Ti掺杂对ZrCo贮氚合金中氦行为的影响研究

采用掠入射X射线衍射（GIXRD）、弹性离子反冲（ERD）、氦热解吸（TDS）、扫描电镜（SEM）对直流磁控溅射法制备的含氦Zr-Co、Zr-Ti-Co薄膜进行分析，分别得到样品物相、氦的深度和浓度分布、氦热解吸图谱以及热解吸前后的表面形貌。氦热解吸实验曲线反映出Ti的掺杂有利于抑制ZrCo贮氚合金中氦的迁移、聚集和发展，提升相应捕陷位置中氦的释放温度；氦热解吸后，Zr0.8Ti0.2Co薄膜样品的晶界密度相比ZrCo薄膜样品更低，降低减少了氦泡迁移的通道，延缓高温下氦泡迁移合并的趋势，表明掺杂Ti可提升ZrCo合金的固氦能力,对高温条件下氦的释放具有抑制作用。     

Ti元素改性ZrCo合金在CO杂质气氛中吸氢行为及影响机制

采用EDS和XRD表征了Ti改性ZrCo合金的相结构及表面元素分布,采用飞行时间二次离子质谱(TOF-SIMS)以及程控升温热解脱附(TPD)方法研究少量CO(1.05%CO+98.95%H_2气氛,体积分数,)对Zr_(0.8)Ti_(0.2)Co合金氢化行为的影响及作用机制。结果表明:在纯氢环境下ZrCo合金和Zr_(0.8)Ti_(0.2)Co合金饱和吸氢时间分别少于2和4 min,饱和吸氢容量分别为1.8%和1.9%(质量分数)。而在含1.05%CO的氢中ZrCo合金和Zr_(0.8)Ti_(0.2)Co合金在2500 min内均未能达到吸氢饱和,吸氢容量分别下降到0.91%和0.48%,Ti改性导致ZrCo合金在CO杂质气氛中的吸氢动力学性能下降。实验表明,通过773 K、0.5 h热抽空处理可恢复至毒化前吸氢性能。     

Zr_(1-x)Nb_xCo(x=0～0.2)合金吸放氢及抗歧化性能研究

采用真空电弧熔炼法制备了Zr_(1-x)Nb_xCo (x=0,0.05,0.1,0.15,0.2)合金,研究了Nb掺杂对ZrCo合金相组成、吸放氢及抗歧化性能的影响。XRD结果表明:Zr_(1-x)NbxCo (x=0～0.2)合金主相为ZrCo相,含有少量ZrCo_2杂相;氢化物为ZrCoH_3相。Nb掺杂有利于ZrCo合金吸放氢性能的提高:ZrCo吸氢反应活化时间为7690 s,Zr_(0.8)Nb_(0.2)Co缩短至380s;ZrCo吸氢反应表观活化能力44.88 kJ·mol~(-1) H_2,Zr_(0.8)Nb_(0.2)Co降低至32.73 kJ·mol~(-1) H_2;10 K/min升温速度下,ZrCo-H系统放氢温度为597.15 K,Zr_(0.8)Nb_(0.2)Co-H系统降低至541.36 K;ZrCo-H系统放氢反应表观活化能为100.55 kJ·mol~(-1) H_2,Zr_(0.8)Nb_(0.2)Co-H系统降低至84.58 kJ·mol~(-1) H_2。放氢模式下798 K保温10 h ZrCo歧化83.68%,Zr_(0.8)Nb_(0.2)Co仅歧化8.71%;Nb掺杂降低合金氢化物8e间隙氢原子数量,减小岐化反应驱动力,提高合金抗歧化性能。     

Al9Fe0.7Ni1.3相对喷射沉积Al-Zn-Mg-Cu-Ni合金组织和性能的影响

本文利用喷射沉积技术合成含Ni的Al-Zn-Mg-Cu合金,合金中的Ni元素以亚微米球状Al₉Fe_0.7Ni_1.3化合物的形式存在。利用扫描电镜和电子背散射衍射、透射电镜以及拉伸测试研究了Al₉Fe_0.7Ni_1.3颗粒对合金固溶处理后组织和性能的影响。结果发现：Al₉Fe_0.7Ni_1.3颗粒主要在晶界附近分布,说明该颗粒在固溶过程中具有有力的抑制再结晶作用。固溶处理后,合金的拉伸强度为603 MPa,断裂延伸率为11.79%,主要断裂方式为穿晶延性断裂。实验结果表明亚微米球状Al₉Fe_0.7Ni_1.3化合物对合金性能有重要影响,可以产生细晶强化和Orowan强化,是合金发生穿晶延性断裂的主要原因。     

Co1.2Mn0.8B化合物的磁性能与磁热效应

采用球磨和固相烧结相结合的方法制备了Co_(1.2)Mn_(0.8)B化合物,并对其晶体结构、磁性能和磁热效应进行了研究。结果表明,Co_(1.2)Mn_(0.8)B化合物的物相为Co_2B单相结构,具有CuAl2型体心正方晶体结构,空间群为I14/mcm;在居里温度TC=175 K附近,化合物发生了铁磁(FM)-顺磁(PM)二级磁相转变,热滞为0.7 K;Co_(1.2)Mn_(0.8)B化合物在外磁场0～5 T变化下的最大磁熵变ΔSM为1.17 J·(kg·K)~(-1),其对应的温度不随外场的变化而变化。     

微观相场法反演Ni0.75AlxV0.25-x合金的原子间相互作用势

采用微观相场法,利用Khachaturyan所给原子间相互作用势与长程序参数关系方程,计算出Ni_(0.75)Al_xV_(0.25-x)合金L1_0、L1_2和DO_(22)相第一近邻原子间相互作用势,并用计算的原子间相互作用势模拟了Ni_(0.75)Al_xV_(0.25-x)合金沉淀过程以及最终形貌。计算结果表明,L1_0、L1_2和DO_(22)相第一近邻原子间相互作用势随温度增大而增大,随浓度增大而增大,且计算得到的随温度和浓度变化的原子间相互作用势与之前的实验值符合较好。计算的原子间相互作用势的模拟结果能依次得到预析出相L1_0、稳定相L1_2和第二相DO_(22),且合金沉淀形貌与实验结果吻合。相场法反演原子间相互作用势,拓宽了相场法在合金设计中的应用范围。     

相场法研究Ni-Al间作用势对Ni75Al14Cr11合金L10预析出相的影响

采用微观相场法研究了Ni_(75)Al_(14)Cr_(11)合金第1个近邻到第4个近邻Ni-Al原子间相互作用势对L1_0预析出相沉淀过程的影响。结果表明,当第3近邻Ni-Al原子间相互作用势增大或第4种近邻Ni-Al原子间相互作用势减少时,L1_0预析出相和L1_2平衡相均提前沉淀,且L1_0预析出相体积分数减少而L1_2相的最终体积分数几乎不变;当第3近邻Ni-Al原子间相互作用势减少或第4近邻Ni-Al原子间相互作用势的增大时,L1_0预析出相和L1_2最终相都会推迟沉淀,且L1_0预析出相和L1_2相体积分数均增大;与上述2种情况相比,改变第1近邻Ni-Al原子间相互作用势对L1_0预析出相沉淀过程的影响较小,而改变第2近邻Ni-Al原子间相互作用势对沉淀过程几乎没有影响。进一步研究表明,Ni-Al原子间相互作用势改变不影响合金的沉淀机制,将影响L1_0预析出相、L1_2平衡相的析出时间、速度和2种相的体积分数,沉淀形貌等,从而影响Ni_(75)Al_(14)Cr_(11)高温合金的结构和性能,对合金优化设计有指导意义。     

冷轧对TiNi合金组织及力学性能的影响

在室温下对TiNi合金进行轧制,采用OM、XRD、DSC、TEM等分析检测技术,研究了冷轧变形量对TiNi合金显微组织演变、力学性能的影响规律,探讨了合金变形的微观机制。结果表明：TiNi合金在冷轧变形过程中,组织发生了B2奥氏体相向B19’马氏体相的转变;随变形量的增加,组织的不均匀变形增加,出现了纳米晶和非晶相。冷轧后的TiNi合金在拉伸过程中仅表现出奥氏体相、马氏体相的弹性变形和塑性变形阶段,应力诱发马氏体相变阶段消失,表现为连续屈服过程。TiNi合金在不同的应变阶段具有不同的变形机制：当应变量为0<ε≤0.3时,合金的主要变形机制为位错滑移;当应变量ε>0.3时,合金以孪生和位错滑移相结合的变形机制进行变形。     

硼含量对有序态(Fe,Co)3V合金环境氢脆的影响

通过在真空和氢气环境下的拉伸实验,研究了硼含量对有序态(Fe,Co)_3V合金力学性能和环境氢脆的影响。结果表明,当在有序态(Fe,Co)_3V合金中添加0.02%B(质量分数)时,相对于无硼合金,合金的晶粒尺寸减小了27.5%,合金在真空和氢气中的抗拉强度和延伸率均达到最大值;而当硼含量继续增加时,合金的晶粒尺寸、合金在真空和氢气中的力学性能均保持不变。无硼有序态(Fe,Co)_3V合金在氢气中呈现严重的环境氢脆,当在合金中添加0.02%B后,合金氢脆因子降低了34.4%,合金的断口形貌由完全沿晶断口转变为穿晶和沿晶的混合断口;当合金中的硼含量继续增加时,合金的氢脆因子不再降低,恒定在50%左右,即硼原子只能部分抑制有序态(Fe,Co)_3V合金在氢气中的环境氢脆。     

Bi2Sn2O7含量对改性Ag/SnO2电接触复合材料性能的影响研究

以SnO2、Bi2Sn2O7为增强相粉体,化学银粉为基体相,采用高能球磨辅助常压烧结工艺制备出系列Bi2Sn2O7改性SnO2增强银基复合材料。考察了Bi2Sn2O7含量、球磨时间、烧结制度对Ag/SnO2-Bi2Sn2O7复合材料物理性能的影响规律。结果表明：随着球磨时间从1h延长至12h,Ag/SnO2-(6 wt.%) Bi2Sn2O7复合粉体从颗粒态向片状结构发生转变,Ag/SnO2-(6 wt.%) Bi2Sn2O7复合材料的电阻率呈逐渐上升趋势而密度呈不断下降趋势。烧结温度的提升和Bi2Sn2O7掺杂量的增加均有助于降低Ag/SnO2-Bi2Sn2O7复合材料的电阻率,且当Bi2Sn2O7掺杂量为12 wt.%、烧结温度900℃时,样品Ag/ (12 wt.%) Bi2Sn2O7的电阻率达到最佳值2.24 μΩ·cm。循环50次的初期电弧烧蚀试验分析可知,相比于纯Ag/SnO2而言,Bi2Sn2O7改性样品表面的烧损面积并未快速扩展至整个表面,且当Bi2Sn2O7含量为6 wt%时,Ag/SnO2-(6 wt.%) Bi2Sn2O7样品表面的烧损面积最小。而当Bi2Sn2O7含量为12 wt.%时, Ag/ (12 wt.%) Bi2Sn2O7表面烧蚀区出现了飞溅现象,这可能归因于其较低的表面硬度(82.38HV0.3)。     

储氚合金ZrCo0.8M0.2 (M = Co, Cu, Cr, Mn, Al)的性能研究

采用电弧熔炼的方法在氩气气氛中熔炼了ZrCo_0.8M_0.2 (M = Co、Cu、Cr、Mn、Al)合金。合金的主相均为ZrCo相,但Cr、Mn和Al部分替代Co后形成了第二相。Cr替代形成了Zr₂Co和ZrCr₂相,Mn替代形成了Zr₂Co和ZrMn₂相,Al替代形成Zr₃Co和Zr₆CoAl₂相。Cr和Mn的替代使合金的晶胞体积减小,而Cu和Al的替代使晶胞体积增大。Cu、Cr、Mn和Al替代后,ZrCo_0.8M_0.2合金的平台压变化不明显,但吸氢量出现了不同程度的降低。Cr和Mn元素的替代明显改善了ZrCo合金在室温下的活化性能。Cr和Mn元素的替代降低了高温下ZrCo合金发生歧化反应的速率,这主要是由于Cr和Mn元素的掺杂减少了氢原子占据不稳定位置8f₂ 和8e的数量,从而降低了歧化反应发生的驱动力。     

An investigation on hydrogen storage kinetics of nanocrystalline and amorphous Mg2Ni1−xCox (x = 0-0.4) alloy prepared by melt spinning

In order to improve the hydrogen storage kinetics of the Mg₂Ni-type alloys, Ni in the alloy was partially substituted by element Co, and melt-spinning technology was used for the preparation of the Mg₂Ni_1−xCo_x (x = 0, 0.1, 0.2, 0.3, 0.4) hydrogen storage alloys. The structures of the as-cast and spun alloys are characterized by XRD, SEM and TEM. The hydrogen absorption and desorption kinetics of the alloys were measured by an automatically controlled Sieverts apparatus. The electrochemical hydrogen storage kinetics of the as-spun alloys is tested by an automatic galvanostatic system. The hydrogen diffusion coefficients in the alloys are calculated by virtue of potential-step method. The electrochemical impedance spectrums (EIS) and the Tafel polarization curves are plotted by an electrochemical workstation. The results show that the substitution of Co for Ni notably enhances the glass forming ability of the Mg₂Ni-type alloy. Furthermore, the substitution of Co for Ni, instead of changing major phase Mg₂Ni, leads to forming secondary phases MgCo₂ and Mg. Both the melt spinning treatment and Co substitution significantly improve the hydrogen absorption and desorption kinetics. The high rate discharge ability, the hydrogen diffusion coefficient and the limiting current density of the alloys significantly increase with raising both the spinning rate and the amount of Co substitution.     

Synthesis and characterization of Al2O3-Ce0.5Zr0.5O2 powders prepared by chemical coprecipitation method

Al₂O₃-Ce_0.5Zr_0.5O₂ catalytic powders were synthesized by the coprecipitation (ACZ-C) and mechanical mixing (ACZ-M) methods, respectively. As-synthesized powders were characterized by XRD, Raman spectroscopy, surface area and thermogravimetric analyses. It was found that the mixing extent of Al³⁺ ions affected the phase development, texture and oxygen storage capacity (OSC) of the Ce_0.5Zr_0.5O₂ powder. Single phase of ACZ-C could be maintained without phase separation and inhibit α-Al₂O₃ formation up to 1200 °C. The specific surface area value of ACZ-C (81.5 m²/g) was larger than that of ACZ-M (62.1 m²/g) and Ce_0.5Zr_0.5O₂ (17.1 m²/g) powders, which were calcined at 1000 °C. In comparison with ACZ-C and Al₂O₃, which were calcined at high temperature (900–1200 °C), it was found that the degradation rate of specific surface area of ACZ-C was lower than that of Al₂O₃. ACZ-C sample showed a higher thermal stability to resist phase separation and crystallite growth, which enhanced the oxygen storage capacity property for Ce_0.5Zr_0.5O₂ powders.     

Hydrogen storage characteristics of nanocrystalline and amorphous Mg2Ni-type alloys prepared by melt spinning

In order to improve the hydrogen storage characteristics of the Mg₂Ni-type alloys, Ni in the alloy is partially substituted by element Mn, and melt-spinning technology is used for the preparation of the Mg₂Ni_1−xMn_x (x = 0, 0.1, 0.2, 0.3, 0.4) hydrogen storage alloys. The microstructures of the as-cast and spun alloys are characterized by XRD, SEM and HRTEM. The hydrogen absorption and desorption kinetics of the alloys are measured by an automatically controlled Sieverts apparatus. The electrochemical performances are tested by an automatic galvanostatic system. The results show that the as-spun Mn-free alloy holds typical nanocrystalline structure, whereas the as-spun alloys containing Mn displays a nanocrystalline and amorphous structure. The hydrogen absorption and desorption capacities and kinetics of the alloys increase with rising spinning rate. Additionally, melt spinning markedly improves the electrochemical hydrogen storage capacity and cycle stability of the alloys containing Mn. With an increase in the spinning rate from 0 (As-casts is defined as spinning rate of 0 m/s) to 30 m/s, the discharge capacity of the (x = 0.3) alloy mounts up from 92.3 to 211.1 mAh/g, and its capacity retaining rate at 20th charging and discharging cycle grows from 36.21% to 76.02%.     

Influence of partial substitution of Ge on crystallization kinetics, microstructure and magnetic property of Fe44Co44−xZr7B5Gex alloys

Partial substitution of Ge for Co in Fe₄₄Co₄₄Zr₇B₅ amorphous alloy is found to have a large influence on crystallization kinetics and magnetic property of the alloy. Activation energy of nanocrystallization of FeCo phase (primary crystallization) decreases by 90 kJ/mol with 4 at.% Ge substitution, while that of precipitations of Zr-type phase from a residual amorphous phase (secondary crystallization) increases by 106 kJ/mol. The suppression of the secondary crystallizations stabilizes the FeCo nanocrystals embedded in the residual amorphous phase for the Fe₄₄Co_44−xZr₇B₅Ge_x until higher temperatures. It is proposed that the stabilization mechanism is attributed to preferential partitioning of Ge in the residual amorphous phase revealed by scanning transmission electron microscopy analysis. Microstructure and coercivity for the annealed alloys are also presented in combination with the effect of the Ge substitutions.     

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。     

Hydrogen storage properties of Zr1-xTixCo intermetallic compound

The intermetallic compound Zr1-xTixCo was prepared and its suitability for hydrogen storage was investigated.The alloys obtained by magnetic levitation melting with the composition of Zr1-xTixCo (x=0, 0.1, 0.2 and 0.3, at.%) show single cubic phase by X-ray diffraction.A single sloping plateau was observed on each isothermal, and pressure-composition-temperature (PCT) measurement results show that the equilibrium hydrogen desorption pressure of Zr1-xTixCo alloy increases with increasing Ti content.The desorption temperatures for supplying 100 kPa hydrogen are about 665, 642, 621 and 614 K for ZrCo, Zr0.9Ti0.1Co, Zr0.8Ti0.2Co and Zr0.7Ti0.3Co alloy, respectively.Repeated hydrogen absorption and desorption cycles do not generate separated ZrCo, TiCo and ZrH2 phases, indicating that alloys have good thermal and hydrogen stabilization.     

Zr1-xCoNbx (x = 0-0.2)合金吸放氢性能及抗歧化机制研究

采用真空电弧熔炼法制备了Zr_1-xCoNb_x (x = 0,0.05,0.1,0.15,0.2)合金,研究了Nb掺杂对合金晶体结构、吸放氢及抗歧化性能的影响。XRD结果表明：Zr_1-xCoNb_x (x = 0-0.2)合金主相为ZrCo相,含有少量ZrCo₂杂相;其氢化物为ZrCoH₃和ZrCo₂相。Nb掺杂极大地提高了合金吸氢动力学性能,ZrCo吸氢反应活化时间为7690 s,Zr_0.8CoNb_0.2缩短至380 s。ZrCo吸氢反应活化能为44.88 kJ mol^_-1 H₂,Zr_0.8CoNb_0.2降低至32.73 kJ mol^_-1 H₂,有利于吸氢反应动力学性能。DSC测量结果表明：ZrCo放氢温度为597.15 K,Zr_0.8CoNb_0.2降低至541.36 K,放氢温度降低,有利于抗歧化性能。ZrCo合金放氢反应活化能为100.55 kJ mol^_-1 H₂,Zr_0.8CoNb_0.2降低至84.58 kJ mol^_-1 H₂。合金歧化程度随着Nb掺杂量增加而降低,798 K保温10 h,ZrCo歧化83.68%,Zr_0.8CoNb_0.2仅歧化8.71%,Nb掺杂降低8f₂和8e位置氢原子数量,减小岐化反应驱动力。     

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.     

DEFORMATION BEHAVIOR AND CONSTITUTIVE EQUATION FOR Zr55Cu30Al10Ni5 BULK METALLIC GLASS IN SUPERCOOLED LIQUID REGION

Zr₅₅Cu₃₀Al₁₀Ni₅块体非晶合金(BMG)在过冷液态区内的单向压缩实验表明: 材料在过冷液态区内的形变行为强烈依赖于温度和变形速率. 随着应变速率的增加, 材料的流变特征由Newtonian流变转变为非Newtonian流变.利用扩展指数本构方程模型建立了非晶合金的流变应力、应变速率和温度的关系.