C／C复合材料防氧化涂层SiC／SiC—MoSi2的制备与抗氧化性能

采用包埋法和涂刷法在C/C复合材料表面依次制备了SiC内涂层和SiC-MoSi2外涂层,借助XRD与SEM对涂层的微观结构进行了分析,研究了涂覆后的C/C复合材料在高温静态空气中的防氧化性能.结果表明:SiC/SiC-MoSi2复合涂层有效缓解了MoSi2与C/C热膨胀不匹配问题,涂层无裂纹;复合涂层在900和1500℃静态空气环境下均可对C/C复合材料有效保护100 h以上;涂层的多层、多相结构以及在高温氧化后表面生成的SiO2薄膜是其具有优异防氧化性能的原因.     

MoSi2涂层高温抗氧化性能研究进展

综述了MoSi2作为C/C复合材料和难熔金属的高温抗氧化涂层的氧化性能的研究进展,比较研究了MoSi2高温抗氧化涂层的制备工艺,提出了MoSi2涂层技术的未来发展方向,即研发高温长寿命高可靠性抗氧化涂层、超高温抗氧化涂层,以满足航空发动机及航天飞机在恶劣工况条件下的使用要求.     

铌表面MoSi2高温涂层的形貌和结构研究

用料浆熔烧法在铌基体表面制备了。MoSi2高温抗氧化涂层。利用SEM，EDS，XRD等仪器分析研究了涂层的结构、元素分布、相分布与抗氧化性能的关系。结果表明：涂层与基体之间达到了冶金结合，通过扩散形成了过渡层，涂层的复合结构有利于提高抗氧化性能，用料浆熔烧法在铌基体表面制备MoSi2涂层是可行的。在氧化环境下，MoSi2涂层能在表面自生成一层SiO2玻璃层，阻止氧的进一步扩散。经2h以上高温氧化后，Si的扩散使涂层主体中形成多孔疏松组织。涂层元素与基体发生互扩散，在界面处形成大量集中孔洞并横向贯穿，使涂层从其主体与过渡层接触的界面处发生横向内部断裂，导致涂层失效。     

磁控溅射法制备碳/碳复合材料 SiC/MoSi2-ZrB2 涂层的结构及抗氧化性能研究

通过磁控溅射法在碳/碳复合材料表面成功制得了SiC/MoSi2-ZrB2陶瓷涂层并对结构及其在高温有氧环境中的抗氧化性能进行了研究。结果表明制备的SiC/MoSi2-ZrB2陶瓷涂层呈柱状晶结构且均匀性良好,其在1273K和1773K的有氧环境中氧化60min失重率分别是5.6×10-2 g/cm2 和 6.3×10-2 g/cm2。     

二硅化钼涂层对碳化硅电热元件高温抗氧化性能的影响

采用MoSi2粉末自烧结方法，在SiC电热元件表面制备一层致密的MoSi2高温抗氧化涂层，并对其高温抗氧化性进行测试。抗氧化试验在空气中1500℃炉温下进行118h和32次热循环，结果表明，带有MoSi2涂层的试样表面致密光洁，且试样抗氧化性能随MoSi2涂层厚度增加。SEM和EPMA显微分析表明，MoSi2涂层与SiC基体结合较好，没有起层和剥落，涂层中Mo分布均匀，损失约为20％。     

C／C复合材料Mo-Si-N抗氧化涂层的制备

在C／C复合材料表面采用熔浆法制备Mo—Si系涂层的烧结过程中通入氮气，开发了Si3N4．MoSi2／Si—SiC（Mo-Si-N系）多层抗氧化涂层，并初步考察了涂层的抗氧化性能。结果表明，多层涂层的致密性主要受制于起始氮化温度。只有在Si熔点以上通入氮气，才能获得致密无缺陷的涂层。多层涂层的底层为SiC，外层为Si3N4，中间层为MoSi2／Si。这种多层涂层的抗氧化性能与涂层中MoSi2的含量有关；MoSi2含量为30％（体积分数，下同）和40％时，与真空中合成的Mo-Si涂层相比，高温抗氧化性能显著改善，抗氧化温度提高到1400℃～1450℃。     

高温气冷堆燃料元件基体石墨的SiC/SiO2抗氧化涂层研究

提高高温气冷堆用石墨的抗氧化性能对改进高温气冷堆的安全性具有重要意义.通过热力学分析确认了SiC/SiO2,复合涂层在高温气冷堆正常服役条件和事故条件下均能保证其长期热稳定性.结合气相反应扩散法、泥浆浸渗法和高温氧化法,在高温气冷堆燃料元件基体石墨表面制备出SiC/SiO2复合涂层;对涂覆SiC/SiO2复合涂层的高温气冷堆燃料元件基体石墨在各种氧化条件下的氧化行为进行了分析.结果表明在高温气冷堆用石墨可能遇到的多种氧化条件下,SiC/SiO2复合涂层均能够保持长期稳定并显著改善基体石墨的抗氧化性能.     

ZrB2-MoSi2/SiC涂层C/C复合材料的制备及氧化性能（英文）

为了提高C/C复合材料的抗氧化性,在C/C复合材料基体上制备了ZrB2-MoSi2/SiC涂层。采用包埋法制备SiC中间层,采用喷涂法制备ZrB2-MoSi2外涂层。用XRD和SEM分别分析、测试所制备涂层的物相组成和显微结构,研究涂层复合材料的高温抗氧化性能。结果表明:C/C复合材料的外涂层由ZrB2、MoSi2和SiC三相组成;在1273K和1773K下分别氧化30h和10h后ZrB2-MoSi2/SiC涂层试样的质量损失分别为5.3%和3.0%,涂层表面长有纳米SiC晶须。C/C复合材料ZrB2-MoSi2/SiC涂层具有自愈合特性和良好的高温抗氧化性能。     

SiZr液相烧结法制备SiC-ZrC涂层对C/SiC复合材料抗氧化性能的影响

使用Si-25％Zr(质量分数)合金通过液相烧结法在C/SiC复合材料表面制备了SiC-ZrC抗氧化涂层,研究了烧结过程中涂层的相结构演化,并测试了1400℃及空气气氛下材料的抗氧化性能,分析了涂层氧化前后显微结构的变化,以及氧化对C/SiC复合材料弯曲性能的影响.结果表明,Zr元素在涂层中以ZrC相的形式存在,ZrC颗粒的引入细化了反应SiC层的组织,在氧化过程中形成致密连续的SiO2薄膜,并在氧化500 s后试样出现增重,制备了SiC-ZrC抗氧化涂层的C/SiC样品在1000 s的氧化实验后弯曲强度下降低于5％.     

炭/炭复合材料表面SiC/ZrSiO4-SiO2复合涂层的抗氧化性能与红外发射特性研究

为提高炭/炭(C/C)复合材料的高温抗氧化性能并降低其红外发射率,采用包埋–刷涂法在其表面制备了SiC/ZrSiO_4-SiO_2复合涂层。借助XRD、SEM等表征分析了涂层的成分与微观结构,并研究了SiC/ZrSiO_4-SiO_2复合涂层包覆C/C复合材料在1500℃动态空气条件下的抗氧化性能,以及在90和500℃下的红外发射率。结果表明:由疏松结构SiC内涂层和镶嵌结构ZrSiO_4-SiO_2外涂层组成的SiC/ZrSiO_4-SiO_2复合涂层具有优异的抗氧化性能,在1500℃流动空气(0.6 L/min)等温氧化条件下氧化50 h后试样的氧化失重率仅为0.03%。在C/C复合材料表面制备SiC/ZrSiO_4-SiO_2复合涂层后其红外发射率明显降低,并随温度升高而越低。复合涂层包覆试样在90℃时3~5μm和8~14μm波段的平均红外发射率分别为0.55和0.66;在500℃时3~5μm和8~14μm波段的平均红外发射率分别为0.48和0.62。SiC/ZrSiO_4-SiO_2复合涂层包覆C/C复合材料可作为优良的低红外发射率高温热结构材料应用于航空航天领域。     

Al2O3包覆改善P2型Na2/3Fe1/2Mn1/2O2正极材料的存储性能

采用超声喷雾热解与高温固相烧结相结合的方法合成P2型Na_2/3Fe_1/2Mn_1/2O₂材料。通过X射线衍射仪、扫描电子显微镜和电化学充放电设备对材料的结构、形貌和电化学性能进行全面的表征。此外,在Na_2/3Fe_1/2Mn_1/2O₂表面包覆Al₂O₃薄层,该包覆层可以抑制Na₂CO₃·H₂O的形成,提高Na_2/3Fe_1/2Mn_1/2O₂材料的存储性能,从而改善其电化学性能。这种简单的表面改性方法为合成高性能钠离子电池正极材料提供了新思路。     

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.     

Synthesis and properties of CaCd2Sb2 and EuCd2Sb2

High density polycrystalline CaCd₂Sb₂ and EuCd₂Sb₂ intermetallics are synthesized by Spark Plasma Sintering and their thermoelectric properties are investigated. X-ray diffraction measurements reveal both materials have a structure in space group, containing a small amount of CdSb as a second phase. Thermoelectric measurements indicate both are p-type conductive materials. The figure of merit value of CaCd₂Sb₂ is 0.04 at 600 K and that of EuCd₂Sb₂ is 0.60 at 617 K. Theoretical calculations show that CaCd₂Sb₂ is a degenerate semiconductor with a band gap of 0.63 eV, while EuCd₂Sb₂ is metallic with DOS of 13.02 electrons/eV. For deeper understanding of the better thermoelectric properties of EuCd₂Sb₂, its low temperature magnetic, transport and heat capacity properties are investigated. Its Nèel temperature is 7.22 K, convinced by heat capacity anomaly at 7.13 K. Hall effect convinced that it is a p-type conductive material. It has high Hall coefficient, high carrier concentration and high carrier mobility of +1.426 cm³/C, 4.38 × 10¹⁸/cm³ and 182.40 cm²/Vs, respectively. They are all in the magnitude of good thermoelectric materials. The Eu 4f level around Fermi energy and antiferromagnetic order may count for the better thermoelectric properties of EuCd₂Sb₂ than that of CaCd₂Sb₂.     

Bi2Sr2CaCu2Ox bulk superconductor with MgO particles embedded

MgO nano-size particles in various concentrations were added to the Bi-2212 superconductor precursor before partial melting. The resulting ceramic superconductors had a transition sharpness and volume fraction which increased with MgO addition up to 9 wt.%. Compositional variations in the superconducting matrix with varying MgO addition were found, with possible important consequences for the pinning mechanism, since compositional variations are expected to be accompanied by variations in T_c. By TEM it was directly documented that MgO particles could be embedded within the superconducting Bi-2212 grains. Hence wetting occurs. Thus, the requirements for MgO to play an effective role in pinning are satisfied. It is suggested that two distinct pinning mechanisms, both related to MgO addition, are likely to be present. Magneto-optic images clearly confirm the improvement of pinning, and screening, with increasing addition of MgO to Bi-2212.     

Gd Mössbauer effect and magnetic properties of GdNi2Sb2, GdCu2Sb2 and GdAl2Ga2

We have investigated the magnetic properties and the ¹⁵⁵Gd Mössbauer spectra of the ThCr₂Si₂-type compounds GdNi₂Sb₂, GdCu₂Sb₂ and GdAl₂Ga₂. These three compounds were found to order antiferromagnetically, with T_N=6.5 K, 15.8 K, and 42.4 K respectively. The electric field gradient V₂₂ derived from the quadrupole splitting of the Mössbauer spectra gives rise to a sign change at the end of the T3d series in GdT₂Sb₂, as was observed previously also for the corresponding compounds with Si and Ge. This behaviour was explained in terms of decreasing hybridization between the Gd valence electron states and the d electron states of the T atoms.     

Corrosion characteristics of LiBH4 film exposed to a CO2/H2O/O2/N2 mixture

LiBH₄ films were prepared by pulsed laser deposition using a LiB target in a background pressure of hydrogen. The corrosion characteristics of LiBH₄ films were measured by exposing them to a gas mixture of CO₂/H₂O/O₂/N₂ at ambient temperature for 1–24 h. Scanning electron microscopy images show some cracks on the surface of corrosion films, which could act as easy paths for H₂O and CO₂ to further react with Li⁺ and B³⁺. The X-ray photoelectron spectroscopy results and theoretical analysis show that LiBH₄ tends to react with H₂O and CO₂ to form Li₂B₄O₇, Li₂CO₃ and LiOH during the corrosion process.     

Fe2+-Ni2+-NH3-NH4+-C2O42-H2O体系的沉淀配合平衡热力学

针对草酸盐配位共沉淀热分解还原法制备超细铁镍合金粉过程中Fe2+-Ni2+-NH3-NH4+-C2O42--H2O体系的溶液平衡建立热力学分析模型,并根据模型进行相关计算,揭示反应体系中各物质随pH值、氨及草酸浓度的变化关系。结果表明:溶液中的Fe主要以[Fe(C2O4)n]2 2n络合物形式存在,而铁氨络合物含量很低。当氨含量较低时,溶液中的Ni主要以[Ni(C2O4)n]2 2n存在;氨含量较高时,在酸性条件下,溶液中的Ni主要以[Ni(C2O4)n]2 2n存在,在碱性条件下,则主要以[Ni(NH3)n]2+存在。低pH值下,Ni的沉淀率较Fe的高,而高pH值下,Ni的沉淀率则较Fe的低。     

Thermodynamic evaluation of phase equilibria in the CaCl2-MgCl2-CaF2-MgF2 system

The phase diagram of the CaCl₂-CaF₂-MgCl₂-MgF₂ reciprocal ternary system was calculated thermodynamically from available data on the common-ion binary subsystems and from available data on the CaCl₂-MgF₂ join. This join is very nearly quasibinary and divides the system into two quasiternary systems: the CaCl₂-MgF₂-CaF₂ system with a ternary eutectic calculated at 724 +-5 °C and the CaC₂-MgF₂-MgCl₂ system with a ternary eutectic calculated at 561 +-5 °C.     

Impact of oxyfuel atmospheres H2O/CO2/O2 and H2O/CO2 on the oxidation of ferritic–martensitic and austenitic steels

In future power plant technologies, oxyfuel, steels are subjected to steam rich and carbon dioxide rich combustion gases. The effect of simulated combustion gases H₂O/CO₂/O₂ (30/69/1 mol%) and H₂O/CO₂ (30/70 mol%) on the corrosion behavior of low alloyed steels, 9–12% chromium steels and an austenitic steel were studied. It was discovered that the formation of protective chromium rich oxides is hampered due to the carburization of the base material and the formation of chromium rich carbides. The kinetics of corrosion and carburization are quantified. The effect of temperature and the effect of gas pressure are analyzed statistically.     

Al2O3-Sm2O3-CeO2电解质的性能（英文）

采用溶胶-凝胶法和低温燃烧技术制备Ce1-xSmxO2（x=0,0.1,0.2,0.3）和掺杂Sm和（2%-8%）Al2O3的二氧化铈;研究其合成、结构、致密化、导电性和热膨胀等性能,并利用XRD研究其结构和相组成。结果表明,于1300°C烧结球团,获得致密的陶瓷,于1250°C在Ce0.8Sm0.2O0.2中加入2%和4%的Al2O3以促进烧结。利用扫描电子显微镜观察烧结后球团的表面形貌,使用双探针交流阻抗谱研究总离子电导率。