ZrB_2含量对Nb-Mo-ZrB_2复合材料氧化行为的影响（英文）

利用热压烧结法,在2400℃烧结温度下,制备了NbMo固溶体(此后记作(Nb,Mo)ss)基陶瓷颗粒增强复合材料。其中,ZrB_2陶瓷增强相的体积分数分别为15%,30%,45%和60%。研究了在800,1000和1200℃下,ZrB_2含量对复合材料抗氧化性和氧化产物演变的作用。结果表明,氧化温度和ZrB_2含量均对复合材料的氧化行为有影响。从氧化速率常数角度讲,ZrB_2-(Nb,Mo)ss复合材料的抗氧化性随ZrB_2含量的增加而提高,随氧化温度的提高而降低。800~1000℃的氧化产物中含有膜状Nb_2Zr_6O_(17)相,能作为屏障阻止氧气向基体扩散,因此在800~1000℃时,复合材料氧化速率较低。然而,在1200℃氧化时未发现Nb_2Zr_6O_(17)相,MoO_3的剧烈挥发和ZrO_2的体积效应破坏了Nb_2Zr_6O_(17)保护层,导致了氧化层严重剥落,材料的抗氧化性极差。综上,结合观察到的氧化产物形貌,详细阐述了不同ZrB_2含量的复合材料在不同温度下的抗氧化机制。     

Zn_²⁺掺杂对共沉淀法制备Ce:Gd₃Ga₃Al₂O₁₂陶瓷粉体闪烁性能的影响

本文利用化学共沉淀法制备Zn_²⁺共掺的Ce:GAGG陶瓷粉体。研究了Zn_²⁺共掺的Ce:GAGG陶瓷前驱粉体的TG/DTA和FTIR曲线；分析了不同煅烧温度对Ce:GAGG陶瓷粉体相、形貌和颗粒度分布的影响；系统研究了Zn_²⁺含量对Ce:GAGG陶瓷粉体光致发光,辐射发光,激发光谱和荧光寿命的影响。研究表明：前驱粉体在883℃的相组成为GdAlO₃相和GAGG相；前驱粉体在煅烧温度为900℃时,完全转化为GAGG相；当煅烧温度为1200℃时,GAGG颗粒尺寸控制在20nm~60nm,分布均匀；随着 Zn_²⁺含量的变化,光致发光和辐射发光强度也相应变化,特别的,当Zn_²⁺含量为0.4mol%时,光致发光和辐射发光强度达到最大值；随着Zn_²⁺掺杂含量的上升,荧光寿命出现下降的趋势。因此,Zn_²⁺含量对Ce:GAGG陶瓷粉体的辐射发光具有明显的影响,对降低荧光寿命具有积极的作用,对于提高GAGG闪烁材料的快速响应具有重要意义。     

超声辅助对共沉淀法制备富锂锰基正极材料Li[Li_0.144Ni_0.136Co_0.136Mn_0.544]O₂性能影响的研究

通过超声辅助共沉淀法成功制备了富锂锰基正极电极材料,研究了不同的超声时间对材料形貌、结构和电化学性能的影响。研究发现,超声辅助能够使材料颗粒更加均匀,结构更合理,有利于材料电化学性能的提升。当合成前躯体材料超声时间为8h时,复合材料的放电比容量最好,在0.1C的初始放电比容量为327.8 mAh g_-1,均高于未超声的复合材料的265.2 mAh g_-1,1C下循环50圈后放电容量为181.6 mAh g_-1,保持率为84.8%。通过循环伏安法测试和电化学交流阻抗测试,发现超声后的复合材料还原氧化峰电流更大,电荷转移阻抗更小,具有较好的倍率性能。     

添加Nb_2O_5对Al_2O_3/TiAl基复合材料在900℃空气中氧化行为的影响

利用热压工艺制备了添加2%、6%和10%Nb2O5的A1203/TiAl基复合材料,并研究了该材料在900℃空气中的高温氧化行为.结果表明:随着Nb2O5含量的增加,复合材料的氧化速率明显下降,其氧化动力学曲线近似于抛物线规律;所有材料氧化120 h后均形成了多层的氧化膜;Nb在表层的富集起到了扩散障的作用,既阻挡了氧原子的继续渗入,也阻碍了Ti原子向外扩散,使得复合材料的抗氧化性能随Nb:O5含量的增加而提高.     

添加Nb对Zr-0.75Sn-0.35Fe-0.15Cr合金高温蒸汽氧化行为的影响

本文熔炼了Zr-0.75Sn-0.35Fe-0.15Cr-xNb（x=0、0.15、0.50、1.00，wt.%）合金，并制备成板状样品。采用TG-DSC研究了4种锆合金在模拟LOCA工况下800~1200 ℃的抗高温蒸汽氧化行为和相变行为，利用金相显微镜分析了氧化样品横截面的显微组织。结果表明，4种锆合金的抗高温蒸汽氧化性能并没有随Nb含量的变化呈单一的变化规律，其氧化动力学大多为线性规律，只有添加0.5%Nb的合金在1000 ℃的氧化动力学发生了两次转折，由线性规律转变为幂指数规律再转变为线性规律；锆合金中基体的相转变温度随着Nb含量的增加而降低，而其氧化物的相变行为并没有随Nb含量的变化呈单一变化趋势，这说明Nb含量对锆合金氧化物的相变行为的影响比对合金相变行为的影响复杂。氧化温度为800 ℃、1000 ℃和1200 ℃时，氧化样品截面组织分别为：ZrO2和α-Zr(O)，ZrO2、α-Zr(O)和原β-Zr层，ZrO2和α-Zr(O)； 800 ℃氧化样品截面各层组织的厚度占比基本不随Nb含量发生变化；1000 ℃氧化样品截面α-Zr(O)层的厚度占比随Nb含量的增加而增大，原β-Zr层的厚度占比正好相反，出现了指状侵入的α-Zr(O)。1200 ℃氧化样品截面显微组织厚度占比随Nb含量的变化比较复杂。这说明Nb有促进β→α-Zr(O)转变的作用。     

High-Temperature Oxidation Behavior of Ti-22Al-27(Nb, Zr) Alloys

研究了Ti2Al Nb基合金Ti-22Al-(27-x)Nb-x Zr(x=0,1,6,at%)在650~800℃的氧化行为。采用XRD和SEM等测试技术对此温度区间形成的氧化层特征进行了分析。结果表明,相比Ti-22Al-27Nb,含锆合金具有较好的抗氧化性能。Ti-22Al-(27-x)Nb-x Zr合金在650℃氧化100 h,主要氧化产物为Ti O2,而在800℃氧化100 h,Ti O2,Al2O3和Al Nb O4为主要产物,但是在Ti-22Al-21Nb-6Zr合金中还有Zr O2生成。Ti-22Al-26Nb-1Zr合金具有优异抗氧化性能,归因于氧化产物细化形成了致密的氧化层,而Ti-22Al-21Nb-6Zr合金,虽然在800℃也形成了较多Al2O3,但是氧化层中的Zr O2为氧的快速扩散提供通道,进而导致该合金氧化增重明显。     

合金元素对Nb-Ti-Al-C合金氧化行为的影响

利用真空非自耗电弧炉制备不同Al含量的Nb-25Ti-8C合金,研究Nb-Ti-Al-C合金的组织结构及其高温氧化行为。研究表明,Nb-25Ti-8C-(0,5,10)Al合金由Nbss和(Nb,Ti)C两相构成;Nb-25Ti-8C-15Al合金由Nbss、(Nb,Ti)C和Nb3Al三相构成。800~1000℃氧化过程中,合金氧化膜为由Nb2O5,Ti O2,Al2O3,Nb O2及Ti Nb2O7多种氧化物构成的混合氧化膜。Ti、Al活性元素可优先与氧发生选择性氧化,抑制氧化物Nb2O5生成,提高氧化膜致密度和合金抗氧化性,并且氧化温度越高,Al元素改善铌合金抗氧化性能效果越明显。Nb-25Ti-8C合金800℃氧化时表现出良好的抗氧化性能,1000℃氧化时Nb-25Ti-8C-x Al合金的抗氧化性能明显优于C-103。随氧化温度升高,氧化膜中Nb2O5含量增加,导致氧化膜与合金基体的内应力增大,引起外层氧化膜脱落。碳化物中C元素以CO2形式挥发导致氧化层表面形成氧化空洞。     

Ti-22Al-27(Nb,Zr)合金的高温氧化行为（英文）

研究了Ti2Al Nb基合金Ti-22Al-(27-x)Nb-x Zr(x=0,1,6,at%)在650~800℃的氧化行为。采用XRD和SEM等测试技术对此温度区间形成的氧化层特征进行了分析。结果表明,相比Ti-22Al-27Nb,含锆合金具有较好的抗氧化性能。Ti-22Al-(27-x)Nb-x Zr合金在650℃氧化100 h,主要氧化产物为Ti O2,而在800℃氧化100 h,Ti O2,Al2O3和Al Nb O4为主要产物,但是在Ti-22Al-21Nb-6Zr合金中还有Zr O2生成。Ti-22Al-26Nb-1Zr合金具有优异抗氧化性能,归因于氧化产物细化形成了致密的氧化层,而Ti-22Al-21Nb-6Zr合金,虽然在800℃也形成了较多Al2O3,但是氧化层中的Zr O2为氧的快速扩散提供通道,进而导致该合金氧化增重明显。     

ZrO_2/ZrW_2O_8陶瓷复合材料制备工艺研究

ZrO_2是一种重要的结构和功能材料,其热膨胀系数与Zr W2O8的负膨胀系数绝对值相近,两者合理调配可以得到任意正、零、负膨胀的陶瓷基复合材料。以ZrO_2陶瓷为基体、Al2O3为烧结助剂,采用两条工艺路线制备ZrO_2/Zr W2O8陶瓷基复合材料:(1)以ZrO_2和Zr W2O8为原料,直接混合然后分别在1200℃和1215℃热压烧结制备复合材料;(2)以ZrO_2(过量)和WO3为原料,采用原位反应法分别在1200℃和1215℃合成负膨胀Zr W2O8陶瓷,然后在相同温度下热压烧结制备复合材料。重点研究不同制备工艺路线(直接混料法或原位反应法+热压烧结),以及在同一种制备方法下、不同热压烧结温度对低膨胀ZrO_2/Zr W2O8陶瓷基复合材料组织形貌、密度和Zr W2O8分解程度的影响。结果表明,无论采用哪种工艺路线,都能制备密度较高的ZrO_2/Zr W2O8陶瓷基复合材料。采用"原位反应+热压烧结法"制备复合材料的密度要高于"直接混料+热压烧结法"制备的复合材料;且Zr W2O8分解程度也较低。直接混料粉在1200℃热压3 h,或者在1215℃热压6 h,所得复合材料的密度约为5.20 g/cm3。     

La2O3改性ZrB2-SiC涂层C/C复合材料全温域抗氧化行为研究

采用高温反应熔渗工艺制备了ZrB2-SiC和La2O3改性ZrB2-SiC涂层C/C复合材料,对比了2种涂层试样在中温(7001100℃)、高温(12001500℃)和超高温(2000℃以上)3个温域范围内的抗氧化性能。结果表明:7001100℃范围内,随着温度的升高,La2O3改性涂层试样的抗氧化性能提升幅度在逐渐提高。1200℃1500℃范围内,涂层均表现出良好的长时抗氧化性能,La2O3改性ZrB2-SiC在1200℃下恒温氧化250 h后,仍保持微量的增重;涂层复合材料良好的高温抗氧化性能主要其在是由于氧化过程中涂层表面形成的La-Si-O复合玻璃层和钉扎相ZrSiO4的协同作用提升了氧化膜的高温稳定性。在2000℃以上的氧乙炔火焰烧蚀环境下,La2O3的添加使得ZrB2-SiC涂层的质量烧蚀率和线烧蚀率均降低了近50%,其主要归因于表层La-Si-O和ZrO2玻璃层对烧蚀缺陷的愈合作用。     

Isothermal oxidation behavior of powder metallurgy beta gamma TiAl–2Nb–2Mo alloy

A new TiAl–2Nb–2Mo beta gamma alloy was synthesized by powder metallurgy process. HIP’ed and vacuum heat treated specimens were isothermally oxidized at 800 °C and 900 °C in air up to 500 h. The TiAl–2Nb–2Mo alloy oxidized parabolically up to 500 h at both 800 °C and 900 °C. The oxides consisted of outer TiO₂ layer, intermediate Al₂O₃ layer, and inner TiO₂ rich mixed layer and the oxidation mechanisms of the alloy were identical at both temperatures. During oxidation, the degradation of lamellar colonies formed a diffusion zone just below the oxide/substrate interface consisting of γ-TiAl matrix and dispersed beta phases which contained high concentration of Nb and Mo. The oxidation rate of the TiAl–2Nb–2Mo alloy is more sensitive to temperature than those of the Ti–48Al–2Nb–2Cr and Ti–48Al–2Nb–2Cr–W alloys.     

The Isothermal and Cyclic Oxidation Behavior of a Titanium Aluminide Alloy at Elevated Temperature

The isothermal and cyclic oxidation behavior of Ti-47Al-2Mn-2Nb with 0.8 vol.% TiB₂ particle-reinforced alloy was investigated in air between 700 and 1000 °C. In the study, the kinetics of isothermal and cyclic oxidation were performed by using a continuous thermogravimetric method which permits mass change measurement under oxidation conditions. The oxide scales and substrates were characterized by scanning electron microscopy with energy-dispersive x-ray analysis and x-ray diffraction. At 700 and 800 °C, the alloy showed an excellent oxidation resistance under isothermal and cyclic conditions. After exposure to air above 800 °C, the outer scale of the alloy was dominated by a fast-growing TiO₂ layer. Under the coarse-grained TiO₂ layer was the Al₂O₃-rich scale, which was fine-grained. At 900 and 1000 °C, the extent of oxidation increased clearly. The oxidation rate follows a parabolic law at 700 and 800 °C. However, the alloy, upon isothermal oxidation at 900 °C, can be divided into several stages. During the cyclic oxidation at 900 and 1000 °C, partial scale spallation takes place, leading to a stepwise mass change.     

Growth Kinetics and Microstructure Evolution of Intermediate Phases in MoSi<Subscript>2</Subscript>-Si<Subscript>3</Subscript>N<Subscript>4</Subscript>-WSi<Subscript>2</Subscript>/Mo Diffusion Couples

The growth kinetics and silicon diffusion coefficients of intermediate silicide phases in MoSi₂-3.5 vol.% Si₃N₄-5.0 vol.% WSi₂/Mo diffusion couple prepared by spark plasma sintering were investigated in temperatures ranging from 1200 to 1500 °C. The intermediate silicide phases were characterized by x-ray diffraction. The microstructures and components of the MoSi₂-Si₃N₄-WSi₂/Mo composites were investigated using scanning electron microscope with energy-dispersive spectroscopy. A special microstructure with MoSi₂ core surrounded by a thin layer of (Mo,W)Si₂ ring was found in the MoSi₂-Si₃N₄-WSi₂ composites. The intermediate layers of Mo₅Si₃ and (Mo,W)₅Si₃ in the MoSi₂-Si₃N₄-WSi₂/Mo diffusion couples were formed at different diffusion stages, which grew parabolically. Activation energy of the growth of intermediate layers in MoSi₂-3.5 vol.% Si₃N₄-5.0 vol.% WSi₂/Mo diffusion couple was calculated to be 316 ± 23 kJ/mol. Besides, the hindering effect of WSi₂ addition on the growth of intermediate layers was illustrated by comparing the silicon diffusion coefficients in MoSi₂-3.5 vol.% Si₃N₄-5.0 vol.% WSi₂/Mo and MoSi₂-3.5 vol.% Si₃N₄/Mo diffusion couples. MoSi₂-3.5 vol.% Si₃N₄-5.0 vol.% WSi₂ coating on Mo substrate exhibited a better high-temperature oxidation resistance in air than that of MoSi₂-3.5 vol.% Si₃N₄ coating.     

AlCoCrFeNiTi_(0.5)高熵合金的高温氧化行为

采用水冷铜坩埚真空感应悬浮熔炼法制备AlCoCrFeNiTi_(0.5)多主元高熵合金,研究合金在800、900、1000和1100℃下的高温氧化行为,采用XRD,SEM及EDS对氧化膜的成分及形貌进行了分析,探索了合金的氧化机制。结果表明,合金的氧化动力学曲线在800和900℃时近似遵循六次方抛物线规律,在1000和1100℃时近似遵循四次方抛物线规律。合金具有优异的抗氧化性,在800、900和1100℃下为抗氧化级别,而在1000℃下为完全抗氧化级别。合金的氧化主要发生在枝晶间和共晶区,呈岛状团聚堆叠生长,1100℃氧化时该区域的氧化物发生明显剥落,氧化产物主要是TiO_2、Fe_2TiO_5和FeCr_2O_4等;而枝晶相的氧化产物较单一,1000℃及以下温度氧化时为弥散分布的Al_2O_3颗粒,1100℃氧化时为致密的Al_2O_3氧化层。高温氧化后,合金基体相结构稳定,未出现软化现象。     

Einfluß von Calcium sowie Cer auf das Oxidationsverhalten hochwarmfester Nickelbasislegierungen

Influence of calcium and cerium on the oxidation behaviour of high temperature strength nickel base alloys Thermogravimetric investigation into the behaviour of Ni alloys having various Al, Co, Cr, Mo, Nb, Ta, Ti, V, W, and Zr contents; the investigations were carried out at temperatures between 800 and 1200°C; the influence of minor additions of Ca and Ce has been studied simultaneously. It turns out, that the improvement of scale adhesion which can be obtained by these additions is limited to a certain temperature range; above specific upper temperature limits the alloying additions lose their efficiency. From among the alloys investigated Inconel 713C turns out to be the alloy having the highest scaling resistance under these conditions. The scale layers formed are very thin and have excellent adhesion properties.     

Nb/Mn/Si合金化的β-γ钛铝合金循环氧化行为（英文）

利用扫描电子显微镜、电子探针、电子背散射衍射和X射线衍射,研究Ti42Al1.5Mn3Nb0.1B合金和Ti42Al1.5Mn3Nb0.1B0.2C0.2Si合金在750～850℃下的循环氧化行为。两种合金的氧化增质曲线大致符合抛物线规律,且在800℃的氧化速率常数较Ti42Al5Mn1W合金的降低。在所有的实验温度下,两种合金表面都生成保护性良好的氧化膜,没有开裂或剥落发生。Nb的添加会抑制TiO₂的生长,促进Al的选择性氧化,使合金形成致密的Al₂O₃层。另外,微量Si元素的添加进一步提高合金的抗氧化性,使其生成更为致密的Al2O3层,在氧化过程中进一步抑制氧的内扩散,降低合金的氧化增质,且其效果在高温下更加明显。     

A thermo-gravimetric and microstructural study of the oxidation of Nbss/Nb5Si3-based in situ composites with Sn addition

The effect of Sn addition on the oxidation of the Nb–24Ti–18Si–5Al–5Cr–2Mo–5Hf–5Sn (at.%) alloy (JG6) in the as cast (AC) and heat treated (HT) conditions was studied at 800 °C and 1200 °C in static air using thermo-gravimetry and microstructural analysis. The oxidation kinetics, morphology and microstructure of the oxide scale and the microstructure of the bulk of the oxidised alloy were investigated. Oxidation occurred by inward oxygen anion diffusion. The oxidation of JG6 at 800 °C and 1200 °C is compared with the oxidation of Sn-free Nb–Ti–Si–Cr–Al–Mo–Hf alloys and is found to have been improved by the addition of Sn. At 800 °C pest oxidation, which was exhibited by the heat treated Nb–24Ti–18Si–5Al–5Cr–2Mo–5Hf alloy (JG4-HT), was eliminated by alloying with 5 at.% Sn. The elimination of pesting at 800 °C is attributed to the nature of the Nb solid solution in the alloy which consists of Sn-rich, Si-rich and Ti lean solid solution usually surrounded by Sn-poor, Si-poor and Ti-rich solid solution. The oxide scales that formed at 1200 °C on JG6 did not separate from the base metal and consisted of Nb₂O₅, TiO₂, SiO₂, HfO₂ and TiNb₂O₇. TiN, instead of TiO₂, and the (Nb,Ti)₅(Sn_1−xSi_x)₃ phase, which is considered as a ternary phase based on Nb₅Sn₂Si, are formed in the diffusion zone of the alloys JG6-AC and JG6-HT after oxidation at 1200 °C. The formation of these phases in the oxidised alloys JG6-AC and JG6-HT controlled the penetration of oxygen into the base material. The better oxidation performance of JG6-AC compared to JG6-HT at 1200 °C is attributed to the formation of Nb₃Sn in the former. It is suggested that the presence of the Sn-poor, Si-poor and Ti-rich Nb_ss in the microstructure is a key to the formation of the Nb₃Sn phase at the scale/diffusion zone interface in the JG6-AC oxidised at 1200 °C.     

反应烧结Ti-22Al-25Nb合金的高温氧化行为

Ti-22Al-25Nb是一种高温结构材料，它的抗氧化性对今后的发展和应用具有重要意义。采用元素粉末和反应烧结法制备了Ti-22Al-25Nb烧结合金，研究了其在静态空气中的氧化行为(923~950℃温度范围内)。不同温度(650 °C, 750 °C, 850 °C, 950 °C)下的最大增重分别为0.15 mg﹒cm-2、0.41 mg·cm-2、1.68 mg·cm-2和6.9 mg·cm-2。研究发现Ti-22Al-25Nb烧结合金具有良好的抗氧化性，特别是在750°C以下（950°C时发生氧化分解）。根据氧化动力学分析，在750℃以下，氧化行为大致遵循抛物线规律，而在850℃以上，氧化行为符合线性规律。讨论了铌合金元素对氧化动力学的影响，通过对氧化形态和相的观察和分析，证明O相（有序Ti2AlNb相）的抗氧化性能优于其它相，其原因可以解释为不同相的Nb含量的差异导致抗氧化性的差异。     

Oxidation of orthorhombic titanium aluminide Tl-22AL-25NB in air between 650 and 1000 °C

The oxidation behavior of orthorhombic titanium aluminide alloy Ti-22Al-25Nb was studied in air between 650 and 1000 °C by isothermal thermogravimetry and postoxidation scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and x-ray diffraction. Microhardness measurements were performed after exposure to gage hardening due to nitrogen and oxygen ingress. The parabolic rate constant of Ti-22Al-25Nb was of the same order as conventional titanium alloys and Ti₃Al-based titanium aluminides at and below 750 °C. Between 800 and 1000 °C, the oxidation resistance of Ti-22Al-25Nb was as good as that of γ-TiAl based aluminides; however, the growth rate changed from parabolic to linear after several tens of hours at 900 and 1000 °C. The mixed oxide scale consisted of TiO₂, AlNbO₄, and Al₂O₃, with TiO₂ being the dominant oxide phase. Underneath the oxide scale, a nitride-containing layer formed in the temperature range investigated, and at 1000 °C, internal oxidation was observed below this layer. In all cases, oxygen diffused deeply into the subsurface zone and caused severe embrittlement. Microhardness measurements revealed that Ti-22Al-25Nb was hardened in a zone as far as 300 μm below the oxide scale when exposed to air at 900 °C for 500 h. The peak hardness depended on exposure time and reached five times the average hardness of the bulk material under the above conditions.