Pressureless Reaction Sintering Method

Fabrication of Gd2O2S:Pr scintillation ceramics by pressureless reaction sintering was investigated. The 2Gd2O3·(Gd,Pr)2(SO4)3·mH2O precursor was made by hydrothermal reaction using commercially available Gd2O3, Pr6O11 and H2SO4 as the starting materials. Then single phase Gd2O2SO4:Pr powder was obtained by calcining the precursor at 750°C for 2 h. The Gd2O2SO4:Pr powder compacts can be sintered to single phase Gd2O2S:Pr ceramics with a relative density of 99% and mean grain size of 30 μm at 1750°C for 2 h ...     

Li2CO3-B2O3-V2O5掺杂ZnO-TiO2陶瓷低温烧结的研究

以Li2CO3、B2O3和V2O53种常见的低熔点氧化物为烧结助剂,用传统固相法制备了Li2CO3-B2O3-V2O5掺杂的ZnO-TiO2微波介质陶瓷,并利用XRD、SEM等研究了ZnO-TiO2陶瓷的烧结行为、物相组成、显微结构特征及微波介电性能等。结果表明,当掺入3%(质量分数)Li2CO3-B2O3-V2O5时,在840℃烧结2h可制备出体积密度为4.99g/cm3的ZnO-TiO2陶瓷,达到理论密度的96.5%以上,εr、Q.f、τf分别约为24、22900GHz、-4×10-6/℃。     

Extended X-ray absorption fine structure (EXAFS) study of secondary phases in Yb2O3-doped Si3N4 ceramics

Liquid-phase sintered Si3N4 doped with Yb2O3 as a sintering aid was characterized by both transmission electron microscopy and extended X-ray absorption fine structure (EXAFS) measurements. Structural information about the secondary phases was obtained with an emphasis being placed on the evaluation of EXAFS data. Two Si3N4 samples were processed which contained either 5 vol% or 10 vol% Yb2O3 as sintering additive. After sintering, only an amorphous secondary phase was observed in the material doped with 5 vol% Yb2O3. The material with the higher Yb2O3 volume fraction underwent a further heat treatment after the densification, in order to crystallize pockets of the secondary phase. This heat treatment resulted in the formation of Yb2Si2O7 at multi-grain junctions, with however, amorphous phases remaining along the grain and phase boundaries. The EXAFS data obtained from the two doped Si3N4 materials were compared with reference spectra obtained on pure Yb2O3 and synthetic Yb2Si2O7. No residual Yb2O3 was determined in the doped Si3N4 materials, independent of the Yb2O3 volume fraction. Compared to synthetic Yb2Si2O7, the secondary phase formed in the 10 vol% Yb2O3 containing material showed only subtle changes in the EXAFS data. A clear distinction between purely amorphous and a combination of crystalline plus amorphous Yb secondary phases was possible, when both doped Si3N4 materials were compared. However, no distinction between the glass phase present at triple junctions and the amorphous residue along grain/phase boundaries was feasible, since a full numerical data evaluation could not be performed.     

Microstructures and Dielectric Properties of Ba1-xSrxTiO3 Ceramics Doped with B2O3-Li2O Glasses for LTCC Technology Applications

Ba1-xSrxTiO3 ceramics, doped with B2O3-Li2O glasses have been fabricated via a traditional ceramic process at a low sintering temperature of 900 ℃ using liquid-phase sintering aids. The microstructures and di- electric properties of B2O3-Li2O glasses doped Ba1-xSrxTiO3 ceramics have been investigated systemat- ically. The temperature dependence dielectric constant and loss reveals that B2O3-Li2O glasses doped Ba1-xSrxTiO3 ceramics have di?usion phase transformation characteristics. For 5 wt% B2O3-Li2O glasses doped Ba0.55Sr0.45TiO3 composites, the tunability is 15.4% under a dc-applied electric field of 30 kV/cm at 10 kHz; the dielectric loss can be controlled about 0.0025; and the Q value is 286. These composite ceramics sintered at low temperature with suitable dielectric constant, low dielectric loss, relatively high tunability and high Q value are promising candidates for multilayer low-temperature co-fired ceramics (LTCC) and potential microwave tunable devices applications.     

SnO2掺杂对BMN陶瓷结构及介电性能的影响

采用固相烧结法制备Ba(Mg_(1/3)Nb_(2/3))O_3+x(x=0~8)%SnO_2(BMSN,x为质量分数)微波介质陶瓷,并研究SnO_2掺杂对Ba(Mg_(1/3)Nb_(2/3))O_3(BMN)微波介质陶瓷结构及介电性能的影响。XRD分析表明,陶瓷体系中存在两种相,主晶相Ba(Mg_(1/3)-Nb_(2/3))O_3和附加相Ba_5Nb_4O_(15)。随着x的增大,BMSN陶瓷体系的相结构逐渐由钙钛矿六方结构转变为立方结构,同时有序相逐渐由1∶2有序结构转变为1∶1有序结构。研究表明:添加适量的SnO_2可以促进液相烧结,当SnO_2掺杂质量分数为6%时,BMN陶瓷致密化烧结温度由纯相时的1 550℃以上降低至1 200℃,表观密度ρ=6.39g/cm3,相对理论密度为99.1%,此时BMSN陶瓷体系拥有优良的微波介电性能——高相对介电常数(ε_r=33.6),接近于零的谐振频率温度系数(τ_f=0.15×10~(-6)℃~(-1)),高品质因数与谐振频率的乘积(Q·f=112 300GHz(8GHz))。     

Effects of Phase Composition on Microstructure and Mechanical Properties of Lu_2O_3-doped Porous Silicon Nitride Ceramics

Porous silicon nitride ceramics(Si3N4) were fabricated by pressureless sintering using different particle size of silicon nitride powder.Lu2O3 was used as sintering additive.According to phase relationships in the ternary system Si3N4-SiO2-Lu2O3,porous Si3N4 ceramics with different phase composition were designed through the change of the content of SiO2 which was formed by the oxidation at 800℃ in air.Porous Si3N4 with different phase compositions was obtained after sintering at 1800℃ in N2atmosphere.A small content of SiO2 favored the formation of secondary phase Lu4Si2O7N2,while large content of SiO2 favored the formation of secondary phase Lu2Si2O7 and Si2N2O.Porous Si3N4 ceramics with secondary phase Lu4Si2O7N2 had a flexural strength of 207 MPa,while that with secondary phase Si2N2O and Lu2Si2O7 had lower flexural strength.     

Recent progress on RE2O3-Mo/W emission materials

RE2O3-Mo/W cathodes were prepared by powder metallurgy method. La2O3-Y2O3-Mo cermet cathodes prepared by traditional sintering method and spark plasma sintering (SPS) exhibit different secondary emission properties. The La2O3-Y2O3-Mo cermet cathode prepared by SPS method has smaller grain size and exhibits better secondary emission performance. Monte carlo calculation results indicate that the secondary electron emission way of the cathode correlates with the grain size. Decreasing the grain size can decrease the positive charging effect of RE2O3 and thus is favorable for the escaping of secondary electrons to vacuum. The Scandia doped tungsten matrix dispenser cathode with a sub-micrometer microstructure of matrix with uniformly distributed nanometer-particles of Scandia has good thermionic emission property. Over 100 A/cm2 full space charge limited current density can be obtained at 950Cb. The cathode surface is covered by a Ba-Sc-O active surface layer with nano-particles distributing mainly on growth steps of W grains, leads to the conspicuous emission property of the cathode.     

V~(5+)-Sr~(2+)共掺杂对TiO_2基压敏陶瓷性能的影响

研究了V~(5+)-Sr~(2+)共掺杂对TiO_2基压敏陶瓷电学性能的影响。采用固相烧结方法制备V~(5+)-Sr~(2+)共掺杂TiO_2样品。利用XRD衍射仪检测物相和SEM测定显微结构。用压敏电阻直流参数仪测定V~(5+)-Sr~(2+)共掺杂TiO_2样品在不同烧结温度和掺杂量下的电学性能。结果表明:掺杂0.35mol%的V_2O_5,XRD衍射仪没有检测到第二相的产生。随着SrCO_3掺杂量以及烧结温度的增加,样品压敏电压和非线性系数都有不同的变化趋势。当烧结温度为1 300℃、Sr~(2+)掺杂量为0.5mol%时,样品的各项电学性能最优:V~(5+)-Sr~(2+)共掺杂TiO_2样品压敏电压达到16.3V/mm,非线性系数α达到5.6。     

Mg4Nb2O9/CaTiO3复合陶瓷的微波介电性能

采用传统固相法制备Mg4Nb2O9/CaTiO3复合陶瓷,研究Li2CO3-V2O5(LV)共掺杂对其烧结特性、微观结构和微波介电性能的影响.实验结果表明:一定量的LV掺杂能够使Mg4Nb2O9/CaTiO3复合陶瓷的烧结温度降至1200℃;XRD和EDX综合分析表明,样品由(Mg4-xCax)Nb2O9/(Ca1-x...