含稀土助烧剂氮化硅陶瓷的热导率、强度及电学性能

高热导率氮化硅陶瓷作为基板材料有着广泛的应用前景.如何在尽可能保持氮化硅陶瓷机械性能的前提下,提高其热导率是其实际应用的关键,而选择适当的烧结助剂是提高热导率的一个重要途径.本文研究了稀土氧化物种类及CaO、MgO烧结助剂对氮化硅陶瓷的热导率及电学和机械性能的影响,分别采用Y2O3-MgO,Y2O3-CaO,CeO2-MgO,CeO2-CaO,La2O3-MgO和La2O3-CaO 6种烧结助剂,采用放电等离子烧结后热处理的工艺制备氮化硅陶瓷.研究结果表明:氮化硅陶瓷的热导率随着烧结助剂稀土元素阳离子半径的增大有减小的趋势;与添加MgO助烧结相比,添加CaO助烧结不利于氮化硅柱状晶的生长,热导率及强度普遍较低,但硬度较高.采用Y2O3-MgO助烧剂和适当的烧结工艺,可以得到热导率高于80 W/m·K、抗弯强度大于1000 MPa、体电阻率大于1×1013Ωm、介电常数小于10、介电损耗小于3×10-3的氮化硅陶瓷.     

粉料表面氧含量对GPS烧结氮化硅陶瓷显微结构的影响

通过研究GPS烧结氮化硅陶瓷的室温和高温抗弯强度、晶界相含量和成分以及晶界析晶相随氮化硅粉料表面氧含量的变化规律，发现当粉料表面氧含量低于1．35mg／m^2时，氮化硅陶瓷在室温下的抗弯强度基本保持不变。试样在1200℃时的抗弯强度明显低于室温强度，且随着粉料表面氧含量的增加有一最高值。由于烧结助剂引入的O和Si在烧结过程中的还原气氛下发生反应而损失，烧结体中晶界相的实际含量显著低于粉料中烧结助剂的加入量。随粉料表面氧含量的增加，氮化硅陶瓷烧结体中的二次析晶相α-Y2Si2O7和β-Y2Si2O7消失，只有β-Si3N4晶相和晶界玻璃相存在。     

Y2O3和La2O3对B4C基陶瓷烧结致密化及其结构和性能的影响

以Al2O3、La2O3、Y2O3和活性碳为烧结助剂,以B4C为基体,采用真空热压烧结技术制备B4C基陶瓷,研究了稀土氧化物对B4C基陶瓷微观结构和性能的影响.结果表明,添加稀土氧化物的试样在1 850 ℃烧结即可得到晶粒排列紧密、性能较佳的B4C基陶瓷.在未添加稀土氧化物的试样中,由于反应生成的新相Al8B4C7较少,烧结不充分,因此试样的性能较低.在添加La2O3的试样中,由于烧结比较充分, 烧结体中的新相LaAlO3含量较大,显微组织较理想,因此性能较佳.在添加Y2O3的试样中,残留的Al2O3和C的量很少,生成的Y3Al5O12也较少,因此性能介于前两者之间.     

添加Y2O3的AlN陶瓷注射成形研究

研究了添加5%和7%Y2O3的AIN陶瓷的注射成形工艺,制备了热导率达162.5W/m@K的AIN陶瓷.利用XRD,SEM,XPS等方法分析了注射成形中Y2O3的添加量、烧结工艺和第2相组成的关系,并发现注射成形AlN陶瓷的晶界第2相对AlN陶瓷的热导性能有显著的影响.     

Yb2O3或Y2O3掺杂Cu-(NiFe2O4-10NiO)惰性阳极的导电性和耐蚀性

在氧分压约为100 Pa的氮气氛下烧结制备了掺杂Y2O3、Yb2O3的10Cu-(NiFe2O4-10NiO)金属陶瓷,并对其进行导电性能测试和10h(Na3A1F6-Al2O3体系中)铝电解实验.采用XRD、SEM和EDS分析稀土氧化物以及其与陶瓷基体反应产物的分布,考查电解实验后材料表层显微结构变化尤其是金属相的流失情况,评价稀土氧化物的添加对金属陶瓷电解初期腐蚀行为的影响.结果表明:掺杂稀土氧化物均使NiO相呈连通迹象,掺杂Yb2O3金属陶瓷晶粒较未掺杂的粗大,其与陶瓷相反应生成物成点线状分布于NiFe2O4相晶界,Y2O3与陶瓷相反应生成物则分布于NiO与NiFe2O4相间;所制备材料具有半导体特征,随着稀土氧化物的掺杂,材料导电性呈下降趋势;掺杂稀土氧化物尤其是Yb2O3有利于提高材料的耐蚀性能.     

微观组织调控对氮化硅强度及热导率的影响

为了通过调控氮化硅陶瓷中β-Si_3N_4柱状晶形貌以得到兼具高热导率和高强度的陶瓷,以不同β-Si_3N4_/α-Si_3N_4配比粉末为起始原料,添加Y2O3和MgO为烧结助剂,采用放电等离子烧结技术(SPS)和后续高温热处理制备烧结致密的氮化硅陶瓷。结果表明:随着β-Si_3N_4粉末含量的增加,烧结后异常长大β-Si_3N_4柱状晶减少,试样抗弯强度下降,同时β-Si3N4柱状晶平均长径比的减小使得晶粒堆积密度减小,柱状晶体积分数响应增加,晶间相含量减少,热导率提高。     

Li2O为烧结助剂的Si3N4陶瓷低温烧结过程研究

分别选用Li2O烧结助剂和Y2O3-Al2O3复合烧结助剂作为对比,无压烧结氮化硅陶瓷,研究了Li2O对烧结致密化过程和相变过程的影响。结果表明,以Li2O作为烧结助剂,烧结系统的共晶液相在1200℃产生,颗粒重排可以在较低的温度下进行,且致密化速度较快,氮化硅的α-β相变过程被促进,在1600oC即可得到发育良好的β-Si3N4棒状晶。     

Y2O3对SPS烧结纳米AlN粉末的影响

利用低温燃烧法合成出了平均粒度为100 nm的AlN粉末,将合成的粉末采用放电等离子(SPS)技术进行低温强化烧结,研究Y2O3对烧结过程以及烧结试样特性的影响.XRD进行物相分析,SEM观察断口形貌,排水法测烧结试样的密度,激光闪光法测烧结试样的热导率.实验表明采用低温燃烧法合成出的AlN粉末具有非常好的烧结性能,采用SPS烧结技术,40 MPa压力下,在1600℃保温4 min,就能得到非常致密的AlN陶瓷;Y2O3对纳米AlN粉末在SPS低温强化烧结过程仍有促进作用,使试样在更低的温度下烧结致密,并且晶粒更细小,从而热导率也较低;加入Y2O3的烧结试样晶界强度增加,断口中有较多的穿晶断裂形式,而不加入Y2O3的烧结试样主要以沿晶形式断裂.     

Y2O3-MgO纳米复相红外透明陶瓷制备及其性能研究

以商用Y2O3、MgO纳米粉体为原料,通过球磨混合方法制备了不同Y2O3/MgO配比的Y2O3-MgO纳米复合粉体,使用X射线衍射、扫描电镜、能量色散谱等表征手段对制备粉体的晶体结构、形貌、成分以及均匀性进行了表征。然后采用热压烧结方法制备Y2O3-MgO复相红外透明陶瓷,使用红外光谱仪、维氏硬度计等测试设备对复相透明陶瓷的光学和力学性能进行了分析。重点研究了粉体配比、热压温度、保温和保压时间等关键制备参数对Y2O3-MgO复相红外透明陶瓷晶粒尺度、致密化程度、光学及力学性能的影响。并通过调控粉体制备工艺和热压烧结工艺,制备出了红外透过率达到~80%的Y2O3-MgO复相红外透明陶瓷。同时在Y2O3:Mg0=1:1时,该复相陶瓷的硬度达到了12.3 GPa。     

β-氮化硅粉烧结氮化硅陶瓷热导率

以自蔓延高温合成β-氮化硅粉为原料,添加稀土化合物Y2O3和MgO复合烧结助剂,采用放电等离子烧结后高温热处理的方法制备氮化硅陶瓷。研究β-氮化硅粉体制备致密氮化硅陶瓷的条件。讨论粉体种类(β-氮化硅或α-氮化硅)及SPS保温时间对氮化硅陶瓷热导率的影响。研究表明,采用β-氮化硅粉体制备的氮化硅陶瓷的热导率比采用相同工艺α-氮化硅粉体制备的氮化硅陶瓷高15%以上。采用SPS工艺在1873K烧结5min,然后再在2173K保温3h可以获得致密的氮化硅陶瓷,其热导率高达105W·(m·K)-1。     

Thermodynamics and phase diagrams in the binary systems Na2O-SiO2, Na2O-GeO2, Na2O-B2O3, Li2O-B2O3, CaO-B2O3, SrO-B2O3, and BaO-B2O3

We applied our model to the enthalpy of mixing data of the binary systems Na₂O-SiO₂, Na₂O-GeO₂, Na₂O-B₂O₃, Li₂O-B₂O₃, CaO-B₂O₃, SrO-B₂O₃, and BaO-B₂O₃. The most stable composition in the liquid, that is where the enthalpy of mixing is most negative, is with a metal-oxygen ratio of 4 to 3, for monovalent metals (Na and Li) and 3 to 4 for divalent metals (Ba and Ca) in liquid silicates or borates. The same applies to the CaO-SiO₂, CaO-Al₂O₃, PbO-B₂O₃, PbO-SiO₂, ZnO-B₂O₃, and ZnO-SiO₂ systems. The oxygen to metal ratio, its constant value in various types of systems, reflects and describes the structure of the liquid. Using the analyzed enthalpies of mixing data and the available phase diagrams, we calculated the enthalpies of formation of the various binary compounds. The results are in excellent agreement with data in the literature that were obtained from direct solid-solid calorimetry.     

Critical evaluation and optimization of the thermodynamic properties and phase diagrams of the CrO-Cr2O3, CrO-Cr2O3-Al2O3, and CrO-Cr2O3-CaO systems

Available thermodynamic and phase diagram data have been critically assessed for all phases in the CrO-Cr₂O₃, CrO-Cr₂O₂-Al₂O₃, and CrO-Cr₂O₂-CaO systems from 298 K to above the liquidus temperatures and for oxygen partial pressures ranging from equilibrium with metallic Cr to equilibrium with air in the case of the first two systems and toP _{O 2} = 10^?3 atm for the CrO-Cr₂O₃-CaO system. All reliable data have been simultaneously optimized to obtain one set of model equations for the Gibbs energy of the liquid slag and all solid phases as functions of composition and temperature. The modified quasichemical model was used for the slag. The models permit phase equilibria to be calculated for regions of composition, temperature, and oxygen potential where data are not available.     

Sintering Behavior and Mechanical Properties of NiAl,Al2O3, and NiAl-Al2O3 Composites

It is commonly known that the properties of sintered materials are strongly related to technological conditions of the densification process. This paper shows the sintering behavior of a NiAl-Al₂O₃ composite, and its individual components sintered separately. Each kind of material was processed via the powder metallurgy route (hot pressing). The progress of sintering at different stages of the process was tested. Changes in the microstructure were examined using scanning and transmission electron microscopy. Metal-ceramics interface was clean and no additional phases were detected. Correlation between the microstructure, density, and mechanical properties of the sintered materials was analyzed. The values of elastic constants of NiAl/Al₂O₃ were close to intermetallic ones due to the volume content of the NiAl phase particularly at low densities, where small alumina particles had no impact on the composite’s stiffness. The influence of the external pressure of 30 MPa seemed crucial for obtaining satisfactory stiffness for three kinds of the studied materials which were characterized by a high dense microstructure with a low number of isolated spherical pores.     

Fabrication and characterization of nano-Y2O3, Al2O3, La2O3 dispersed mechanically alloyed and liquid phase sintered WNi for structural application

The investigation involves the fabrication of various nano oxide (Y₂O₃, Al₂O₃, La₂O₃) dispersed WNi alloys by mechanical alloying for 10 h and sintering in Ar atmosphere at 1400 °C, 1500 °C for 2 h. The selected composition for the study is W₈₉Ni₁₀(Y₂O₃)₁ (alloy A), W₈₉Ni₁₀(Al₂O₃)₁ (alloy B) and W₈₉Ni₁₀(La₂O₃)₁ (alloy C) (in weight%). Alloy A exhibit least crystallite size and maximum lattice strain at 10 h of milling. The lattice parameter of W exhibits expansion and contraction behavior during the milling. Microstructure of sintered alloys reveals the presence of both faceted and nearly spherical shaped grains. Bimodal grain size distribution is higher in alloy A at 1500 °C as compared to other alloys and 1400 °C sintering temperature. Texture study and Young's Modulus value reveals that hardness of alloy A is higher against alloy B and alloy C. Maximum % relative sintered density, mean hardness, compressive strength of 89%, 5.53 GPa, 2.25 GPa respectively has been achieved in alloy A at 1500 °C.     

Y2O3含量对SiO2-Al2O3-B2O3-K2O-Li2O系统微晶玻璃的析晶及性能的影响

以SiO2-Al2O3-B2O3-K2O-Li2O为玻璃组成,P2O5和ZrO2为复合成核剂,Sb2O3为澄清剂,Y2O3为添加物,通过传统熔体冷却方法制得了该系统基础玻璃.利用DSC、XRD、SEM及性能测试等手段,研究了Y2O3含量的变化对玻璃析晶行为、析出晶相种类、晶粒尺寸、晶粒分布以及微晶玻璃的力学性能的影响.研究结果表明:随着Y2O3含量的增加,玻璃的析晶峰值温度升高,且析晶峰也逐渐变宽、变钝;Y2O3的加入并不影响微晶玻璃中主晶相的组成,但对其微观结构有明显影响;当Y2O3含量低于2.0%(摩尔分数)时,微晶玻璃的抗弯强度随Y2O3含量增加而增加;当Y2O3含量为2.0%时,获得微晶玻璃的抗弯强度值最高,达到217 MPa;当2.0%≤x(Y2O3)≤2.5%时,抗弯强度反而降低;当Y2O3含量为2.5%时,获得的微晶玻璃具有良好的半透明性,并具有较好的力学性能(抗弯强度为198 MPa);与一步法热处理相比,采用两步晶化热处理有利于提高微晶玻璃的力学性能.     

Gd2 O3 -Yb2 O3 -Y2 O3 -ZrO2 热障涂层材料的热物理性能

目的通过多元稀土氧化物掺杂改性YSZ,提高传统热障涂层的性能。方法使用化学共沉淀法制备不同掺杂量的Gd2O3-Yb2O3-Y2O3-Zr O2(GYYZO)材料,并分别使用冷等静压-烧结和等离子喷涂工艺制备块材和涂层。通过测试块材的热导率和热膨胀系数,分析评价材料的热物理性能。对高温退火处理后的涂层进行X射线衍射分析,评价不同成分涂层的高温相稳定性。结果氧化锆基材料的热导率和热膨胀系数随总掺杂量升高而降低。氧化锆中稀土氧化物总掺杂量为5.5%~9.84%(摩尔分数)时,在1000℃下的热导率为1.25~1.56 W/(m·K),相对8YSZ材料下降了22%~37.5%;在200~1300℃的热膨胀系数为(10~11.1)×10-6/K,与传统8YSZ材料相当。在1400℃长时间退火处理后,低掺杂量GYYZO涂层中的单斜相含量明显低于8YSZ涂层。结论多元稀土氧化物掺杂改性氧化锆材料具有良好的高温相稳定性、低热导率和适当的热膨胀系数,可以作为高性能热障涂层的备选材料。     

ZnO-Al2O3-B2O3-SiO2系微晶玻璃的研究

研究了能与可伐合金匹配封接的ZnO-Al2O3-B2O3-SiO2系微晶玻璃,其膨胀系数为5.2×10-6/℃,采用该微晶玻璃的封接器件绝缘电阻可达1×1013Q·cm.通过对该微晶玻璃的差热曲线分析,确定了其热处理制度;用X射线衍射仪和扫描电镜研究了该系统的主晶相,其主晶相为ZnAl2 O4、ZnB2O4和少量的NaSiAl2O4晶体.通过控制碱金属离子进入晶格,可明显提高微晶玻璃的绝缘电阻.     

La2O3-Gd2O3-Mo secondary emission material

A new kind of materials La2O3-Gd2O3-Mo has been produced by powder metallurgy method.The composition and microstructure of the material were studied by XRD and SEM.It shows that no chemical reaction takes place among La2O3,Gd2O3,Mo and the rare earth oxides exist along molybdenum grain boundaries and in the pores.The emission property measurement results of this material show that adding rare earth oxide into molybdenum can improve the secondary emission coefficient of the emitter,and the emission property depends on the activation temperature.After La2O3-Gd2O3-Mo was activated at 1360℃,the maximum secondary emission coefficient can be high to 2.62,which has exceeded that for practical uses(2.0).     

Fe2O3对SiO2-Al2O3-MgO-Fe2O3-F-系玻璃陶瓷析晶的影响

采用高温熔融法制备不同Fe2O3含量的SiO2-Al2O3-MgO-Fe2O3-F-系基础玻璃,应用扫描电子显微镜(SEM)和X射线衍射(XRD)等技术研究了Fe2O3含量对玻璃析晶的影响规律.结果表明在所研究的玻璃体系中,当玻璃中引入2.0%(质量分数,下同)Fe2O3后,促进了玻璃体的分相,在800℃较低温度下析出氟云母晶体,氟云母晶体的形状受到分相区尺寸的限制.提高析晶温度有利于氟云母晶体的析出.当玻璃中Fe2O3提高到6.0%后,仍能获得透明玻璃体,但是在重新加热时首先形成FeFe2O4相,而抑制了云母晶体的析出.     

Effects of Al2O3 content on densification,microstructure, mechanical properties and oxidation resistance of TaC-Al2O3 composites

TaC-Al₂O₃ composites were prepared by hot pressing. Influence of Al₂O₃ content ranging from 10 to 40 vol. % on densification, phase composition, microstructure, mechanical properties and oxidation behavior of the TaC-Al₂O₃ composites was investigated. With 30 and 40 vol. % Al₂O₃ addition a closed porosity was achieved. The Al₂O₃ particles were uniformly distributed among TaC grains retarding grain growth and resulting in refined microstructures with grains below 2 μm in size. The most densified composite with 40 vol. % Al₂O₃ addition exhibited good mechanical properties with a Vickers’ hardness of 17.8 GPa, a flexural strength of 485 MPa and a fracture toughness of 5.4 MPa·m^1/2. After holding at 700°C for 3 h in air, the dense 30 and 40 vol. % Al₂O₃ compositions showed hardly noticeable and mainly surface oxidation, whereas less densified TaC-Al₂O₃ composites with 10 and 20 vol. % Al₂O₃ content and with open porosity were disintegrated to powders.