ZrB2增韧Al2O3陶瓷制备工艺及其对复相陶瓷力学性能影响

Al₂O₃陶瓷因具有很高的强度和耐蚀性受到广泛关注。但由于相对较差的韧性限制了其广泛应用。Al₂O₃陶瓷增韧的方式很多,本文采用微米ZrB₂来增韧氧化铝陶瓷,探讨复相陶瓷烧结工艺,并研究工艺参数对复相陶瓷力学性能及韧性的影响。结果表明：采用单因素法得到两种陶瓷最佳工艺参数分别是纯α-Al₂O₃陶瓷烧结温度为1500℃,成型压力为450MPa,保温时间为8h,球料比为1/2,保压时间为10min;ZrB₂(wt,20%)+α-Al₂O₃ (wt,80%)复相陶瓷烧结温度为1450℃,成型压力为450MPa,保温时间为8h,球料比为1/2,保压时间为10min。其中成型压力、烧结温度和保温时间对复相陶瓷硬度及致密度影响最大。ZrB₂的加入,在降低陶瓷烧结温度的同时,可以将纯α-Al₂O₃陶瓷的断裂韧性由5.2±0.3MPa.m^_1/2提高到6.7±0.2MPa.m^_1/2。     

ZrO2纳米颗粒对Al-12.5%Si合金PEO陶瓷层性能的影响

采用外加ZrO₂纳米颗粒的电解液体系在Al-12.5%Si合金表面制备ZrO₂- Al₂O₃- SiO₂三相PEO陶瓷层。利用SEM和XRD对陶瓷层微观结构和物相进行分析,并对其隔热及热冲击性能进行测试。结果表明：ZrO₂纳米颗粒显著提高了膜层的致密度和结合性,并有效减弱了Si元素对PEO成膜的抑制作用,提高了成膜速率;三相PEO陶瓷层的主要物相为SiO₂及高温稳定相α-Al₂O₃和c-ZrO₂,其独特的微结构和成分致使ZrO₂纳米颗粒改性的陶瓷层具有良好的热防护性能和热冲击性能。     

载体中ZrO2/Al2O3比对Pt/ZrO2-Al2O3催化剂性能的影响

相比汽油车而言,柴油车具有高效、低油耗的优势已得到广泛应用。本实验以ZrO₂作为改性剂,探究了ZrO₂与Al₂O₃的质量比对催化剂的影响。研究结果表明：随着ZrO₂的加入,Pt粒子先减小后增大;Pt粒子与载体的交互作用先增大后减小。活性实验数据分析表明,ZrO₂的最佳添加量为40 wt%,CO和C₃H₆完全氧化温度分别降低20 _oC 、25 _oC。贵金属在催化剂的分散度以及贵金属与载体的相互作用随着ZrO₂与Al₂O₃质量比的变化而变化。Pt粒子越小,其与载体的交互作用越强,这表明催化剂性能越强。     

空气反应钎焊ZrO2与GH3536接头组织与力学性能

采用Al₂TiO₅颗粒增强的Ag-CuO-Al₂TiO₅复合钎料,在钎焊温度为1050 ℃保温30 min工艺参数下,对ZrO₂陶瓷与GH3536合金进行了空气反应钎焊(RAB),分析了钎焊接头的界面结构及其形成机制;同时研究了接头在800 ℃氧化不同时间的组织演变规律及其对连接性能的影响。结果表明,钎焊过程中Al₂TiO₅颗粒分解产生Al₂O₃和TiO₂,TiO₂与ZrO₂陶瓷反应生成ZrTiO₄相。GH3536侧金属元素发生氧化形成尖晶石层,并分别与钎缝中的Al₂O₃、CuO反应,在钎缝中生成细密分布的NiAl₂O₄相及紧邻尖晶石层的团块状NiCuO₂相。ZrO₂/GH3536接头高温氧化1000 h后,钎缝中NiAl₂O₄呈团块状分布,Cr₂O₃薄层保持稳定;尖晶石层内部元素均匀化,厚度有明显增加。接头强度随着氧化时间的延长先降低后稳定在20 MPa。     

基于磁过滤技术的热障涂层表面Al2O3 覆盖层抗CMAS腐蚀性能

为了提高热障涂层（TBC）的抗沉积物（主要成分为CaO、MgO、Al₂O₃和SiO₂,简称CMAS）腐蚀性能,采用磁过滤阴极真空电弧（FCVA）技术在TBC表面上制备了致密的Al₂O₃覆盖层,比较和分析了Al₂O₃改性TBC和沉积态TBC的润湿行为和抗CMAS腐蚀性能。结果表明：使用FCVA技术制备Al₂O₃覆盖层的过程对7%（质量分数）氧化钇稳定的氧化锆（7YSZ）相的结构无明显影响,且经Al₂O₃改性的TBC综合性能均优于沉积态TBC。在1250 ℃、CMAS腐蚀条件下,Al₂O₃覆盖层有效地限制了熔融CMAS在TBC表面上的扩散行为。同时,Al₂O₃填充了7YSZ柱状晶之间的间隔并且阻碍了熔融CMAS的渗透,证明了FCVA可作为一种制备Al₂O₃涂层的新方法以提高TBC的抗CMAS腐蚀性能,且Al₂O₃涂层及其制备过程对TBC的热震性能均无消极影响。     

三元共晶成分Al_2O_3/YAG/ZrO_2粉体及陶瓷的制备与组织性能

采用醇水共沉淀法制备了三元共晶成分Al_2O_3/YAG/ZrO_2粉体,在600~1350℃温度范围煅烧后研究其物相转变过程。经1300℃煅烧后Al_2O_3/YAG/ZrO_2共晶成分粉体的物相由α-Al_2O_3、c-ZrO_2和YAG构成,且具有α-Al_2O_3相包裹c-ZrO_2相的特殊结构。将煅烧粉体在1550℃下热压烧结,制备具有内晶型结构的共晶成分Al_2O_3/YAG/ZrO_2复相陶瓷,其致密度、室温抗弯强度、断裂韧性和高温(1000℃)抗弯强度分别为98.8%、420 MPa、3.69 MPa·m~(1/2)和464 MPa,并对复相陶瓷组织结构的形成机理进行了探讨。     

γ-TiAl合金表面Al2O3/Al复合涂层的抗高温熔盐腐蚀性能研究

采用磁控溅射技术于γ-TiAl合金表面制备Al₂O₃/Al复合涂层。在850 °C下、 100 wt.% Na₂SO₄熔盐中观测Al₂O₃/Al复合涂层的高温腐蚀行为。结果表明,Al₂O₃/Al复合涂层具备由Al₂O₃表层、富Al中间层以及互扩散层组成的梯度结构,因而有效地提高了基体γ-TiAl合金的抗高温腐蚀性能。在腐蚀实验后,涂层试样表面相结构为Al₂O₃,TiO₂和TiAl₃。致密的Al₂O₃/Al复合涂层有效地抑制了O_2-,S_-和Na₊对基体γ-TiAl合金的侵蚀。并且,Al₂O₃/Al复合涂层的梯度结构亦使其表现出了优异的抗开裂和抗剥落性能。     

Ba(Mg1/3Ta2/3)O3热障涂层的制备及抗热震性能研究

本文以BaCO₃、MgO、Ta₂O₅为原料,采用固相反应法合成了Ba(Mg_1/3Ta_2/3)O₃(简称BMT)陶瓷粉末,利用大气等离子喷涂技术制备了BMT/YSZ双层陶瓷涂层。利用XRD、SEM和金相显微镜检测了BMT粉体及涂层的物相组成和显微结构。采用水淬法考核了涂层的抗热震性能。结果表明：1450℃下煅烧4h可合成出具有复合钙钛矿结构的BMT粉末,粉末具有良好的高温相结构稳定性。等离子喷涂制备的BMT/YSZ涂层组织致密,涂层系统中各界面结合紧密。涂层在室温至1150℃间热震9次后发生片状剥落,剥落位置位于BMT层间,BMT材料低的断裂韧性和第二相Ba₃Ta₅O₁₅的存在是导致涂层失效的主要原因。     

ZrB2-玻璃陶瓷复合材料氧化分析

对ZrB₂-玻璃陶瓷复合材料氧化行为进行热力学分析,对氧化形成的氧化层进行物相分析和显微结构分析。结果表明：在1000°C-1400°C的反应温度范围内,ZrB₂氧化生成ZrO₂,B₂O₃玻璃相,氧化产物ZrO₂与SiO₂反应生成ZrSiO₄,当温度低于1177°C(1450K)时,氧化层主要包括ZrO₂,B₂O₃玻璃相,ZrSiO₄。当氧化温度超过1177°C(1450K)时,B₂O₃玻璃相蒸发,此时SiO₂玻璃相具有良好的流动性,氧化层主要包括ZrO₂,SiO₂玻璃相,ZrSiO₄。氧化过程中的反应产物B₂O₃玻璃相,ZrSiO₄和流动性良好的SiO₂玻璃相,均对氧气向基体的扩散均起到了良好的阻碍作用。     

Al2O3/Ti2AlN复合材料在900℃,1000℃和1100℃空气中的氧化行为

利用综合热分析仪、背散射扫描电镜(BSE)和能谱分析(EDS)对Al₂O₃/Ti₂AlN复合材料在900 ℃,1 000 ℃和1 100 ℃/20 h空气中连续氧化20h后的氧化增重及氧化层截面进行了研究。结果表明：Al₂O₃/Ti₂AlN复合材料在空气中的氧化行为符合抛物线规律,在900 ℃,1 000 ℃和1 100 ℃/20 h氧化增重分别为2.78×10_-2 kg/m₂、10.4 ×10_-2 kg/m₂、21.9 ×10_-2 kg/m₂,抛物线速率常数相应为1.08×10_-8 kg₂/m₄s、1.44×10_-7 kg₂/m₄s、6.56×10_-7 kg₂/m₄s,氧化激活能为274 kJ/mol。氧化层主要由TiO₂和Al₂O₃组成的,连续的Al₂O₃次外层可以提高其抗氧化性能。氧化层结构的改变是由于氧化温度对Ti₄₊、Al₃₊由基体表面向外扩散和O_2-向内扩散的影响,以及TiO₂和Al₂O₃在不同温度下的形核生长速率导致的。对Al₂O₃/Ti₂AlN而言,控制材料与氧化气氛的界面是提高该材料抗氧化性能的关键。     

Effects of K2O-Li2O doping on surface and catalytic properties of Fe2O3/Cr2O3 system

The effects of K₂O and Li₂O-doping (0.5, 0.75 and 1.5 mol%) of Fe₂O₃/Cr₂O₃ system on its surface and the catalytic properties were investigated. Pure and differently doped solids were calcined in air at 400-600 °C. The formula of the un-doped calcined solid was 0.85Fe₂O₃:0.15Cr₂O₃. The techniques employed were TGA, DTA, XRD, N₂ adsorption at −196 °C and catalytic oxidation of CO oxidation by O₂ at 200-300 °C. The results revealed that DTA curves of pure mixed solids consisted of one endothermic peak and two exothermic peaks. Pure and doped mixed solids calcined at 400 °C are amorphous in nature and turned to α-Fe₂O₃ upon heating at 500 and 600 °C. K₂O and Li₂O doping conducted at 500 or 600 °C modified the degree of crystallinity and crystallite size of all phases present which consisted of a mixture of nanocrystalline α- and γ-Fe₂O₃ together with K₂FeO₄ and LiFe₅O₈ phases. However, the heavily Li₂O-doped sample consisted only of LiFe₅O₈ phase. The specific surface area of the system investigated decreased to an extent proportional to the amount of K₂O and Li₂O added. On the other hand, the catalytic activity was found to increase by increasing the amount of K₂O and Li₂O added. The maximum increase in the catalytic activity, expressed as the reaction rate constant (k) measured at 200 °C, attained 30.8% and 26.5% for K₂O and Li₂O doping, respectively. The doping process did not modify the activation energy of the catalyzed reaction but rather increased the concentration of the active sites without changing their energetic nature.     

Fe2O3-CaO-TiO2 体系下铁酸钙的合成过程及TiO2 和CaTiO3 的影响

为了确定高钛型钒钛磁铁矿烧结过程中铁酸钙的生成是受TiO₂还是TiO₂和CaO形成的CaTiO₃影响,首先利用Fe₂O₃和CaO的纯试剂合成了铁酸钙,并研究了TiO₂和CaTiO₃对钛铁酸钙 （FCT） 形成的影响。在Factsage 7.0软件进行热力学计算的基础上,通过在空气气氛下进行烧结,获得了在1023~1423 K温度范围内、不同烧结时间的不同样品。通过X射线衍射和扫描电镜-能谱分析等表征手段,对烧结样品的物相转变和微观结构变化进行了表征。发现FCT的形成过程主要分为2个阶段：前一阶段为1023~1223 K温度范围内Fe₂O₃与CaO之间的反应,合成产物为Ca₂Fe₂O₅,反应方程式为“Fe₂O₃(s)+ 2CaO(s)= Ca₂Fe₂O₅(s)”;后一阶段为1223~1423 K温度范围内Ca₂Fe₂O₅和Fe₂O₃的反应,主要产物为CaFe₂O₄,反应为“Ca₂Fe₂O₅(s)+ Fe₂O₃(s)= 2CaFe₂O₄(s)”,该阶段尤其是温度为1423 K时,反应速率显著加快,随温度的升高CaTiO₃显著增加。然而,Ti元素在铁酸钙中的固溶很难实现,TiO₂与铁酸钙之间的反应不是形成FCT的有效途径。随着保温时间的延长,CaTiO₃和FCT相界中Fe元素含量增加。FCT主要是通过Fe组分在CaTiO₃中固溶形成的,主要反应是“Fe₂O₃+CaTiO₃(s)=FCT(s)”。     

等离子球化制备球形CaF2/BaF2共晶粉末*

探究了使用大气等离子喷涂设备制备适合热喷涂使用的球形CaF2/BaF2共晶粉末的可能性。68%BaF2、32%CaF2粉末(质量分数)经过1 100℃真空烧结后,形成致密的块状氟化物共晶。机械破碎后的氟化物共晶经过等离子焰流重熔后得到了球形的氟化物共晶。使用F14-1流动性和松装密度测定仪测量球化前后粉末的流动性和松装密度。采用扫描电子显微镜,XRD表征球化前后粉末的形貌和物相组成。结果表明:球化后的粉末呈现较好的球形,球化后粉末的流动性和松装密度较球化前也有较大的改善:球化后共晶粉末的流动时间为55.20s/50g,松装密度为1.89g/cm3;另外,球化后共晶粉末还表现出良好的高温润滑性能:含有10%CaF2/BaF2共晶(质量分数)的镍基涂层在600℃和800℃的平均摩擦因数都小于0.3。     

In-situ TiB2 and Al2O3 formation by DC plasma spraying

In-situ plasma spraying (IPS) is a promising process to fabricate composite coatings with in-situ formed thermodynamically stable phases. In the present study, mechanically alloyed Al-12Si, B₂O₃ and TiO₂ powder was deposited onto an aluminum substrate using atmospheric plasma spraying (APS). It has been observed that, during the coating process, TiB₂ and Al₂O₃ are in-situ formed through the reaction between starting powders and finely dispersed in hypereutectic Al-Si matrix alloy. Also, obtained results demonstrate that in-situ reaction intensity strongly depends on spray conditions.     

CVD deposition and characterization of coloured Al2O3/ZrO2 multilayers

Coloured Al₂O₃/ZrO₂ multilayers have been deposited onto WC-Co based inserts by a CVD process. Through physical as well as optical analysis of such multilayers, colour is believed to originate from interference. The coatings are obtained with good process reproducibility. It was found that the ZrO₂ process used in the multilayer, with ZrCl₄ as the only metal chloride precursor, results in a mixture of tetragonal and monoclinic ZrO₂ phases. However by adding a relatively small amount of AlCl₃ during such a process results in ZrO₂ layers being composed of predominantly tetragonal ZrO₂ phase. Corresponding multilayers seem to have a more fine grained and smoother morphology whereas multilayers containing monoclinic ZrO₂ phase seem to be less perfect with existence of larger grains of ZrO₂ which are believed to scatter light and alter the reflectance of such a multilayer. In addition to this, such multilayers were found to be free of or with greatly reduced amount of thermal cracks, normally present in pure CVD grown Al₂O₃ layers.It is believed that, in the studied Al₂O₃/ZrO₂ multilayers, the observed tetragonal ZrO₂ phase is the result of a size effect, where small enough ZrO₂ crystallites energetically favor the tetragonal phase. However as the ZrO₂ crystallite size distribution is shifted to larger sizes it is believed that a mixture of crystallites with both stable and metastable tetragonal phases as well as a stable monoclinic phase is obtained. The proposed metastable tetragonal ZrO₂ phase may in fact explain the absence of thermal cracks in such multilayers through a transformation toughening mechanism, well known in ZrO₂ based ceramics.     

Modification of TiO2 nanorods by Bi2MoO6 nanoparticles for high performance visible-light photocatalysis

In this work, TiO₂ nanorods were prepared by a hydrothermal process and then Bi₂MoO₆ nanoparticles were deposited onto the TiO₂ nanorods by a solvothermal process. The nanostructured Bi₂MoO₆/TiO₂ composites were extensively characterized by X-ray diffraction, scanning and transmission electron microscopy, X-ray photoelectron spectroscopy and UV-vis diffuse reflectance spectroscopy. The photocatalytic activity of the Bi₂MoO₆/TiO₂ composites was evaluated by degradation of methylene blue. The Bi₂MoO₆/TiO₂ composites exhibit higher catalytic activity than pure Bi₂MoO₆ and TiO₂ for degradation of methylene blue under visible light irradiation (λ > 420 nm). Further investigation revealed that the ratio of Bi₂MoO₆ to TiO₂ in the composites greatly influenced their photocatalytic activity. The experimental results indicated that the composite with Bi₂MoO₆:TiO₂ = 1:3 exhibited the highest photocatalytic activity. The enhancement mechanism of the composite catalysts was also discussed.     

Preparation and characteristic of spherical Li3V2(PO4)3

Spherical Li₃V₂(PO₄)₃ was synthesized by using N₂H₄ as reducer. The products were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that single-phase, spherical and well-dispersed Li₃V₂(PO₄)₃ has been successfully synthesized in our experimental process. Electrochemical behaviors have been characterized by charge/discharge measurements. The initial discharge capacities of Li₃V₂(PO₄)₃ were 123 mAh g⁻¹ in the voltage range of 3.0–4.3 V and 132 mAh g⁻¹ in the voltage range of 3.0–4.8 V.     

Preparation and properties of sintered molybdenum doped with La2O3/MoSi2

Sintered Mo with the addition of La₂O₃/MoSi₂ was prepared via the process of solid–solid doping + powder metallurgy. X-ray diffraction experiment, hardness test, three-point bending test and high-temperature tensile test were carried out to characterize the samples. The XRD pattern of a typical sample shows that the sintered Mo was mainly composed of Mo, La₂O₃ and Mo₅Si₃. Mo₅Si₃ was probably formed through the reaction between MoSi₂ and the Mo matrix. Densities and fracture toughnesses of both doped Mo and pure Mo were measured and contrasted. Sintered Mo with the addition of 0.2 wt% La₂O₃/MoSi₂ has the highest toughness, while more addition of La₂O₃/MoSi₂ has smaller effect on improving toughness or even embrittles Mo. The results of three-point bending test and high-temperature tensile test show that the bending strength and high-temperature tensile strength of doped Mo are both higher than those of pure Mo. The formation of Mo₅Si₃ improves the high-temperature strength. The La₂O₃/Mo₅Si₃ dispersed in the Mo matrix refined the grains, and thus strengthened the Mo matrix by dispersion strengthening and grain refinement.     

CuInSe2 nano-crystallite reaction kinetics using solid state reaction from Cu2Se and In2Se3 powders

The reaction mechanism and CuInSe₂ formation kinetics using a solid state reaction from Cu₂Se and In₂Se₃ powders synthesized using a heating up process were investigated using X-ray diffractomy (XRD) and transmission electron microscopy (TEM). It was observed that the CuInSe₂ phase increased gradually, accompanied with a decrease in γ-In₂Se₃ with no intermediate phase as the calcination temperature and soaking time were increased. The reaction kinetics was analyzed using the Avrami and polynomial kinetic model, suggesting that CuInSe₂ formation from Cu₂Se and In₂Se₃ powders follows a diffusion-controlled reaction with an apparent activation energy of about 122.5-182.3 kJ/mol. Cu₂Se and In₂Se₃ phases react and directly transform into CIS without the occurrence of any intermediate phase and the size of the newly formed CuInSe₂ crystallites was close to that of the Cu₂Se reactant particle based on the TEM results, which indicated that the solid reaction kinetics may be dominated by the diffusion of In³⁺ ions.     

Mechanochemical synthesis of Al2O3-TiB2 nanocomposite powder from Al-TiO2-H3BO3 mixture

Alumina-titanium diboride nanocomposite (Al₂O₃-TiB₂) was produced using mixtures of titanium dioxide, acid boric and pure aluminum as raw materials via mechanochemical process. The phase transformation and structural characterization during mechanochemical process were utilized by X-ray diffractometry (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and thermogravimetric analyses (TG-DTA) techniques. A thermodynamic appraisal showed that the reaction between TiO₂, B₂O₃ and Al is highly exothermic and should be self-sustaining. XRD analyses exhibited that the Al₂O₃-TiB₂ nanocomposite was formed after 1.5 h milling time. The results indicate that increasing milling time up to 40 h had no significant effect other than refining the crystallite size.