纳米Y_2O_3对高Nb-TiAl合金高温抗蠕变性能的影响

在不同温度、不同应力条件下对高Nb-TiAl合金进行蠕变测试,结合扫描电子显微镜(SEM)、透射电子显微镜(TEM)等分析手段探究纳米Y_2O_3对Ti-45Al-6Nb-2.5V合金高温抗蠕变性能的影响。铸态高Nb-TiAl合金组织为α2/γ层片结构,纳米Y_2O_3的添加可显著细化合金组织并改善合金的高温拉伸性能。蠕变分析结果得出,添加0.15%(原子分数)纳米Y_2O_3会显著改善Ti-45Al-6Nb-2.5V合金的抗蠕变性能,在800℃/300MPa条件下,合金稳态蠕变速率由2.389×10-7 s-1降至1.500×10-7 s-1;在850℃/250 MPa条件下,合金的蠕变寿命由14.10 h延长至61.50 h。添加纳米Y_2O_3提高合金蠕变抗力的机制是Y_2O_3与基体具有较高的结合强度,可以有效阻碍位错运动,减弱孔洞萌生的倾向。经分析,2种合金在800℃/300 MPa下的蠕变行为主要受位错攀移与孪晶控制,蠕变损伤断裂机理为孔洞萌生与裂纹扩展。     

La2O3含量对Al2O3/Cu基复合材料组织与性能的影响

以La₂O₃粉、Al粉、CuO粉为反应物原料、纯铜为基体,采用原位合成技术和近熔点铸造法制备颗粒增强Cu基复合材料,研究La₂O₃对Al-CuO体系制备的Cu基复合材料组织及性能的影响。结果表明：添加La₂O₃可获得纳米Al₂O₃颗粒,且弥散分布于Cu基体中,制备的材料组织更加细小、均匀,其材料的电导率及摩擦磨损性能明显提高。当添加0.6%wtLa₂O₃,复合材料的电导率达到90.2%IACS,磨损量达到最小,相比未添加La₂O₃,其导电率提高10.1%,磨损量减小36.6%。     

钽表面铜掺杂Ta2O5纳米棒的制备及抗菌性能研究

本实验采用两步水热法在钽基体表面制备出掺杂Cu_²⁺的Ta₂O₅纳米棒薄膜。采用XRD、SEM、XPS等方法分析了材料的物相和表面微观结构。用ICP检测了样品在生理盐水中离子析出浓度,最后通过平板计数法检验了不同含量铜掺杂Ta₂O₅薄膜的抗菌能力。结果表明,通过两步水热处理,在钽表面生成了简单斜方晶体结构的Ta₂O₅纳米棒阵列,Cu_²⁺的掺杂不会对纳米棒薄膜的微观形貌和物相造成显著影响。随时间的增加,掺铜薄膜的铜离子析出速率逐渐趋于平缓。平板计数法表明,Cu_²⁺ 的掺杂量达到2.68At%时,铜掺杂Ta₂O₅纳米棒薄膜的抗菌性能最好,抗菌率达99.2%。     

NaCl-KCl-NdCl3-AlCl3熔盐体系电解制备Nd-Al合金及机理

在700℃的NaCl-KCl体系中,采用循环伏安法、方波伏安法和开路计时电位法等电化学测试方法研究了钨电极上Nd(Ⅲ)的电化学行为以及与Al(Ⅲ)共沉积的电化学过程。结果表明:在低扫描速率(0.1～0.5V·s~(-1))下,NaCl-KCl-NdCl_3熔盐中Nd(Ⅲ)的还原是一步交换3个电子的准可逆过程,该还原过程由扩散步骤控制,扩散系数约为1.2×10~(-5) cm~2·s~(-1)。将AlCl_3引入NaCl-KCl-NdCl_3熔体后,循环伏安、方波伏安以及开路计时电位测试结果表明,电解过程中形成了3种Nd-Al金属间化合物(Nd_3Al_(11)、NdAl_3和NdAl_2),其形成机理为Nd在预先沉积的Al上发生欠电位沉积。通过电动势法,计算了700℃时Nd-Al金属间化合物的热力学参数,如两相共存下Nd的活度和相对偏摩尔吉布斯自由能以及Nd-Al金属间化合物的标准吉布斯自由能。在-2.3 V下进行恒电位电解5 h制备了Nd-Al合金,所得合金由Nd_3Al_(11)、NdAl_3、NdAl_2和Al4种物相组成。     

Ti-6Al-3Nb-2Zr-1Mo钛合金热变形行为及加工图

利用Gleeble-3800热模拟试验机,在变形温度为820-1060℃及应变速率为0.001-1s_-1参数范围内对Ti-6Al-3Nb-2Zr-1Mo钛合金进行等温恒应变速率压缩试验。建立了该合金的高温变形本构方程,得到两相区和单相区的表面激活能分别为764.714 和126.936 kJ/mol。基于DMM和Prasad失稳准则建立了应变为0.4和0.7时的热加工图。分析加工图发现: Ti-6Al-3Nb-2Zr-1Mo钛合金在840–1060 ℃,应变速率为0.001–0.1 s_-1,之间主要发生DRV/DRX,此区间变形时耗散率峰值51%分别出现在940℃/0.001s_-1和880℃/1s_-1,其变形后微观组织演变机制与热加工图匹配较好,当变形发生在820℃,较高应变速率(≥1s_-1)下该合金加工时易发生流变失稳现象。     

TiAl基铸造合金的蠕变行为研究

研究了名义成分为Ti-46Al-2Cr-2Nb-0.15B合金在700～850℃,140～300MPa的蠕变条件下的蠕变性能和蠕变机制。研究表明,在蠕变过程中随着温度和载荷的增加,合金的最小蠕变速率随之增大;TiAl基合金在700～850℃,140～300MPa下的最小蠕变速率可用蠕变方程εmin=A(σ)4.7exp(-280/RT)来描述;在该蠕变条件下的蠕变行为主要受位错攀移控制。     

结构有序化金属间Pt3Co纳米线用于强化电催化氧还原性能

氧还原反应(ORR)之于燃料电池,金属空气电池等清洁能源转化装置十分重要,因此设计并合成高效且稳定的阴极氧还原催化剂已是目前热门的发展课题。为了达到精准合成材料,且最大程度地使用铂的目的,我们在此使用多孔氧化铝模板(AAO)进行恒电位沉积,在一定浓度的溶液中合成Pt₃Co一维合金纳米线。随后,合金纳米线在真空环境下进行高温退火,分别在400 ℃和650 ℃转变为无序相和有序相Pt₃Co纳米线并通过结构表征证明其已实现有序化转变。合金催化剂在AAO模板内退火,有效地防止了其在高温环境中产生团聚。通过磷酸和铬酸的溶解,合金纳米线从AAO中释放,并用于电催化氧还原反应测试。正如预期一样,与无序Pt₃Co纳米线和商业Pt/C颗粒相比,有序Pt₃Co纳米线表现出更好的半波电位和质量活性,证实了有序Pt₃Co纳米线在元素分布和晶格结构上的优势。此外,有序和无序Pt₃Co纳米线在经过5000次耐久性循环测试后,仍然比Pt/C颗粒具有更强的稳定性。由此可以看出,有序Pt₃Co纳米线作为一种可接受的,具有潜在商业价值的催化材料,成为未来燃料电池催化剂的备选材料。     

Y元素对铸造Ti-6Al-4V合金微观组织与力学性能的影响

本文研究了Y元素合金化对铸造Ti-6Al-4V合金微观组织与力学性能的影响。铸态合金微观组织与力学性能分别利用金相显微镜、扫描电镜、透射电镜和拉伸试验进行表征。结果显示,Ti-6Al-4V合金呈现典型的魏氏组织特征。添加Y元素后,合金中形成Y2O3颗粒并分布在初生β晶粒的晶界处,同时在晶界两侧形成平行的α/β层片结构,而晶粒内部形成相互交叉的α/β层片结构,即Y2O3明显改变了Ti基体片层组织形貌。相比于Ti-6Al-4V合金,添加Y元素之后,合金的屈服强度和抗拉强度稍有提高,但是平行的α/β层片结构和Y2O3颗粒引起合金由解理断裂向延晶断裂转变,进而导致延伸率显著减小。所以,Ti基体微观组织变化对合金力学性能同样具有重要作用。     

耐腐蚀性能和拉伸性能提升的 α 型钛合金设计

通过2个电子参数（结合次数Bo_t和d轨道能级Md_t）提出了新设计的α型钛（α-Ti）合金。新设计合金Ti-5Al-4Zr-3.6Sn、改性合金Ti-5Al-3Sn-1.9Zr和参考合金Ti-5Al-2.5Sn具有相同的Bo_t值（3.847）以及不同的Md_t值（2.430,2.426,2.422）。测试了3种α-Ti合金的极限抗拉伸强度（σ_UTS）、断裂应变（?_f）和热盐腐蚀性能。3种α-Ti合金均采用冷坩埚悬浮熔炼技术进行制备。结果表明,3种合金样品均具有均匀的微观结构。在3种α-Ti合金中测量到的α单相晶粒尺寸约为600 μm。Ti-5Al-4Zr-3.6Sn合金的σ_UTS和?_f值为801 MPa和16%,Ti-5Al-3Sn-1.9Zr合金的σ_UTS和?_f值为708 MPa和15%,Ti-5Al-2.5Sn合金的σ_UTS和?_f值为603 MPa和15%。热盐腐蚀测试进行28.8 ks后显示Ti-5Al-4Zr-3.6Sn、Ti-5Al-3Sn-1.9Zr和Ti-5Al-2.5Sn合金的失重率为2.61%、2.83%和3.10%。σ_UTS、?_f和耐热盐腐蚀结果表明,新设计合金Ti-5Al-4Zr-3.6Sn是一种有实际应用潜力的钛合金材料。     

挤压态Mg-8Gd-1Er-0.5Zr合金的蠕变性能研究

本文研究了挤压态Mg-8Gd-1Er-0.5Zr合金在不同温度(150-200 ℃)和应力(50-70 MPa)条件下100 h的蠕变行为,利用OM、TEM等手段观察了蠕变过程中的组织演变规律,并对蠕变机理进行了分析。研究结果表明,在本文试验条件下,合金表现出优异的蠕变性能,所有的蠕变曲线均呈现出减速蠕变和稳态蠕变两个阶段;在150 ℃/50 MPa时稳态蠕变速率仅为6.48×10-11s-1 ,蠕变量为0.007%;在200 ℃/50 MPa时稳态蠕变速率为4.26×10-9s-1,蠕变量为0.226%;温度较低时(150 ℃)主要为扩散蠕变控制机制,温度较高时(175 ℃、200 ℃)蠕变机制以位错蠕变为主。蠕变过程中晶内析出的β′相与镁基体具有一定的位相关系：(020)_β′∥_Mg,[001] _β′∥[0001]_Mg,阻碍位错运动,而晶界析出的β相可以钉扎晶界。二者协同作用,促进合金高温蠕变性能的提高。     

高阻尼高强度铸态SiCp/Mg94Zn5Y1 复合材料的综合性能

采用铸造方法制备具有不同SiC_p含量（0.5%~2.0%，质量分数，下同）的SiC_p/Mg₉₄Zn₅Y₁复合材料，并研究了复合材料的力学性能和阻尼性能。通过扫描电子显微镜和X射线衍射仪测试复合材料的微观组织结构和物相组成。在基体中加入SiC_p之后，SiC_p均匀分布在基体中，增强体细化了复合材料的微观组织结构。SiC_p/Mg₉₄Zn₅Y₁复合材料包括α-Mg、I相（准晶相）和SiC_p相。分别使用动态热机械分析仪和AG-X试验机测试了SiC_p/Mg₉₄Zn₅Y₁复合材料的阻尼性能和力学性能。复合材料的力学性能优于Mg₉₄Zn₅Y₁合金，1.0%SiC_p/Mg₉₄Zn₅Y₁复合材料的抗压缩强度高达350 MPa；所有复合材料的阻尼性能都远高于基体合金的阻尼性能，其中0.5%SiC_p/Mg₉₄Zn₅Y₁复合材料具有最佳的阻尼性能。此外，根据功效系数法，SiC_p含量为1.0%的SiC_p/Mg₉₄Zn₅Y₁复合材料具有良好的综合性能。     

Al0.5Nb1.5TiV2Zr0.5 难熔高熵合金组织和力学性能

采用真空电弧熔炼制备了Al_0.5Nb_1.5TiV₂Zr_0.5高熵合金,并研究了其微观组织、密度及力学性能。结果表明,Al_0.5Nb_1.5TiV₂Zr_0.5合金由为90.6%(体积分数)的体心立方相和9.4%(体积分数)的C14-Laves第二相组成。合金基体相富含Ti和V,第二相富含Al和Zr。合金的密度为6284 kg/m3,维氏硬度为5197.9 MPa。合金的屈服强度随温度升高而降低,由室温下1082.9 MPa降低到1073 K下的645.0MPa。压缩应变由室温下的27.20%降低到873 K下的14.94%,这与合金中原子间的相互作用力随温度升高而降低有关。在1073 K时合金应变超过50%,表现出良好的塑性而未发生断裂。压缩测试结果表明,合金韧脆转变温度在873～1073 K之间。     

High dielectric constant of (Ba0.96Ca0.04)(Ti0.85Zr0.15)O3 multilayer ceramic capacitors with Cu doped Ni electrodes

A nickel paste with Cu dopant was used as the internal electrodes in multi-layer ceramic capacitors (MLCCs) using barium titanate (Ba_0.96Ca_0.04)(Ti_0.85Zr_0.15)O₃ ceramic (BCTZ) with copper endtermination. The sintering behaviors of the MLCC and the interfacial structure between the Ni/Cu electrodes and the BCTZ dielectrics have been investigated. The thermal shrinkage and sheet resistance of the Ni/Cu alloys sintered at 1220 °C for 2 h in a reducing atmosphere were measured using thermal analysis techniques (TMA) and four-point probe equipment. The composition distributions, microstructures and line defects were examined using microstructural analysis techniques (SEM/HRTEM) coupled with energy-dispersive spectroscopy (EDS). The Cu alloyed with Ni significantly improves the continuity of the electrode in the MLCC; this is due to there being no mutual trigger reaction between Ni and BCTZ dielectrics. In terms of the electrical properties, the results showed that Ni paste with Cu dopant improves the dielectric constant of the MLCC, but the dielectric loss (tan δ) is a slightly when higher compared to standard MLCC.     

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.     

改进型镁扩散法制备高临界电流密度MgB2超导体性能研究

本文采用一种改进型镁扩散法成功制备出密度达到1.95g/cm₃的MgB₂超导块材。论文研究了不同的热处理条件对MgB₂块材的超导转变温度(T_c)和临界电流密度(J_c)性能的影响。采用最佳热处理条件制备的MgB₂超导体T_c和J_c分别达到了38.1K和0.53MA/cm₂(10K,自场)。为了改进镁扩散法MgB₂超导体中弱的高场磁通钉扎性能,本文还研究了nano-Pr₆O₁₁和C掺杂对MgB₂超导体的临界电流密度和不可逆场(H_irr)的影响。结果表明C掺杂的MgB₂超导体临界电流密度在10K,6T下达到了10₄A/cm₂,该结果比未掺杂MgB₂超导体在同样条件下性能提高了两个量级,甚至比固态反应法制备的nano-C掺杂MgB₂超导体性能更好。利用该方法制备的nano-Pr₆O₁₁掺杂的MgB₂超导体在10K,2T下也比未掺杂样品J_c提高达9.4倍。根据大量的实验结果和理论分析我们提出基于改进型镁扩散法和化学掺杂,包括纳米粒子和C掺杂,很有可能是一种制备高性能MgB₂超导体非常有效的途径。     

Sinterability and dielectric properties of Ba0.55Sr0.4Ca0.05TiO3-CaTiSiO5-Mg2TiO4 composite ceramics

The composite ceramics of Ba_0.55Sr_0.4Ca_0.05TiO₃-CaTiSiO₅-Mg₂TiO₄ (BSCT-CTS-MT) were prepared by the conventional solid-state route. The sintering performance, phase structures, morphologies, and dielectric properties of the composite ceramics were investigated. The BSCT-CTS-MT ceramics were sintered at 1100 °C and possessed dense microstructure. The dielectric constant was tailored from 1196 to 141 as the amount of Mg₂TiO₄ increased from 0 to 50 wt%. The dielectric constant and dielectric loss of 40 wt% Ba_0.55Sr_0.4Ca_0.05TiO₃-10 wt% CaTiSiO₅-50 wt% Mg₂TiO₄ was 141 and 0.0020, respectively, and the tunability was 8.64% under a DC electric field of 8.0 kV/cm. The Curie peaks were broadened and depressed after the addition of CaTiSiO₅. The optimistic dielectric properties made it a promising candidate for the application of tunable capacitors and phase shifters.     

Sol-gel synthesis of Bi3.25La0.75Ti3O12 nanotubes

Ferroelectric Bi_3.25La_0.75Ti₃O₁₂ (BLT) nanotubes were synthesized by sol-gel technique using nanochannel porous anodic aluminum oxide (AAO) templates, and were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM). BLT nanotubes with diameter of around 240 nm and the wall thickness of about 25 nm exhibited a single orthorhombic perovskite structure and highly preferential crystal growth along the [1 1 7] orientation, which have smooth wall morphologies and well-defined diameters corresponding to the diameter of the applied template. The formation mechanism of BLT nanotubes was 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.     

Low temperature sintering and microwave dielectric properties of (Mg0.7Zn0.3)0.95Co0.05TiO3 ceramics with BaCu(B2O5) additions

The effects of BaCu(B₂O₅) additives on the sintering temperature and microwave dielectric properties of (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics were investigated. The (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics were not able to be sintered below 1000 °C. However, when BaCu(B₂O₅) were added, they were sintered below 1000 °C and had the good microwave dielectric properties. It was suggested that a liquid phase with the composition of BaCu(B₂O₅) was formed during the sintering and assisted the densification of the (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics at low temperature. BaCu(B₂O₅) powders were produced and used to reduce the sintering temperature of the (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics. Good microwave dielectric properties of Q × f = 35,000 GHz, ?_r = 18.5.0 and τ_f = −51 ppm/°C were obtained for the (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics containing 7 wt.% mol% BaCu(B₂O₅) sintered at 950 °C for 4 h.     

废旧锂离子电池中Li, Fe和V的回收及xLiFePO4-yLi3V2(PO4)3的制备

由于LiFePO_4和Li_3V_2(PO_4)_3材料的特征相近,制备方法类似,提供了一种从废旧LiFePO_4和Li_3V_2(PO_4)_3混合电池中回收Li、Fe和V,再制备xLiFePO_4-yLi_3V_2(PO_4)_3的方法。在空气气氛中600℃热处理1h后,去除粘结剂PVDF使活性物质与集流体分离。调节Li、Fe、V和P摩尔比,球磨、锻烧,配制不同比例的xLiFePO_4-yLi_3V_2(PO_4)_3(x:y=5:1,7:1,9:1)复合电极材料。表征了其形貌、结构和电化学性能,结果表明,回收制备的复合材料将同时具备LiFePO_4和Li_3V_2(PO_4)_3两种材料的电化学性能,能显著改善LiFePO_4的倍率性能。