复合阻隔法的阻隔效应原理及其在扩散连接中的应用

以TiAl金属间化合物增压涡轮与 4 0Cr钢轴的扩散连接为背景 ,提出了复合阻隔法扩散连接工艺 ,并探讨了阻隔效应原理 ,建立了从材料的扩散连接性角度出发的原子半径、原子电负性阻隔层选择原则。利用本文的扩散连接阻隔效应原理 ,确定了TiAl金属间化合物增压涡轮与 4 0Cr钢轴的扩散连接复合阻隔层为Ti/V/Cu ,由此得到的扩散连接接头在V/Cu及Cu/ 4 0Cr的连接界面处出现了对连接性能有利的无限固溶体层 ,在TiAl/Ti的接触面上生成了能够强化接头强度的Ti3 Al TiAl双相层和Ti的固溶体层 ,与TiAl/ 4 0Cr直接扩散连接相比 ,Ti/V/Cu复合阻隔层的加入 ,避免了在TiAl/4 0Cr的接触面上TiC、Ti3 Al、FeAl、FeAl2 金属间化合物脆性相的产生 ,接头强度高达4 2 0MPa ,因此利用本文的阻隔效应原理可以很好地进行复合阻隔层的选择     

Ti-Ni钎焊Cf/SiBCN陶瓷接头界面组织及机理分析

使用Ti-Ni高温钎料实现C_f/SiBCN陶瓷自身连接.分别研究了钎料成分、钎料箔片叠层方式以及钎焊温度对焊接界面组织形貌的影响.结果表明,在Ni元素含量超过50%且以Ni/Ti/Ni方式叠层得到的接头界面良好,其中Ni元素深入陶瓷基体,与Si元素发生反应,在陶瓷内形成扩散层结构,扩散层内的Ni,Si元素成梯度分布,而Ti元素以化合物的形式弥散分布在焊缝中间部分的钎料层中试验发现,提高钎焊温度有利于Ni元素的扩散,在以Ni/Ti/Ni叠层、Ni元素含量低于50%时,提高钎焊温度至1 300℃得到的接头没有显著裂纹,中间层的钛化合物分布更加弥散.     

Ti/Cu/Ti部分瞬间液相连接Si_3N_4的界面反应和连接强度

用Ti/Cu/Ti多层中间层在 12 73K进行氮化硅陶瓷部分瞬间液相连接 ,实验考察了保温时间对连接强度的影响。用SEM ,EPMA和XRD对连接界面进行微观分析 ,并用扩散路径理论 ,研究了界面反应产物的形成过程。结果表明 :在连接过程中 ,Cu与Ti相互扩散 ,形成Ti活度较高的液相 ,并与氮化硅发生反应 ,在界面形成Si3N4 /TiN/Ti5Si3 Ti5Si4 TiSi2 /TiSi2 Cu3Ti2 (Si) /Cu的梯度层。保温时间主要是通过影响接头反应层厚度和残余热应力大小而影响接头的连接强度     

TiAl/V/Cu/40Cr钢扩散连接界面组织结构对接头强度的影响

扩散连接界面组织结构是影响连接性能的关键因素，不同的界面组织结构及生成相所决定的接合强度不同，研究了TiAl/V/Cu/40Cr钢的扩散连接，结果显示，在V/Cu及Cu/40Cr的连接界面处出现了对连接性能有利的无限固溶体层，而在TiAl/V界面处有金属间化合物层出现，接头全部断裂于TiAl/V界面处，TiAl/V界面生成的金属间化合物V5Al8脆性相严重弱化了接头性能，使接头强度仅为200MPa。     

电场激活Ti/Ni扩散偶连接界面相变规律与力学性能的研究

本试验采用电场激活扩散连接技术(FADB)实现了Ti/Ni的扩散连接。研究了Ti/Ni两种材料发生界面扩散反应时新相的生成规律及其对连接强度的影响。利用扫描电子显微镜及能谱仪观察和分析了扩散层的显微组织、相组成和界面元素分布。采用万能试验机对扩散层的抗剪切性能进行了测试。研究结果表明,在电场作用下,Ti与Ni通过固相扩散形成了良好的冶金结合界面,界面处金属间化合物的生成次序依次为Ni3Ti、Ni Ti2、Ni Ti。当扩散温度≥750℃时,Ti表现出超塑性和良好的扩散性,促使扩散层中的Ni3Ti转变成富钛层,该富钛层的形成有利于接头强度的提高。界面的剪切强度随着电流的增大而增大,当电流为930~1200 A时,界面的剪切强度可达90.54 MPa。     

Ag元素对真空扩散焊Cu/Al界面组织及性能的影响

通过添加不同厚度的Ag中间层,采用真空扩散焊工艺进行Cu/Al异质金属连接。利用扫描电镜(SEM)及能谱仪(EDS)对界面的元素分布及相组成进行分析,采用剪切试验及电化学腐蚀能测试对异质复合接头力学及耐腐蚀性能进行了分析。结果表明,Ag中间层可以有效抑制Al和Cu界面生成脆性金属间化合物相,Ag以较快的方式扩散进入Al基体的晶界中。界面上生成宽度较窄的Cu、Al化合物。与Cu/Al直接连接相比,添加Ag箔的界面电化学腐蚀电位有明显提升,表明Ag元素的添加有效改善了Cu/Al接触界面的耐腐蚀性能。     

Mg/Al真空扩散焊接头界面的显微组织和力学性能

对Mg/Al异种金属进行真空扩散焊接,采用SEM和XRD等手段分析接头界面微观结构和相成分,研究Mg/Al界面组织结构的演变规律,测试接头的抗弯强度。结果表明:真空扩散焊接能够实现Mg1/Al1060的连接;扩散焊接过程中,界面发生扩散反应生成中间相Mg_2Al_3和Mg_(17)Al_(12),且Mg_2Al_3相生长速率要快于Mg_(17)Al_(12)相;中间相由初始的岛状组织,经纵向长大相互连接,最后形成均匀平直的扩散反应层;接头最高抗弯强度为36.3MPa,断裂发生在扩散反应层,属于准解理断裂。     

用中间层为非活性金属FeNi/Cu的Si3N4陶瓷与Ni的扩散连接

采用非活性金属中间层FeNi/Cu在高、低真空条件下进行了Si3N4陶瓷与Ni的扩散连接,然后对部分接头进行了热等静压(HIP)后处理,测定了连接接头的四点弯曲强度,用扫描电镜(SEM)、电子探针(EPMA)和X射线衍射仪(XRD)对连接界面区域进行了分析.结果表明,采用非活性金属中间层扩散连接Si3N4陶瓷与Ni,在高真空和低真空条件下均能获得高强度连接,连接界面处没有形成Ni-Si化合物反应层,连接时间对接头强度的影响不明显.上述特征与用活性金属中间层连接时的情况截然不同.本文的连接方法有着重要的工程应用前景.     

活性金属部分瞬间液相连接氮化硅陶瓷的研究

采用Ti/Cu/Ti多层中间层在1273 K温度下进行氮化硅陶瓷部分瞬间液相连接,考察了保温时间对连接强度的影响,并对连接界面进行了SEM,EPMA和XRD分析.结果表明,通过Cu-Ti二元扩散促使液相与氮化硅发生界面反应,形成Si3N4/TiN/Ti5Si3+Ti5Si4+TiSi2/TiSi2+Cu3Ti2(Si)/Cu的梯度层.保温时间影响接头反应层厚度,从而影响接头的连接强度根据活性金属部分瞬间液相连接陶瓷的界面行为,建立了活性金属部分瞬间液相连接陶瓷的理论模型.该模型较好地解释了Ti/Cu/Ti和Ti/Ni/Ti连接氮化硅陶瓷的异同点和连接工艺参数的选择.     

中间层厚度对TLP扩散连接TC4组织和性能的影响

采用电沉积Ni/Cu层作为中间层实现了TC4钛合金瞬时液相（TLP）扩散连接,采用扫描电子显微镜、能谱仪和X射线衍射仪研究了Cu层厚度对TC4钛合金接头界面微观组织和力学性能的影响,并结合Ti-Cu和Ti-Ni二元相图阐明了反应机制。结果表明,瞬时液相扩散连接接头的典型界面组织为TC4/α-Ti+Ti2(Cu, Ni)/TC4,其中Ni元素均以固溶体的形式存在于接头中。随着电沉积Cu层厚度增加,扩散层和焊缝宽度增加,接头中央未焊合的孔洞消失,反应层中开始出现连续的Ti2(Cu, Ni)金属间化合物层且宽度逐渐增加。接头抗拉强度在电沉积Cu层厚度为15 μm时达到最大值500 MPa。断裂分析表明,所有TLP扩散连接接头均以解理断裂方式在焊缝处断裂。     

Fe3O4/SiO2/Bi2WO6磁性复合光催化剂的制备及其光催化性能

钨酸铋(Bi₂WO₆),结构最简单的Aurivillius相化合物,是近期受到研究者关注的新型光催化材料。然而,光催化剂粉末在反应介质中难被回收,工业化应用成本较高。本文用三步方法合成了可回收的Fe₃O₄/SiO₂/Bi₂WO₆磁性复合光催化剂,通过溶剂热法合成具有磁性的Fe₃O₄,用溶胶凝胶法在Fe₃O₄表面覆盖SiO₂层,后将磁性颗粒与Bi₂WO₆纳米片相结合。光催化剂的形貌结构及性能通过XRD、SEM、PL、UV-vis进行表征测试。结果表明,直径约500 nm的Fe₃O₄微球附着在边长约500 nm的Bi₂WO₆纳米片的表面,SiO₂在两者之间起到了粘连作用。光催化剂Fe₃O₄/SiO₂/Bi₂WO₆对于罗丹明B的光降解活性较好,且有一定磁性,可以通过外加磁场将其从溶液中分离,有较大的应用潜力。     

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.     

Synthesis and characterization of Y3Al5O12 and ZrO2-Y2O3 thermal barrier coatings by combustion spray pyrolysis

Y₃Al₅O₁₂ and ZrO₂-Y₂O₃ (8 mol% YSZ) coatings for potential application as thermal barrier coatings were prepared by combustion spray pyrolysis. Thermal cycling of as deposited coatings on stainless steel and FeCrAlY bond coat substrates was carried out at 1000 °C and 1200 °C to determine the thermal fatigue response. Structural and morphological studies on Y₃Al₅O₁₂ and 8 mol% YSZ coatings before and after thermal cycling have been carried out. It has been noted that the coatings on FeCrAlY substrates remain intact after 50 cycles between room temperature and 1200 °C, whereas the coatings on stainless steel show some minor damage such as peeling off near the periphery after 50 cycles at 1000 °C. Thermal diffusivity values of Y₃Al₅O₁₂ and 8 mol% YSZ films were measured by using photo thermal deflection spectroscopy and the values are lower than those of coatings produced by conventional techniques such as EBPVD and APS.     

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.     

BN/Al2O3 复合粉末及其聚合物基复合材料的制备与导热性能

采用固-液相共混法制备了多种BN/Al₂O₃复合粉末,通过冻融法和表面修饰法对BN进行了改性处理,改变表面修饰剂类型和摩尔比得到了前驱体和烧结态BN/Al₂O₃复合粉末,并利用机械混合法制备了聚合物基BN/Al₂O₃复合材料,并测试分析了其导热性能。结果表明,经冻融处理的BN分散性和界面相容性明显优于未经冻融处理的BN。多巴胺对BN的改性效果优于聚乙二醇。采用多巴胺作为表面修饰剂且BN与Al(NO₃)₃的摩尔比为1:1时,能够得到纳米Al₂O₃均匀包覆的微米BN粉末,即BN/Al₂O₃微纳复合粉末,其聚合物基复合材料的导热系数可达0.62 W·m^-1·K^-1,是纯聚合物导热系数的3倍,是采用纯微米BN粉末制备的聚合物基复合材料导热系数的1.5倍。在BN表面附着的Al₂O₃可以形成层状热传导通道,能够有效提高聚合物基BN/Al₂O₃复合材料的热导率。     

Gd3+掺杂La2Mo2O9的相稳定性及热导率

La2Mo2O9具有极低的热导率,但其在580℃左右会发生α-β相变,严重影响其性能和应用。本实验以Gd203掺杂La2Mo2O9制备了一系列La2-xGdxMo2O9 (x=0.0~0.5)固溶体,研究了掺杂Gd3+对La2Mo2O9相稳定性和热导率的影响。结果表明,随着Gd3+掺杂量的增加,相变得到有效抑制,当x≥0.2时样品以β相存在。样品的热导率随Gd3+掺杂量的增加先减小后增加,室温下在x=0.2时达到最低,此后缓慢上升,但所有样品的热导率均小于1 W/(m·K)。     

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)”。     

Improved capacity and rate capability of Ru-doped and carbon-coated Li4Ti5O12 anode material

Pure Li₄Ti₅O₁₂, modified Li₄Ti₅O₁₂/C, Li₄Ru_0.01Ti_4.99O₁₂ and Li₄Ru_0.01Ti_4.99O₁₂/C were successfully prepared by a modified solid-state method and its electrochemical properties were investigated. From the XRD patterns, the added sugar or doped Ru did not affect the spinel structure. The results of electrochemical properties revealed that Li₄Ru_0.01Ti_4.99O₁₂/C showed 120 and 110 mAh/g at 5 and 10 C rate after 100 charge/discharge cycles. Li₄Ru_0.01Ti_4.99O₁₂/C exhibited the best rate capability and the highest capacity at 5 and 10 C charge/discharge rate owing to the increase of electronic conductivity and the reduction of interface resistance between particles of Li₄Ti₅O₁₂.It is expected that the Li₄Ru_0.01Ti_4.99O₁₂/C will be a promising anode material to be used in high-rate lithium ion battery.     

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.     

SNDC/La2Mo2O9复合电解质材料的制备及性能表征

本文采用甘氨酸-硝酸盐法(GNP)和溶胶凝胶法分别合成了Sm_0.1Nd_0.1Ce_0.8O_1.9(SNDC) 和La₂Mo₂O₉(LAMOX)粉末,并用常压烧结的方法制备了不同比例的SNDC和LAMOX的复合材料,通过XRD和SEM等手段表征了不同复合比例样品的物相和表面形貌并测试了烧结样品的电导率。结果表明,复合样品的电导率在相变点前后随着复合量增加变化趋势相反,其中LAMOX含量为20mol%的样品在550℃时的电导率能达到0.01S/cm,高于同温度下SNDC电导率。