Al2TiO5／ZrO2纳米复相陶瓷的制备及性能研究

以氧氯化锆((ZrOCl2·8H2O)、硫酸铝(Al2(SO4)3·18H2O)、硫酸氧钛(TiOSO4·2H2O)为初始原料,以氨水为沉淀剂,将液相共沉淀法得到的Al2TiO5/ZrO2纳米复合粉体前驱体,经1000℃焙烧2h,制备了ZrO2含量(w)为2%、5%、8%的Al2TiO5/ZrO2纳米复合粉体;复合粉体经造粒后以100Mpa压力成型试样,试样尺寸为53mm×10mm×10mm,经1350、1400、1450、1500℃2h制备了Al2TiO5/ZrO2(缩写AT/Z)纳米复相陶瓷试样。研究了ZrO2含量、烧结温度对试样的烧结性能、热膨胀性能、抗热震性能的影响,并借助XRD、SEM分析了试样的物相组成、显微结构。结果表明:随着ZrO2含量的增加和烧结温度的提高,试样的显气孔率减小,抗弯强度增大。烧结温度为1500℃、ZrO2含量(w)为5%的ATZ-54试样,抗弯强度最大,为103.2MPa;在1250℃的热膨胀率仅为0.08%,其热膨胀系数α约为0.65×10-6℃-1;AT/Z纳米复相陶瓷试样具有细晶镶嵌结构;从室温到1100℃急冷急热冲击31次后,试样表面仍保持完整,抗热震性能明显高于其他...     

MgO/CaZrO3和MgO/ZrO2复合物的工艺、烧结和性能

白云石-氧化锆和氧化镁-氧化锆两批料成比例配制了用于各种高温环境下的MgO/CaZrO3和MgO/ZrO2复合物。这些批料是在不同烧结温度下所制备的,即1400、1500和1600℃。用XRD和具有EDAX的扫描电子显微镜对所制备试样的晶相成分进行了研究分析。对烧成参数(体积密度和显气孔率),常温耐压强度和耐火性能(永久线变化PLC),抗热震性(TC),耐火度和荷软(RUL)也进行了研究。这两种复合物都具有良好的烧结性、机械和耐火性能。不过,白云石-氧化锆混合物还具有独特的性能。除了这些复合物(特别是白云石-氧化锆)具有完全致密的显微结构外,还具有良好的烧结性、机械和耐火性能,可以用作工程材料和用于高温环境下,特别是用于烧制石灰、白云石、镁砂和波特兰水泥的回转窑和竖窑中。     

先驱体转化法制备莫来石毡/氧化锆多孔复合材料的显微结构与力学性能

以ZrO2前驱体混合液作为浸渍液,莫来石毡为前驱体附着骨架,采用真空压力浸渍工艺制备出莫来石毡/氧化锆多孔复合材料。研究了不同烧结温度(1 300、1 350、1 400和1 450℃)下该多孔复合材料的物相组成、体积密度、开口气孔率、压缩强度及显微结构。结果表明,烧结之后的多孔复合材料发生了四方相氧化锆到单斜相氧化锆的转变,相转变过程直接导致较低烧结温度(1 300和1 350℃)下制备的多孔复合材料体积密度低于烧结前的;而在较高烧结温度下,晶粒间更加紧密联结并生长出大晶粒,材料致密化程度和压缩强度提高,其中,1 450℃烧结制备的多孔复合材料体积密度为2.16g/cm3,开口气孔率约为46.5%,平均压缩强度达到31.6MPa。     

ZrO2-Al2TiO5复相材料的抗热冲击性能

以不同粒径的部分稳定ZrO2 (partially stabilized zirconia,PSZ)粉体为原料,采用共沉淀法包覆Al2TiO5纳米颗粒层,经高温烧结制备了高强度低膨胀的ZrO2-Al2TiO5复相材料.研究了原料粒径、Al2TiO5含量、烧成温度对复相材料的烧结性能、相组成、显微结构以及抗热冲击性能的影响.结果表明:随烧成温度的提高,PSZ各粒径样品的显气孔率呈逐步减小的规律,抗折强度呈逐步增大的趋势.随样品中纳米Al2TiO5含量的增加,单斜氧化锆到四方氧化锆的相变温度不断降低.在1 500℃烧结的、Al2TiO5含量为5%(质量分数,下同)、ZrO2(平均粒径为0.8μm)的样品,其显气孔率最小,为6.29%;抗折强度最大,为53.14MPa;室温到1100℃急冷急热冲击20次后,样品仍保持完整,仅在表面出现轻微剥落,抗热震性能明显高于其他样品.     

煅烧温度对莫来石质多孔陶瓷材料结构与性能的影响

以粉煤灰漂珠和α-Al2O3粉为原料,AlF3和V2O5作为添加剂,采用挤制成型工艺与无压烧结技术制备了莫来石质多孔陶瓷材料,研究了煅烧温度(分别为1100℃、1200℃、1300℃、1350℃)对试样的物相组成、莫来石质多孔陶瓷的显微结构以及性能的影响,并阐述了粉煤灰漂珠球体表面形成莫来石的机理过程。采用X射线衍射仪(XRD)、场发射扫描电子显微镜(SEM)和力学性能测定等手段表征了制备的莫来石质多孔陶瓷材料。结果表明:煅烧温度的提高有助于针状莫来石晶体的形成,莫来石晶体依托漂珠球壳生长;当煅烧温度从1100℃增加至1350℃,试样中的气孔率先增大后减小,而体积密度和抗压强度则先减小后增大;经1300℃烧制的试样综合性能较佳,气孔率为72.8%,体积密度为0.83 g·cm-3,抗压强度为15.4 MPa。这为固体废弃物粉煤灰漂珠的资源化应用以及多孔隙的莫来石质陶瓷材料的制备提供了新的研究思路。     

钛合金熔炼用Y2O3–Al2O3–MgO–CaO系耐火材料的设计与制备

坩埚耐火材料对钛合金熔炼的质量非常重要,为开发高性能新型坩埚材料,以工业Y₂O₃和Al₂O₃–MgO–CaO系粉末(AMC)为原料,制备出Y₂O₃–Al₂O₃–MgO–CaO系复合耐火材料,研究了烧结温度(1 500℃、1 600℃)和AMC含量(0、25%、50%、75%和100%,质量分数)对所制备耐火材料的物相组成、烧结性能(线收缩率、体积收缩率、显气孔率、体积密度)、常温耐压强度、抗热震性能和显微结构的影响。结果表明：相对于Y₂O₃和AMC材料,复合材料的性能均有所提高;提高烧结温度,其性能更佳;且随着AMC含量的提高,复合材料的线收缩率、体积收缩率、体积密度和常温耐压强度随之增大,显气孔率降低;当AMC的质量含量为75%时,1 500℃烧结3 h制得复合材料的综合性能最优,其显气孔率为4.37%,常温耐压强度为274.99 MPa,3次水冷热震后残余强度为16...     

不同造孔剂对钢包永久衬用隔热浇注料的影响

钢水冶炼过程中通常利用保温隔热材料来提高钢包周转过程中的保温性能,以保证连铸钢水温度的变化适应炉外精炼过程和连铸过程的工艺需要.为了研制高气孔率、高强度的保温隔热材料,以烧结莫来石为骨料,研究了四种不同造孔剂(菱镁矿粉、聚苯乙烯球、塑料颗粒和漂珠)对浇注料显气孔率及强度的影响.实验结果表明添加菱镁矿粉作造孔剂时,与未添加或添加其他造孔剂相比,烧后试样显气孔率较低,而且当加入量超过10%时,试样强度出现显著提升;添加聚苯乙烯球、塑料颗粒或漂珠做造孔剂均能够明显提升烧后试样的显气孔率,其中添加聚苯乙烯球、塑料颗粒的试样随着造孔剂引入量的增加强度出现明显降低,而添加漂珠的试样随漂珠引入量的增加强度变化不明显;复合添加10%菱镁矿粉和5%塑料颗粒时试样气孔率为29.34%、耐压强度为42 MPa,体积密度为1.98 g·cm-3,综合指标最高,最适合于做为莫来石质钢包保温隔热浇注料的造孔剂.     

六铝酸钙/镁铝尖晶石复相材料的制备及性能

以白云石和工业γ-Al2O3为原料,在不同烧结温度下制备了六铝酸钙/镁铝尖晶石复相材料。研究了Al2O3加入量和烧结温度对六铝酸钙/镁铝尖晶石复相相料的物相组成及性能的影响。结果表明:当Al2O3加入量为90.32%(质量分数)时,在1500,1550,1600℃和1650℃下均能够制备出无杂相六铝酸钙/尖晶石复相相料。随烧结温度提高,复相相料的体积密度和抗折强度先下降后提高,而显气孔率总是呈下降趋势。当烧结温度为1650℃时,所制备的复相材料的体积密度、显气孔率和弯曲强度分别为2.07g/cm3,48.78%和54.3MPa。     

氧化锆滑板制备工艺对其性能和显微结构的影响

分别以电熔CaO稳定ZrO2(CZ,粒度分为5级,最大为1 mm,最小为5μm),电熔CaO、Y2O3复合稳定ZrO2(YCZ,其d50<5μm)和两种电熔MgO、Y2O3复合稳定ZrO2(MZY1和MZY2,粒度均为d50<5μm)为主要原料,分别采用传统颗粒级配和微粉造粒料两种工艺制备了氧化锆滑板试样,研究了原料种类、原料粒度、烧成温度对氧化锆滑板力学性能和显微结构的影响。结果表明:采用微粉造粒料制备的试样比采用传统颗粒级配方式制备的具有更高的强度和体积密度,以及更低的显气孔率;采用微粉造粒料制备的试样的抗热震性与烧成温度、稳定剂的种类和含量、氧化锆原料中SiO2和A l2O3杂质的含量等有关;采用传统颗粒级配制成的氧化锆试样难以烧结致密,颗粒与基质结合稍差,存在粗大气孔;而以造粒料制成的试样烧结致密,并有相当数量的微气孔和微裂纹。     

TiO2加入量对MgO-TiO2熟料性能和显微结构的影响

以w(MgO)=96.14%的轻烧氧化镁和w(TiO2)>99.0%的分析纯TiO2为原料,分别加入质量分数0、5%、10%、15%、20%的TiO2,混合均匀,压制成型为30 mm×5 mm的试样,分别在1 500和1 600℃保温3 h烧结,制备得到MgO-TiO2熟料,并研究了熟料的体积密度、显气孔率、抗水化性能、物相组成和显微结构。结果表明:由于TiO2和MgO间的固溶和尖晶石反应,使得方镁石晶粒逐渐长大,反应过程中生成的Mg2TiO4分布在方镁石晶粒周围,降低了试样的显气孔率,提高了熟料的抗水化性能;TiO2添加量为5%(w)时熟料最致密,继续增加时,由于生成的Mg2TiO4体积膨胀,显气孔率有所增大;随着煅烧温度升高,熟料致密度提高,当温度为1 600℃时,能够获得抗水化性能良好的致密熟料。     

Improvement of coke resistance of Ni/Al2O3 catalyst in CH4/CO2 reforming by ZrO2 addition

This work investigates the improvement of Ni/Al₂O₃ catalyst stability by ZrO₂ addition for H₂ gas production from CH₄/CO₂ reforming reactions. The initial effect of Ni addition was followed by the effect of increasing operating temperature to 500–700 °C as well as the effect of ZrO₂ loading and the promoted catalyst preparation methods by using a feed gas mixture at a CH₄:CO₂ ratio of 1:1.25. The experimental results showed that a high reaction temperature of 700 °C was favored by an endothermic dry reforming reaction. In this reaction the deactivation of Ni/Al₂O₃ was mainly due to coke deposition. This deactivation was evidently inhibited by ZrO₂, as it enhances dissociation of CO₂ forming oxygen intermediates near the contact between ZrO₂ and nickel where the deposited coke is gasified afterwards. The texture of the catalyst or BET surface area was affected by the catalyst preparation method. The change of the catalyst texture resulted from the formation of ZrO₂–Al₂O₃ composite and the plugging of Al₂O₃ pore by ZrO₂. The 15% Ni/10% ZrO₂/Al₂O₃ co-impregnated catalyst showed a higher BET surface area and catalytic activity than the sequentially impregnated catalyst whereas coke inhibition capability of the promoted catalysts prepared by either method was comparable. Further study on long-term catalyst stability should be made.     

Phase diagram of the Al2O3-HfO2-Y2O3 system

The phase diagram of the Al₂O₃-HfO₂-Y₂O₃ system was first constructed in the temperature range 1200-2800 °C. The phase transformations in the system are completed in eutectic reactions. No ternary compounds or regions of appreciable solid solution were found in the components or binaries in this system. Four new ternary and three new quasibinary eutectics were found. The minimum melting temperature is 1755 °C and it corresponds to the ternary eutectic Al₂O₃ + HfO₂ + Y₃Al₅O₁₂. The solidus surface projection, the schematic of the alloy crystallization path and the vertical sections present the complete phase diagram of the Al₂O₃-HfO₂-Y₂O₃ system.     

Dielectric and ferroelectric properties of Ba0.8Sr0.2Ti1−5x/4NbxO3 ceramics

Ba_0.8Sr_0.2Ti_1−5x/4Nb_xO₃ ceramics, x = 0, 0.01, 0.05, 0.10, were fabricated by conventional solid-state reaction. With increasing niobium content the ferroelectric phase transition temperature decreases linearly, and the dispersivity of the transition increases. Niobium B-site decreases transition temperature more pronounced than Sr²⁺ at A-site. The heterovalent substitution of Nb⁵⁺ in low content causes local defect dipole, while more substitutions introduce disorder to disturb the long-range dipole correlation. Ba_0.8Sr_0.2Ti_1−0.5/4Nb_0.1O₃ ceramic shows weak ferroelectric loop at room temperature far from its transition temperature, 153 K.     

Surface of LiCo1/3Ni1/3Mn1/3O2 modified by CeO2-coating

A novel method to improve the cycling performance of LiCo_1/3Ni_1/3Mn_1/3O₂ in lithium-ion batteries by 1.0 wt.% CeO₂-coating is presented in this work. The crystalline structure and morphology of the synthesized powder have been characterized by XRD, SEM, TEM and their electrochemical performances were evaluated by CV, EIS and galvonostatic charge/discharge tests. It is found that CeO₂ forms a layer on the surface of LiCo_1/3Ni_1/3Mn_1/3O₂ without destroying the crystal structure of the core material. Electrochemical test indicates that CeO₂-coating could improve the cycling performance of LiCo_1/3Ni_1/3Mn_1/3O₂. At room temperature, the capacity retention of 1.0 wt.% CeO₂-coated material is 93.2% after 12 cycles at 3.0 C while that of the bare sample is only 86.6%. ICP-OES proves the coating layer could protect the dissolution of the transition metal ions from LiCo_1/3Ni_1/3Mn_1/3O₂. From the analysis of EIS, the improvement of cycle ability could be attributed to the suppression of the reaction between cathode and electrolyte.     

Effect of HfO2 content on the microstructure and piezoelectric properties of (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free ceramics

(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃–xHfO₂ [BNBT–xHfO₂] lead-free ceramics were prepared using the conventional solid-state reaction method. Effects of HfO₂ content on their microstructures and electrical properties were systematically studied. A pure perovskite phase was observed in all the ceramics with x=0–0.07 wt%. Adding optimum HfO₂ content can induce dense microstructures and improve their piezoelectric properties, and a high depolarization temperature was also obtained. The ceramics with x=0.03 wt% possess optimum electrical properties (i.e., d₃₃~168 pC/N, k_p~32.1%, Q_m~130, ε_r~715, tan δ~0.026, and T_d~106 °C, showing that HfO₂-modified BNBT ceramics are promising materials for piezoelectric applications.     

Investigation of hydrogen transport through Mm(Ni3.6Co0.7Mn0.4Al0.3)1.12 and Zr0.65Ti0.35Ni1.2V0.4Mn0.4 hydride electrodes by analysis of anodic current transient

Hydrogen transport through such metal-hydride electrodes as Mm(Ni_3.6Co_0.7Mn_0.4Al_0.3)_1.12 and Zr_0.65Ti_0.35Ni_1.2V_0.4Mn_0.4 was investigated in 6 M KOH solution by using potentiostatic current transient technique. From the shape of the anodic current transient and the dependence of the initial current density on the discharging potential, the boundary conditions at the electrode surface were established during hydrogen extraction from the as-annealed and as-surface-treated electrodes. Especially, it was experimentally confirmed that the diffusion-limited boundary condition is no longer valid at the electrode surface during hydrogen transport in case hydrogen diffusion is coupled with either the interfacial charge transfer reaction or the hydrogen transfer reaction between adsorbed state on the electrode surface and absorbed state at the electrode sub-surface. From the transition behaviour of the boundary condition, it was further recognised that the boundary condition at the electrode surface during hydrogen transport is not fixed at the specific electrode/electrolyte system by itself, but it is rather simultaneously determined even at any electrode/electrolyte system by the potential step and the nature of the electrode surface, depending upon e.g. the presence or absence of the surface oxide scales.     

A bi-layered composite cathode of La0.8Sr0.2MnO3-YSZ and La0.8Sr0.2MnO3-La0.4Ce0.6O1.8 for IT-SOFCs

A bi-layered composite cathode of La_0.8Sr_0.2MnO₃ (LSM)-YSZ and LSM-La_0.4Ce_0.6O_1.8 (LDC) was fabricated for anode-supported solid oxide fuel cells with a thin YSZ electrolyte film. The cell with the bi-layered composite cathode displayed better performance than the cell with the corresponding single-layered composite cathode of LSM-LDC or LSM-YSZ. At 650 °C, the cell with the bi-layered composite cathode gave a higher maximum power density than the cells with the single-layered LSM-LDC and LSM-YSZ composite cathodes, by 52% and 175%, respectively. The impedance spectra results show that the thin LSM-YSZ interlayer not only improves the cathode/electrolyte interface but also reduces the polarization resistance of the cathode. The activation energy for oxygen reduction on the bi-layered composite cathode is much smaller than that on LSM-YSZ composite cathode, and it is suggested that the special redox property of Ce⁴⁺/Ce³⁺ in LDC facilitates the oxygen reduction process on the bi-layered composite cathode. The cell with the bi-layered composite cathode operated quite stably during a 100 h run.     

A study on electrochemical characteristics of LiCoO2/LiNi1/3Mn1/3Co1/3O2 mixed cathode for Li secondary battery

In this study, the LiCoO₂/LiNi_1/3Mn_1/3Co_1/3O₂ mixed cathode electrodes were prepared and their electrochemical performances were measured in a high cut-off voltage. As the contents of LiNi_1/3Mn_1/3Co_1/3O₂ in the mixed cathode increases, the reversible specific capacity and cycleability of the electrode enhanced, but the rate capability deteriorated. On the contrary, the rate capability of the cathode enhanced but the reversible specific capacity and cycleability deteriorated, according to increasing the contents of LiCoO₂ in the mixed cathode. The cell of LiCoO₂/LiNi_1/3Mn_1/3Co_1/3O₂ (50:50, wt.%) mixed cathode delivers a discharge capacity of ca. 168 mAh/g at a 0.2 C rate. The capacity of the cell decreased with the current rate and a useful capacity of ca. 152 mAh/g was obtained at a 2.0 C rate. However, the cell shows very stable cycleability: the discharge capacity of the cell after 20th charge/discharge cycling maintains ca. 163 mAh/g.     

Synthesis and electrochemical characteristics of Al2O3-coated LiNi1/3Co1/3Mn1/3O2 cathode materials for lithium ion batteries

LiNi_1/3Co_1/3Mn_1/3O₂ cathode materials have been coated with Al₂O₃ nano-particles using sol-gel processing to improve its electrochemical properties. The X-ray diffraction (XRD) pattern of the as-prepared Al₂O₃ nano-particles was indexed to the cubic structure of the γ-Al₂O₃ phase and had an average size of ∼4 nm. The XRD showed that the structure of LiNi_1/3Co_1/3Mn_1/3O₂ was not affected by the Al₂O₃ coating. However, the Al₂O₃ coatings on LiNi_1/3Co_1/3Mn_1/3O₂ improved the cyclic life performance and rate capability without decreasing its initial discharge capacity. These electrochemical properties were also compared with those of LiAlO₂-coated LiNi_1/3Co_1/3Mn_1/3O₂ cathode material. The electrochemical impedance spectroscopy (EIS) was studied to understand the enhanced electrochemical properties of the Al₂O₃-coated LiNi_1/3Co_1/3Mn_1/3O₂ compared to uncoated LiNi_1/3Co_1/3Mn_1/3O₂.     

Chemical zoning of calcium aluminoferrite formed during melt crystallization in CaO-SiO2-Al2O3-Fe2O3 pseudoquaternary system

In the CaO-SiO₂-Al₂O₃-Fe₂O₃ pseudoquaternary system, the solid solutions of Ca₂(Al_xFe_1−x)₂O₅, with x<0.7 (ferrite), Ca₂SiO₄ (belite), Ca₃Al₂O₆ (C₃A) and Ca₁₂Al₁₄O₃₃ (C₁₂A₇), were crystallized out of a complete melt during cooling at 8.3 °C/min. Upon cooling to 1370 °C, both the crystals of ferrite with x=0.41 and belite would start to nucleate from the melt. During further cooling, the x value of the precipitating ferrite would progressively increase and eventually approach 0.7. At ambient temperature, the ferrite crystals had a zonal structure, the x value of which successively increased from the cores toward the rims. The value of 0.45 was confirmed for the cores by EPMA. The chemical formula of the rims was determined to be Ca_2.03[Al_1.27Fe_0.68Si_0.02]_Σ1.97O₅ (x=0.65). As the crystallization of ferrite and belite proceeded, the coexisting melt would become progressively enriched in the aluminate components. After the termination of the ferrite crystallization, the C₃A and belite would immediately crystallize out of the melt, followed by the nucleation of C₁₂A₇. The C₁₂A₇ accommodated about 2.1 mass% Fe₂O₃ in the chemical formula Ca_12.03[Al_13.61Fe_0.37]_Σ13.98O₃₃, being free from the other foreign oxides (SiO₂ and P₂O₅).