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。     

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。     

溶胶-凝胶法制备La1-xSrxMnO3及其电磁性能研究

采用溶胶凝胶法,制备了La_1-xSr_xMnO₃(LSMO)纳米微粉。探究了Sr^₂₊的掺杂量对LSMO晶体结构、磁学性质、电磁特性和微波吸收性能的影响。结果表明,随Sr^₂₊含量的升高,样品的晶格常数和Mn-O-Mn键角增大,平均晶粒尺寸逐渐下降,样品出现从反铁磁性向铁磁性的转变,复介电常数呈先增大后减小的趋势。在2~18GHz内,x=0的样品在厚度为2mm时有最佳吸波效果,反射率小于-10dB对应的有效吸波频段为12.5~18GHz;Sr^₂₊的掺杂可使吸波频段有效的向低频移动,在X波段内,x=0.2的样品在厚度为2.3mm时的有效带宽达2.6GHz,证明LSMO是一种性能优异的介电损耗型吸波材料。     

复合储氢合金Mg1.8Zr0.2Ni- (1.2-x)Ni -xMgTi3结构和电化学性能研究

为改善Mg₂Ni储氢合金电化学性能,采用机械合金化法(Mechanical Alloying,MA),分别制备出改性合金Mg_1.8 Zr Ni以及MgTi₃,按一定比例和Ni混合球磨,制备出纳米晶或非晶化的Mg_1.8Zr_0.2Ni- (1.2-x)Ni -xMgTi₃复合储氢合金。研究结果表明,经部分取代改性和包覆修饰后的复合储氢合金,其表面和内部形成较多的纳米级褶皱、空隙层状和多相结构缺陷。随着MgTi₃含量增加,Mg_1.8Zr_0.2Ni- (1.2-x)Ni -xMgTi₃复合储氢合金初始放电比容量也逐渐增加,当MgTi₃含量为x=0.5时,合金初始放电比容量为973.3 mAh.g_-1。但MgTi3含量超过x=0.5时,其初始放电比容量又有所下降,研究表明添加MgTi₃却不利于复合储氢合金的循环稳定性和高倍率放电性能。通过对Mg_1.8Zr_0.2Ni- (1.0-x)Ni -xMgTi₃复合储氢合金进行线性极化、阳极极化和交流阻抗测试,进一步研究了系列合金电极的表面电化学反应、电荷转移过程、氢在合金中的扩散情况以及它们的电化学性能。     

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。     

晶界添加Ho63.3Fe36.7 对NdFeB再生磁体组织与性能的影响

采用一种高效、绿色的物理方法对NdFeB废旧磁体表面进行清理并回收利用。通过晶界添加低熔点Ho_63.3Fe_36.7合金制备NdFeB再生磁体。在未添加Ho_63.3Fe_36.7的磁体中,没有足够的富Nd相隔离Nd₂Fe₁₄B相,从而导致磁体性能较差;随着Ho_63.3Fe_36.7合金的加入,晶界相变得清晰且连续。在质量分数2%Ho_63.3Fe_36.7添加量下,钕铁硼再生磁体获得最佳磁性能[(BH)_max+H_cj=1756.07]。此时矫顽力增加123 kA/m（约提高9.1%）,磁体的最大能积由290.94 kJ/m³下降到281.07 kJ/m³,而剩磁少量下降。通过对再生磁体显微组织和成分的分析可知,磁体晶界处形成了(Nd, Pr, Ho)₂Fe₁₄B壳层,这能够提高磁体的矫顽力。而X射线衍射分析表明,磁体I₍₀₀₆₎/I₍₁₀₅₎的衍射峰强度比从0.92提高到1.32。这说明磁体取向度提高,可以减弱对剩磁的影响,从而使得再生磁体在保持剩磁的同时提高磁体的矫顽力。     

长期时效N10276合金在CO2/H2S/Cl- 环境中的腐蚀行为

通过电化学阻抗与循环动电位极化的方法研究了在CO₂/Cl^-以及CO₂/H₂S/Cl^-溶液体系中、长期时效前后N10276合金的腐蚀机理。结果表明,阻抗弧的低频区间出现了一个不完整的容抗弧,并且随H₂S浓度的增加（10~100 μL/L）转变为Warburg阻抗,其主要原因是高含量H₂S相关吸附物。H₂S可以增加合金腐蚀速率。相比较而言,长期时效处理主要作用于合金点蚀的形成,其中,经过长期时效处理的奥氏体组织内存在大量的第二相（富含Mo与Ni的μ相）,而析出物周围的区域成为优先腐蚀区域,进而导致了N10276合金点蚀的发生。     

Cu含量对新型AlNiZrCoYSi高熵非晶合金非晶形成能力与耐腐蚀性能的影响

采用高真空电弧熔炼喷射成形技术制备了一种新型Al_17.5Ni₂₀Zr_17.5Co₂₀Y₂₀Si₅高熵非晶合金条带,并研究了Cu元素的添加及含量变化对Al_17.5Ni₂₀Zr_17.5Co₂₀Y₂₀Si₅高熵非晶合金耐腐蚀性能的影响。利用X射线衍射仪(XRD)、差示扫描量热仪(DSC)、显微硬度计分别研究了合金材料的非晶形成能力与硬度;通过极化曲线(Tafel)和Nyquist图等电化学方法考察了高熵非晶合金室温下在3.5 wt.% NaCl水溶液中的耐腐蚀性能。结果表明：四种(AlNiZrCo)_75-xCu_xY₂₀Si₅(x=0, 10, 14, 15)近等原子比高熵非晶合金均呈现典型的非晶态衍射峰,Cu含量对AlNiZrCoYSi高熵非晶合金的非晶形成能力影响不大,但会降低合金的抗腐蚀性能,且上述合金的维氏显微硬度均超过470 HV_0.1。其中,Al_17.5Ni₂₀Zr_17.5Co₂₀Y₂₀Si₅高熵非晶合金的耐腐蚀性能最佳,其自腐蚀电位(E_corr)为-0.248 V,自腐蚀电流密度(i_corr)为1.63 μA/cm^₂,极化电阻(R_p)为24.56 kΩ.cm^₂,该材料在解决严苛海洋环境下防腐耐磨问题具有较大的应用潜力。     

La0.4Sr0.6Co0.7Fe0.2Nb0.1O3- δ -Gd0.2Ce0.8O2- δ 应用于可逆固体氧化物电池对称电极

为制备一种高催化性的对称型固体氧化物电池电极,采用一步法合成了La_0.4Sr_0.6Co_0.7Fe_0.2Nb_0.1O_3-δ-Gd_0.2Ce_0.8O_2-δ（LSCFN-GDC）。以LSCFN-GDC为电池阳极和阴极,La_0.8Sr_0.2Ga_0.83Mg_0.17O_3-δ（LSGM）为电解质,采用流延和丝网印刷工艺制备了结构为LSCFN-GDC||LSGM||LSCFN-GDC的电解质支撑型固体氧化物电池。分别采用固体氧化物燃料电池（SOFC）及固体氧化物电解池（SOEC）2种模式对对称电池性能进行了测试。在850 ℃测试温度下,分别采用湿H₂（3% H₂O）、H₂（0.01% H₂S）、CH₄和C₃H₈为燃料气,电池最大功率密度分别为1.036、0.996、0.479和0.952 W/cm²,电解H₂（50% H₂O）时,1.3 V电解电压下电池电流密度为0.943 A/cm²。LSCFN-GDC具有良好的耐积碳、抗硫和氧化还原稳定性能,能够在湿H₂（0.01% H₂S）、CH₄、H₂（3% H₂O）及H₂（50% H₂O）环境中稳定运行700 h。实验结果表明,一步合成法是一种简便而优化的电极制备方法,LSCFN-GDC||LSGM||LSCFN-GDC固体氧化物电池（SOC）具有广阔的应用前景。     

(Zr55All0Ni5Cu30)0.97Ce0.03非晶合金在含Cl-介质中的腐蚀电化学行为研究

  用电化学技术方法研究了Zr₅₅Al_l0Ni₅Cu₃₀和(Zr₅₅Al_l0Ni₅Cu₃₀)_0.97Ce_0.03非晶合金在含Cl^-介质中的腐蚀电化学行为及添加稀土Ce的影响.结果表明：随Cl^-浓度增加,两种非晶合金的腐蚀速度加快;添加稀土Ce后提高合金耐蚀性;随极化电位的提高,两种非晶合金在0.05 mol/L Na₂SO₄及含Cl^-介质中均出现钝化特征,维钝电流密度随Cl^-浓度增加而减小;Zr₅₅Al_l0Ni₅Cu₃₀非晶合金的电化学阻抗谱由单容抗弧组成(Zr₅₅Al_l0Ni₅Cu₃₀)_0.97Ce_0.03非晶合金的交流阻抗谱在Cl^-浓度较低时呈单容抗弧特征,而随Cl^-浓度的增加,单容抗弧变为双容抗弧.     

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。     

Corrosion behavior of Zr–Nb–Cr cladding alloys

Zr-Nb-Cr alloys were used to evaluate the effects of alloying elements Nb and Cr on corrosion behavior of zirconium alloys. The microstructures of both Zr substrates and oxide films formed on zirconium alloys were characterized. Corrosion tests reveal that the corro- sion resistance of ZrxNb0.1Cr （x = 0.2, 0.5, 0.8, 1.1; wt%） alloys is first improved and then decreased with the increase of the Nb content. The best corrosion resistance can be obtained when the Nb concentration in the Zr matrix is nearly at the equilibrium solution, which is closely responsible for the formation of columnar oxide grains with protective characteristics. The Cr addition degrades the corrosion resistance of the Zrl.lNb alloy, which is ascribed to Zr（Cr,Fe,Nb）2 precipitates with a much larger size than β-Nb.     

The oxidation of Co−Nb alloys under low oxygen pressures at 600–800°C

The oxidation of two Co–Nb alloys containing 15 and 30 wt.% Nb has been studied at 600–800° C in H₂–CO₂ mixtures providing an oxygen pressure of 10^–24 atm at 600°C and 10^–20 atm at 700 and 800°C, below the dissociation pressure of cobalt oxide. At 600 and 700°C both alloys showed only a region of internal oxidation composed, of a mixture of alpha cobalt and of niobium oxides (NbO₂ and Nb₂O₅) and at 700°C also the double oxide CoNb₂O₆, which formed from the Nb-rich Co₃Nb phase. No Nb-depleted layer formed in the alloy at the interface with the region of internal oxidation at these temperatures. Upon oxidation at 800°C a transition between internal and external oxidation of niobium was observed, especially for Co–30Nb. This corrosion mode is associated with the development of a single-phase, Nb-depleted region at the surface of the alloy. The corrosion mechanism of these alloys is examined with special reference to the effect of the low solubility of niobium in cobalt and to the relation between the microstructures of the alloys and of the scales.     

Effect of Nb on the high-temperature sulfidation behavior of cobalt

The sulfidation behavior of Co-Nb alloys containing up to 30wt.% Nb was studied in sulfur vapor at a pressure of 0.01 atm in the temperature range of 600–700°C. Increasing niobium content decreased the sulfidation rate, following the parabolic rate law. An activation energy of 25.6 kcal/mole was obtained for Co-10Nb, Co-20Nb, and Co-25Nb, while a value of 20.5 kcal/mole was found for Co-30Nb. All were two-phase alloys, consisting of solid solution -Co and the intermetallic compound, NbCo₃. The two-phase alloys formed a rather thick outer layer of cobalt sulfides and a heterophasic inner layer that was complex. The inner layer always contained the mixed sulfide CoNb₂S₄ which, depending on the alloy composition, coexisted with cobalt sulfide, NbS₂, and / or NbCo₃ particles. Short-time sulfidations showed that the solid solution initially sulfidized rapidly to form nodules of cobalt sulfide, whereas the NbCo₃ phase formed a thin protective layer of NbS₂. The nodules grew laterally until they coalesced into the continuous, outer thick layer, while the NbS₂ completely or partially reacted with the cobalt sulfide to form CoNb₂S₄. Platinum markers were always found at the interface between the inner and outer scales, the location of the original metal surface.     

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。     

Effect of Al on high-temperature corrosion of Co-15a/oNb alloys in H2-H2O-H2S environments

Co–15 at.% Nb alloys containing up to 15 at.% Al were corroded in gaseous H₂–H₂O–H₂S mixtures over the temperature range of 600–900°C. The corrosion kinetics followed the parabolic rate law at all temperatures. Corrosion resistance improved with increasing Al content except at 900°C. Duplex scales formed on alloys consisting of an outer layer of cobalt sulfide and a heterophasic inner layer. A small amount of Al₂O₃ was found only on Co–15Nb–15Al. Contrary to what formed in Co–Nb binary alloys, neither NbS₂ nor NbO₂ were found in the inner layer of all alloys, but Nb₃S₄ did form. The absence of NbS₂ and NbO₂ is due to the formation of stable Al₂O₃ and Al₂S₃ that effectively blocked the inward diffusion of oxygen and sulfur, respectively, and to the reduction of activity of Nb by Al additions in the alloys. Intercalation of ions in the empty hexagonal channels of Nb₃S₄ is associated with the blockage of the transport of cobalt. An unknown phase (possibly Al_0.5NbS₂) was detected. Alloys corroded at 900°C were abnormally fast and formed a scale containing CoNb₃S₆ and Co. Pt markers were found at the interface between the inner and outer layers.     

The high-temperature corrosion behavior of Co-Nb alloys in mixed-gas atmospheres

The corrosion of Co-Nb alloys containing up to 30 wt.% Nb in H₂-H₂S-H₂O gas mixtures was studied over the temperature range of 600–800°C. The gas composition falls in the stability region of cobalt sulfide and Nb₂O₅ in the phase diagrams of the Co-O-S and Nb-O-S systems at all temperatures studied. Duplex scales, consisting of an outer layer of cobalt sulfide and a complex, heterophasic inner layer, were formed at all temperatures studied. In addition to cobalt sulfide and CoNb₃S₆, a small amount of NbO₂ was found in the inner layer. The reason for the formation of NbO₂ over that of Nb₂O₅ in the scale is that the outer sulfide scale lowers the oxygen activity within the scale into the NbO₂-stability region. Two-stage kinetics were observed for all alloys, including an initial irregular stage usually followed by a steady-state parabolic stage. The steady-state parabolic rate constants decreased with increasing amounts of Nb, except for Co-20Nb corroded at 700°C. Nearly identical kinetics were observed for Co-20Nb corroded at 600°C and 700°C. The presence of NbO₂ particles leads only to a limited decrease of the available cross-section area for the outward-diffusing metal ions. The activation energies for all alloys are similar and are in agreement with those obtained in a study of the sulfidation of the same alloys. The primary corrosion mechanism involves an outward Co transport.     

Partial and integral enthalpy of molten Ag–Al–Cu alloys

The partial and integral enthalpies of mixing of molten, ternary Ag–Al–Cu alloys were determined at 1146 K using a calorimeter of the Tian–Calvet type. Measurements were performed starting from pure Al to about 40 at.% Al along three sections with Ag:Cu ratios of about 1:3, 1:1 and 3:1. The values of the partial enthalpies of Cu, h_Cu≅−40 kJ mol⁻¹, are rather constant from 1>x_Al>0.6. The values of the partial enthalpies of Ag decrease from h_Ag=+5 kJ mol⁻¹ to −10 kJ mol⁻¹. The minimum values at about 40 at.% Al for the integral molar enthalpy are −18 kJ mol⁻¹ for Cu:Ag=3:1, −12.5 kJ mol⁻¹ for Cu:Ag=1:1 and −8,5 kJ mol⁻¹ for Cu:Ag=1:3; the error is ±5%. This behaviour is in agreement with the concept of Fermi enthalpy and corresponds to a transfer of one electron from aluminium to the not fully occupied bands of copper and silver, respectively. The existence of a ternary liquid non-stoichiometric compound with a very broad range of stability is claimed for alloys with about 0<x(Al)<0.5, too.