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。     

Zr-1.0Fe-0.2Cu合金在400 ℃/10.3 MPa过热蒸汽中的腐蚀行为

以高纯锆为母材制备Zr-1.0Fe-0.2Cu合金,并在400 ℃/10.3 MPa过热蒸汽中进行腐蚀实验。用SEM和TEM对合金基体及其腐蚀后生成氧化膜的显微组织进行研究。结果表明：Zr-1.0Fe-0.2Cu合金中只存在底心正交的Zr₃Fe第二相,Cu元素易偏聚在Zr₃Fe相内,使其不易以Zr₂Cu相的形式析出,Cu元素的添加能够细化合金中Zr₃Fe第二相。Zr-1.0Fe-0.2Cu合金在 400 ℃/10.3 MPa过热蒸汽中腐蚀100 d后,耐腐蚀性能优于Zr-1.0Fe以及Zr-4重熔合金,表明添加少量的Cu元素有利于改善合金的耐腐蚀性能。在腐蚀氧化过程中,含Cu的Zr₃Fe相会滞后于合金基体α-Zr相氧化而进入氧化膜。随着氧化进程的加深,第二相中的Zr元素氧化后会以t-ZrO₂的形式存在,Fe元素则氧化成m-Fe₃O₄。伴随着第二相的氧化进程,合金元素Cu和Fe会在氧化膜中扩散流失,不再呈现聚集状态。     

Ni48Co1Mn37In14- x Al x 磁性记忆合金马氏体相变、力学性能和耐腐蚀性能

采用电弧熔炼的材料制备方法，研究了微量的主族元素Al掺杂对Ni₄₈Co₁Mn₃₇In_14-xAl_x (0≤x≤2)磁性形状记忆合金显微组织、晶体结构、马氏体相变、力学性能和耐腐蚀性能的影响。结果表明：用Al替代部分In，合金的晶粒尺寸明显减小，掺杂2at%的Al元素，平均晶粒尺寸缩小到10 μm左右，大约为未掺杂样品的三十五分之一；当Al掺杂量在0.25at%~2at%时，金属Al完全固溶到基体中，而且Al在合金中的固溶度随掺杂量的增加有所提升，当Al掺杂量为2at%时，Al在基体中的固溶度接近2at%；随着Al对In的取代，室温下合金由L2₁立方奥氏体与单斜6M马氏体的两相结构转变为单一的6M调制马氏体相结构，晶胞体积逐渐减小，马氏体相变温度呈现上升趋势；合金抗压强度不断增大，Ni₄₈Co₁Mn₃₇In₁₂Al₂的抗压缩断裂强度与Ni₄₈Co₁Mn₃₇In₁₄相比提高了160%，压缩应变也由5.46%增加到6.36%；适量的Al替代In后，合金在人工海水中的耐腐蚀性能总体呈现不断增强的趋势，Ni₄₈Co₁Mn₃₇In₁₂Al₂合金的耐腐蚀性能明显高于Ni₄₈Co₁Mn₃₇In₁₄合金，且其耐腐蚀性接近于304不锈钢。     

具有高非晶形成能力的高熵合金Cu29Zr32Ti15Al5Ni19

用铜模吸铸法成功地合成了由两个固溶体相构成的高熵合金(HEA) Cu₂₉Zr₃₂Ti₁₅Al₅Ni₁₉和相同成分的非晶态合金(HE-BMG)。实验结果表明该成分的高熵合金具有高的非晶形成能力。铸态高熵合金Cu₂₉Zr₃₂Ti₁₅Al₅Ni₁₉的抗压强度为1127MPa。在750℃保温2小时后的Cu₂₉Zr₃₂Ti₁₅Al₅Ni₁₉高熵合金的硬度仍高达826HV。     

MODIFICATION OF ZENER'S TWO--PARAMETER IN THE SUPERELEMENT MODEL FOR Fe--Σ Xi--C ALLOY SYSTEMS

根据Aaronson提出的超组元模型, 借助A_e3的实验数据, 提出了修正的置换型元素 X_i(X_i=Si, Mn, Ni, Co, Mo, Al, Cu, Cr) 的Zener两参数, 修正中考虑了合金元素间的交互作用. 修正后的超组元模型的预测精度明显改善: A_e3计算值与实验值的标准差为10.8 ℃, 与Thermo--Calc计算值的标准差为2.35 ℃; A_e1计算值与实验值的标准差为6.8 ℃. 按照马氏体相变热力学的计算方法, 采用经修正的参数计算了马氏体相变开始温度M_s, 提高了M_s点的预测精度, 计算值与实验值的标准差为25.3 ℃.     

稀土对La0.6R0.2Mg0.2（NiCoAlMn）3.3储氢合金相结构和电化学性能的影响

以La0.6R0.2Mg0.2Ni2.8Co0.2Al0.2Mn0.1(R=La、Ce、Pr、Nd、Y)合金为研究对象,研究稀土元素R部分替代La后对合金相结构和相组成及电化学性能的影响。X射线衍射(XRD)和显微电子探针(EPMA)方法分析结果表明,合金La0.8Mg0.2Ni2.8Co0.2Al0.2Mn0.1退火组织主要由Ce2Ni7型相(或Gd2Co7型)、PuNi3型相和CaCu5型相组成;Pr、Ce、Nd元素的替代对合金的相组成没有明显影响,而Y元素替代使合金中CaCu5型相明显减少,Ce2Ni7型(或Gd2Co7型)相显著增加,其相丰度达到79.03%。Y元素替代时合金中Gd2Co7型相基本消失。电化学测试和分析表明,稀土元素R替代La后对合金电极活化性能影响不大,其中Pr、Nd、Y部分替代La在一定程度上提高了合金的最大放电容量,而元素Y替代时合金电极容量最高达到392.6mAh/g;Y元素部分替代La使合金电极的循环稳定性得到明显提高,S100达到90.3%。     

Cu添加对La0.7Ce0.3Fe11.54-xCuxMn0.16Si1.3合金及其氢化物磁性能的影响

La(Fe, Si)₁₃系合金是具有一级相变大磁热效应的磁制冷合金,被认为是极具应用前景的磁热效应材料之一。本文采用高频感应悬浮炉制备了添加不同Cu元素比例的La_0.7Ce_0.3Fe_11.54-xCu_xMn_0.16Si_1.3(x=0, 0.05, 0.1, 0.15)合金。并利用粉末XRD衍射仪,扫描电镜(SEM)对合金的相组成、微观组织结构进行了研究,采用多功能振动样品磁强计VersaLab对合金的磁性能进行了分析。添加Cu元素后,合金的居里温度提高,但氢化后添加Cu的合金居里温度反而偏低。随着Cu元素提高磁热性能下降,但La_0.7Ce_0.3Fe_11.44Cu_0.1Mn_0.16Si_1.3H_1.68合金的最大等温磁熵变仍高达8.5 J/kg.K(0 ~ 2 T),相对制冷能力RCP提高(118 J/kg),磁滞明显降低。     

AlCrCuFeNbxNiTi高熵合金组织与性能研究

采用电弧熔炼制备了AlCrCuFeNb_xNiTi (x = 0, 0.25, 0.5, 1.0)高熵合金,研究不同Nb含量对AlCrCuFeNb_xNiTi高熵合金显微组织和力学性能的影响。研究表明：AlCrCuFeNb_xNiTi (x = 0, 0.25, 0.5, 1.0)高熵合金物相主要包含有序FCC的L2₁相和Laves相,还有少量的BCC(A2)和FCC相;Nb元素的添加能促进Laves相的生成且对Cu元素的偏析具有一定的抑制效果;通过相判据参数计算找到了适合AlCrCuFeNb_xNiTi高熵合金的相形成判据;添加适量的Nb元素能够改善AlCrCuFeNiTi六元高熵合金的力学性能;AlCrCuFeNb_0.5NiTi 高熵合金具有较好的综合力学性能,抗压强度达到1587.4 MPa,硬度达到568.8 HV;Nb元素含量过高时会形成过多的Laves相使合金表现出过早脆化现象。     

Ce17Fe78-xB6Mx (M=Cu, Al, Ga; x=0-1.0)快淬合金永磁性能研究

本文基于熔体快淬技术,研究了低熔点元素Cu、Al和Ga添加对Ce₁₇Fe₇₈B₆合金磁性能的影响。三类低熔点元素的加入,均降低了合金的磁化强度,而矫顽力有一定程度的提升。其中,Cu和Ga元素添加可优化晶粒尺寸分布,且Ga添加对Ce₁₇Fe₇₈B₆合金矫顽力的提升最为有效。研究发现,Ce₁₇Fe₇₈B₆合金回复曲线轻微开口;当Ga添加量为0.75 at.%时,合金具有较优异的综合磁性能,回复曲线完全闭合。适量Ga元素添加明显增强了Ce-Fe-B基合金晶间短程交换耦合作用,减小了合金平均回复磁导率,有效降低了Ce-Fe-B基合金在周期性反向磁场中的能量损失。     

Hf对Zr-Al-Ni-Cu金属玻璃弛豫行为的影响

通过测定快淬态和退火态比热与温度的关系,研究了Hf元素对Zr₇₀Al_7.5Ni₈Cu_14.5（70Zr）、Zr₅₅Al₁₀Ni₅Cu₃₀（55Zr）和(Zr_0.75Hf_0.25)₆₅Al_7.5Ni₁₀Cu_17.5（65Zr_0.75Hf_0.25）厘米级金属玻璃焓和硬度弛豫的影响。结果显示：70Zr和55Zr合金的结构弛豫表现为单峰现象,在退火温度（T_a）接近玻璃转变温度（T_g）时出现弛豫峰;而65Zr_0.75Hf_0.25合金的结构弛豫表现为双峰现象,分别在523和648 K（接近T_g）时出现焓弛豫峰。70Zr和55Zr合金在T_g温度附近出现明显的单峰弛豫行为,表明合金在T_g之前的整个温度范围内具有较高的抵抗退火诱导结构弛豫的能力;另一方面,65Zr_0.75Hf_0.25合金在523 K附近出现一个弛豫子峰,可能是由于Zr-Hf原子对的键合性较弱,混合焓接近于零,随后在T_g附近出现明显的主弛豫。65Zr_0.75Hf_0.25和(Zr_0.5Hf_0.5)₆₅Al_7.5Ni₁₀Cu_17.5（65Zr_0.5Hf_0.5）合金的硬度也表现出类似的双峰现象,导致第一峰的T_a与焓弛豫峰的T_a一致。结果表明,满足非晶形成三原则的Zr、Al、Ni和Cu组成的类二十面体中程有序结构在低T_a温度下保持稳定;只有背离非晶形成三原则的65Zr_0.75Hf_0.25和65Zr_0.5Hf_0.5金属玻璃焓弛豫和硬度弛豫出现了双峰,表明形成大块金属玻璃非必要组元的增加将导致合金结构在低温退火过程中的不稳定性。     

ZrCo和Zr0.7Hf0.3Co合金中氦泡演化和氦热释放研究

采用混合能量离子注入法在ZrCo及Zr_(0.7)Hf_(0.3)Co合金中引入氦,利用透射电镜观察氦泡形貌随贮存时间的演化。结果表明Zr_(0.7)Hf_(0.3)Co中氦泡平均尺寸比ZrCo更小,随贮存时间的延长,两者均被观察到氦泡的合并与长大。利用氦热释放谱研究贮存时间对氦热释放行为的影响,当贮存时间达到105d时,ZrCo中氦的总释放量和在较低温度下的释放分数均减少;而Zr_(0.7)Hf_(0.3)Co合金在贮存的175d内,较低温度下释放分数逐渐增加,总释放量无明显变化,这表明Zr_(0.7)Hf_(0.3)Co比ZrCo具有更优异的固氦性能。     

Zr-Co(Cu)-Al bulk metallic glasses with optimal glass-forming ability and their compressive properties

The formation of bulk metallic glasses (BMGs) in the ternary Zr₅₆Co₂₈Al₁₆ and quaternary Zr₅₆Co_28–xCu_xAl₁₆ (x=2, 4, 5, 6, 7, mole fraction, %) glassy alloys was investigated via the copper mold suction casting method. The main purpose of this work was to locate the optimal BMG-forming composition for the quaternary ZrCo(Cu)Al alloys and to improve the plasticity of the parent alloy. The X-ray diffractometry (XRD), transmission electron microscopy (TEM) and differential scanning calorimetry (DSC) were used to investigate the glassy alloys structure and their glass forming ability (GFA). In addition, the compression test, microhardness, nano-indentation and scanning electron microscopy (SEM) were utilized to discuss the possible mechanisms involved in the enhanced plasticity achievement. The highest GFA among Cu-containing alloys was found for the Zr₅₆Co₂₂Cu₆Al₁₆ alloy, which was similar to that of the base alloy. Furthermore, the plasticity of the base alloy increased significantly from 3.3% to 6% for the Zr₅₆Co₂₂Cu₆Al₁₆ BMG. The variations in the plasticity and GFA of the alloys were discussed by considering the positive heat of mixing within Cu and Co elements.     

Phase formation regularities in nanometer powders of Al-Cu-X ternary alloys prepared by gas evaporation process

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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.     

Sulfidation properties of TiAl–2 at.% X (X=V,Fe, Co,Cu, Nb,Mo, Ag and W) alloys at 1173 K and 1.3 Pa sulfur pressure in an H2S–H2 gas mixture

TiAl–2 at. % X (X=V, Fe, Co, Cu, Nb, Mo, Ag and W) alloys were sulfidized at 1173 K for 86.4 ks at a 1.3 Pa sulfur pressure in an H₂–H₂S gas mixture. The structure, phases, and compositions of the external sulfide scale and alloy surface layer were measured using EPMA and X-RD. The TiAl–2Ag and –2Cu alloys sulfidized faster than TiAl, and the alloy surface layer was thicker than that of TiAl. Sulfidation amounts of the TiAl–2X (X=V, Co, Fe, Mo, W and Nb) alloys were almost the same as that of TiAl, while the thickness of the alloy surface layer decreased in the order: V>Co>Fe>Mo>[Cr (by Narita T, Izumu T, Yatagai M, Yoshioka T. Intermetallics, 2000;8:371)]>W>Nb. The sulfide scale was composed of multi-layer structures: an outermost (rich in Ti-sulfides), an outer (rich in Al₂S₃), an inner (a mixture of Ti-sulfides and Al₂S₃), and an innermost (rich in Ti-sulfides) layer. The alloy surface layer also had a multi-layer structure, and was classified into four groups: group 1 for TiAl–2V and –2Co alloys as well as TiAl binary alloy where the surface layer consists of alloy substrate/TiAl₂/TiAl₃/sulfide scale, group 2 for TiAl–2Nb, –2Mo, and –2W (and also– 2Cr) alloys with alloy substrate/TiAl₂/TiAl₃/(Nb, Mo, W or Cr)–Al alloy/sulfide scale, group 3 for TiAl–2Cu and –2Ag alloys with alloy substrate/TiAl₂/Ti (Al, Ag or Cu)₃ with an L1₂ structure/TiAl₃/sulfide scale, and group 4 for TiAl–2Fe alloy with alloy substrate/TiAl₂/Ti(Al,Fe)₃ with an L1₂ structure/TiAl₃/FeAl₃/sulfide scale. Diffusion paths for these four groups were shown in a tentative Ti–Al–X ternary phase diagram.     

提高KF-AlF3-Al2O3熔体中Cu-Al基阳极的耐腐蚀性

采用恒电流和动电位极化技术研究经预氧化的和未经预氧化的Cu-Al基阳极(Cu-10Al和Cu-9.8Al-2Mn)在KF-AlF₃-Al₂O₃熔体中的阳极行为。将合金在700℃下进行短时间(8 h)氧化,然后在800℃下施以0.4 A/cm²的电流密度进行1 h恒电流极化。测定扫描速率为0.01 V/s的动电位曲线。对在阳极表面冻结的熔体样品进行XRD分析,并在实验后对阳极进行SEM分析,以研究合金表面形成的氧化皮的物相。所有阳极材料的稳态电位都在2.30~2.50 V(vs Al/AlF₃)范围内。根据动电位极化获得的数据计算阳极的腐蚀速率。结果表明,经预氧化的阳极比未经预氧化的阳极具有更低的腐蚀速率。     

Influence of oxygen on the crystallization behavior of Zr65Cu27.5Al7.5 and Zr66.7Cu33.3 metallic glasses

The influence of oxygen on the crystallization behavior of Zr_65−xCu_27.5Al_7.5O_x (x=0.14, 0.43 and 0.82) and Zr_66.7−xCu_33.3O_x (x=0.14 and 0.82) metallic glasses has been studied. The supercooled liquid regime (ΔT_x) decreases with increase in oxygen content for the Zr–Cu–Al alloy, while it increases for the Zr–Cu metallic glass. In the case of the Zr–Cu metallic glass, the crystallization product (Zr₂Cu) is not influenced by the oxygen content, while in Zr–Cu–Al alloys the oxygen level has a strong influence on the crystallization sequence. At low oxygen level (x=0.14), the ternary glass crystallizes polymorphously to Zr₂(Cu,Al). At higher oxygen content, the ternary amorphous alloy crystallizes in two stages by primary crystallization into an icosahedral phase and subsequently to the stable Zr₂(Cu,Al) phase. Three-dimensional atom probe results have shown that the composition of the icosahedral and amorphous phases is close to Zr₇₅Cu₁₅Al₅O₅ and Zr₆₂Cu₂₄Al₁₄, respectively.     

Effects of substituting Ni with M (M=Cu, Al and Mn) on microstructures and electrochemical characteristics of La-Mg-Ni system (PuNi3-type) electrode alloys

In order to improve the electrochemical cycle stability of La-Mg-Ni system (PuNi3-type) hydrogen storage alloy, Ni in the alloys was partially substituted by M (M=Cu, Al, Mn). A new La-Mg-Ni system electrode alloys La0.7Mg0.3Ni2.55-xCo0.45Mx (M=Cu, Al, Mn;x =0,0.1) were prepared by casting and rapid quenching. The effects of element substitution and rapid quenching on the microstructures and electrochemical performances of the alloys were investigated. The results by XRD, SEM and TEM show that the alloys havea multiphase structure, including the (La, Mg)Ni3 phase, the LaNi5 phase and the LaNi2 phase. The rapid quenching and element substitution have an imperceptible influence on the phase compositions of the alloys, but both change the phase abundance of the alloys. The rapid quenching significantly improves the composition homogeneity of the alloys and markedly decreases the grain size of the alloys. The Cu substitution promotes the formation of an amorphous phase in the as-quenched alloy, and a reversal result by the Al substitution. The electrochemical measurement indicates that the element substitution decreases the discharge capacity of the alloys, whereas it obviously improves the cycle stability of the alloys. The positive influence of element substitution on the cycle life of the alloys is in sequence Al＞Cu＞Mn, and negative influence on the discharge capacity is in sequence Al＞Mn＞Cu. The rapid quenching significantly enhances the cycle stability of the alloys, but it leads to a different extent decrease of thedischarge capacity of the alloys.     

Site occupancy in ternary L12 ordered alloys as determined by diffraction: observations on (Al,Cr)3 Ti alloys

The nature and occurrence of point defects have been studied in L1₂ ordered (Al,Cr)₃Ti alloys. Four compositions were investigated, two stochiometric alloys with either 9 or 12 at. pct. Cr, and two nonstoichiometric alloys with 10 at. pct. Cr and either 23 or 27 at. pct. Ti. Measurements of lattice parameter, density, and composition were combined to calculate the average number of atoms per unit cell. No variation in this quantity was detected with alloy composition, suggesting that the dominant point defects in these ordered phases are antisite defects rather than constitutional vacancies. A lack of constitutional vacancies was further supported by comparisons of measured and calculated superlattice peak intensities. The common method of regression fitting calculated and measured X-ray diffraction intensities using a single wavelength is shown to be unable to define the two independent order parameters unambiguously, calling into question the results of such previous studies on these ternary alloys. Only if an assumption is made that one type of site substitution dominates the antisite formation can the method be used to estimate the solution for the dominant behavior. Assuming that one type of substitution dominates the antisite formation on β (Ti) sites, the measurements performed in this study suggest a small amount of Cr, but not Al, substitution on β sites, and that most of the Cr is on α (Al) sites. Increasing the Cr level in stoichiometric alloys causes more Cr to occupy β sites, displacing some Ti to α sites, thus creating more antisite defects. The Ti deficiency in hypostoichiometric alloys is alleviated by enhanced substitution of Cr on β sites. However, the excess Ti in hyperstoichiometric alloys greatly decreases any Cr substitution on β sites.