A_2B_7型La_(0.64)Gd_(0.2)Mg_(0.16(1+x))Ni_(3.1)Co_(0.3)Al_(0.1)储氢合金微观组织和电化学性能

以综合电化学性能较佳的低镁含量合金La0.64Gd0.2Mg0.16Ni3.1Co0.3Al0.1为基础,通过改变Mg元素含量的添加方式,用感应熔炼方法与热处理制备了La0.64Gd0.2Mg0.16(1+x)Ni3.1Co0.3Al0.1系列合金,系统研究了该条件下镁元素成分波动(Mg过量值x)对La-Mg-Ni系A2B7型合金微观结构和电化学性能的影响规律。合金相结构分析表明,合金退火组织由主相Ce2Ni7(Gd2Co7)型以及Pr5Co19型、Pu Ni3型和Ca Cu5型多相组成,随Mg过量值x增加,合金中主相Ce2Ni7型相丰度呈现先增加后减小的趋势;当Mg过量值0x≤50%时,合金组织的Ce2Ni7型主相相丰度达到81.04%~87.18%;x=0,80%时,Ce2Ni7型主相丰度减小至76.3%以下。电化学测试结果表明,随Mg过量值x增加,合金电极最大放电容量呈先增加后降低趋势,x=10%时合金具有最高电化学放电容量(384.6 m Ah·g-1);当Mg过量值x在5%~50%范围内变化时,其电极循环稳定性均保持在S100≥90%,此时镁元素成分波动变化对合金电极循环稳定性的影响不敏感。合金电极的高倍率放电性能(HRD)随Mg过量值的增加呈先增大后减小趋势,其中电极表面的电荷转移速率是影响合金电化学反应动力学性能的主要控制步骤。     

替代方式对稀土系储氢合金电化学性能的影响

本文采用Co、Mn、Cu同时替代La Mg2Ni9中的Ni,并且与Cu单独替代时合金的电化学性能进行了比较,实验结果表明,与单元替代相比,多元替代有着较高的放电容量和较好的活化性能,但是其循环稳定性较差,文章系统的分析了产生此种现象的原因。此外,通过对综合性能最佳的合金La Mg2Ni2.7Co2.1Mn2.7Cu1.5进行X衍射分析,从微观角度进一步研究了储氢合金成分对合金电化学性能的影响,认为La4Co3和Mg Co Cu0.9Ni0.1可能是提高合金的最大放电容量的原因。     

Mg_(22)Y_2Ni_(10)Cu_2储氢合金活化和吸氢性能

在0.04 MPa氦气保护下,采用中频感应熔炼炉冶炼了,以少量Y和Cu分别替代部分Mg和Ni的Mg_2Ni型储氢合金,并对合金的结构形貌、相组成、气态吸氢活化与性能进行了系统的研究。研究结果表明:铸态Mg_(22)Y_2Ni_(10)Cu_2合金具有典型的片层状共晶组织特征,其组成相为Mg_2Ni,YMgNi_4和少量的Mg相;合金在3 MPa,300℃下5次吸放氢完全活化,Mg和Mg_2Ni相能够可逆吸放氢,但在首次活化过程中,Mg_2Ni相只有部分转变为Mg_2NiH_4,而Mg相则能够完全转变为MgH_2;同时发现YMgNi_4相虽多次吸放氢循环后,都未发现有非晶化现象发生,表明该相与REMgNi_4(RE=La,Nd)等其他拉弗斯相相比,具有更高的结构稳定性;合金的吸氢动力学曲线用Avrami-Erofofeev法拟合后表明合金吸氢是一维形核和长大过程;测试了合金的平衡压力-浓度等温(PCT)曲线,计算合金的热力学参数为Mg相的氢化焓变(ΔH)和熵变(ΔS)分别为-78.1 kJ·mol~(-1),-133.9J·K~(-1)·mol~(-1),而Mg_2Ni相的氢化ΔH和ΔS则分别为-51.8 kJ·mol~(-1),-103.0J·K~(-1)·mol~(-1),合金的热力学性能明显改善,表明添加Y和Cu对Mg_2Ni型合金的吸氢性能具有一定的催化作用。     

Sn的添加对Mg-Cu-Y块体金属玻璃形成能力的影响

通过熔体铜模浇注方法制备了Mg65Cu25-xSnxY10（X=2，4，6）合金，并对它们的玻璃形成能力及晶化行为进行了研究。利用X射线衍射确定合金的非晶态性质，差示扫描量热计（DSC）分析合金的玻璃转变、晶化和熔化行为。结果表明：在Mg65Cu25-xSnxY10合金体系中，当X=2时，合金的玻璃形成能力最强，能形成的完全玻璃态试样的最大尺寸为3．2mm，其过冷液相区△Tx和约化玻璃转变温度Trg分别为57．6和0．586。同时合金的熔化曲线表现为单一吸热峰。随着sn含量的增加，非晶合金的玻璃转变温度Tg及初始晶化温度Txl。均呈现下降趋势，同时合金的玻璃形成能力逐渐下降。当X=4和6时，合金的晶化行为表现为明显的多级晶化。     

热重法研究BaRE(Cu0.5Fe0.5)2O5+δ的氧含量变化及其透氧性能

用热重法研究了BaRE(Cu0.5Fe0.5)2O5+δ(RE=Lu～Pr)样品的氧含量的变化.结果表明仅RE=Pr、Nd、Gd时样品的氧含量随温度和氧分压变化而变化,其它样品的氧含量基本不发生变化.用暂态热重法研究了氧在RE=Pr、Nd、Gd样品的表面反应速度,发现氧在表面吸附速率比脱附要快.     

自旋梯状化合物Sr14(Cu1-xZnx)24O41的电输运及磁学性质

采用标准固相反应法制备了Sr14(Cu1-xZnx)24O41(x=0,0.01,0.02,0.03)系列多晶样品.X射线衍射谱表明所有样品均呈单相,且样品晶格常数大小随Zn掺杂量x的变化存在微弱波动.X射线光电子能谱表明Sr14Cu24O41中Cu离子以+2价形式存在,Zn掺杂对体系中Cu离子化合价不造成影响.磁化率测量结果表明在10~300 K温度范围内Zn掺杂使体系磁化率降低,拟合结果表明随着Zn掺杂量x的增大,居里-外斯项对体系磁化率贡献逐渐减弱,二聚体耦合能JD逐渐降低,每个分子中Cu O2自旋链内二聚体个数ND与自由Cu2+离子自旋数NF均逐渐减少,进一步分析显示替换二聚体内Cu2+离子的Zn2+离子数少于替换自由Cu2+离子的Zn2+离子数.电阻率测量结果表明Sr14Cu24O41体系具有半导体特性,并且Zn掺杂会使体系电阻率降低,降低程度随掺杂量x增大而增大,但并未使体系发生金属-绝缘体转变.认为电阻率降低可能是由于Zn2+离子掺杂使体系内Cu O2自旋链中二聚体发生退耦,破坏了电荷有序超结构,从而使更多的空穴释放出来并转移到导电性好的Cu2O3自旋梯子中所致.     

热处理对A_2B_7型La_(0.6)Sm_(0.15)Nd_(0.1)Mg_(0.15)Ni_(3.4)Al_(0.1)贮氢合金微观结构和电化学性能的影响

采用感应熔炼法制备了La_(0.6)Sm_(0.15)Nd_(0.1)Mg_(0.15)Ni_(3.4)Al_(0.1)合金,研究了在975℃下经不同时间(t=0、12h、24 h和48 h)热处理对合金相结构及电化学性能的影响。X射线衍射(XRD)分析表明,熔炼得到的La_(0.6)Sm_(0.15)Nd_(0.1)Mg_(0.15)Ni_(3.4)Al_(0.1)合金由CaCu_5型、Ce_2Ni_7型和Gd_2Co_7型三种晶体结构构成,t=24 h时,合金中仅存在Ce2Ni7型晶体结构。元素分析表明,合金相结构的转变是由于在热处理过程中,合金构成元素的扩散以及Mg元素的烧损造成的。电化学测试表明,随热处理时间的增加,合金电极活化次数变化不大,而最大放电容量、高倍率放电性能呈现先增加后降低的趋势,其中,t=24 h时合金的最大放电容量为363.81 mAh/g,电流密度为1600 m A/g时合金的高倍率放电性能达到92.65%。     

RE(RE=Nd,Sm,Pr)部分替代La对A_2B_7型合金电化学贮氢性能的影响

La-Mg-Ni系A2B7型合金由于其高的放电容量被认为是最具希望的Ni-MH电池负极材料,然而,低的电化学循环稳定性制约着合金的实际应用。为了改善La-Mg-Ni系A2B7型合金的电化学贮氢性能,用RE(RE=Nd,Sm,Pr)部分替代合金中的La,用感应熔炼及退火工艺制备了La0.8-xRExMg0.2Ni3.35Al0.1Si0.05(RE=Nd,Sm,Pr;x=0,0.2)电极合金。为了抑制Mg在熔炼过程中的挥发,熔炼过程中采用氦气作为保护气氛。用X射线衍射(XRD)和扫描电镜(SEM)分析了铸态及退火态合金的微观结构,并测试了铸态及退火态合金的电化学贮氢性能,比较了不同稀土元素替代La对合金电化学性能的影响。结果表明,铸态及退火态合金包含两个主相,具有Ce2Ni7型结构的(La,Mg)2Ni7相以及Ca Cu5型结构的La Ni5相。RE(RE=Nd,Sm,Pr)部分替代La未影响合金的相组成,但使合金的相含量发生明显改变。此外,元素替代使铸态及退火态合金的组织明显细化。RE(RE=Nd,Sm,Pr)部分替代La显著改善了合金的电化学贮氢性能,包括电化学循环稳定性、放电容量及电化学动力学性能。     

新型(Fe,Co)-Zr-RE-B非晶合金的热稳定性和磁性

利用旋铸技术制备了一种新型的含稀土元素的铁基非晶合金。研究了Nd含量对Fe70Co8Zr7-xNdxB15(x=0～6%原子数分数)合金的非晶形成能力、热稳定性和磁性能的影响。当该合金系的Nd含量在0～6%(原子数分数)变化时,其饱和磁感应强度(Js)在1.10T～1.37T范围内变化,矫顽力(Hc)在2.28A/m～8.15A/m范围内变化。Js随Nd含量的增加而增加,当Nd含量为2%和3%时,其Hc值均在3A/m以下,且在Nd含量为2%时,具有最高的非晶形成能力(glassformationability简称GFA)即大的ΔTx(达61K);同时又有良好的软磁性能,其Js和Hc值分别为1.25T和2.28A/m。经对比得出,Fe70Co8Zr5RE2B15(RE=Ce、Pr、Gd和Tb)合金与Fe70Co8Zr5Nd2B15具有相近的非晶形成能力和磁性能。     

稀土对机械合金化制备碳钢表面铬合金层的影响

以纯铬粉和Cr+RE[w(RE)=10%]硅铁粉末组合为原始粉末,利用行星球磨机,制备高铬合金层.采用X射线衍射、扫描电镜、能谱等方法分析合金层成分、显微结构及元素分布,并用多种实验手段检测合金层的显微硬度、抗热剥落能力及在NaCl和H2SO4腐蚀介质中的耐蚀性,以探讨稀土元素对合金层性能的影响.实验结果表明,合金层的显微硬度显著提高,抗剥落能力得到明显改善,在质量分数为3.5%的NaCl溶液中的耐腐蚀性能也得到较大提高.     

Effect of Yttrium on Microstructures and Preparation and Structure of Mg2-xRExNi (RE=La,Ce,Pr,Nd,Y) Ternary Alloys

A series of Mg2-xNdxNi(x=0.05,0.1,0.2,0.3)alloys and Mg1.95RE0.05Ni(RE= La,Ce,Pr,Nd,Y)ternary alloys were prepared by ball milling of mixted powder of Mg,Ni,RE and sintering under the protection of argon.XRD analysis shows that Mg2-xNdxNi(x=0.05,0.1)and Mg1.95RE0.05Ni consist of single phase with the same crystal structure as Mg2Ni.While three-phase alloys including Mg2Ni,NdNi and NdMgNi4 were formed in Mg1.8Nd0.2Ni and Mg1.7Nd0.3Ni alloys respectively.The lattice constants of Mg2Ni in those ternary alloys were calculated.The decomposition of Mg2Ni occurs in the milling process of Mg2Ni and Mg1.95RE0.05 Ni alloys respectively.For the latter,another earlier reaction occurs in milling process,which means that atoms of RE are separated from crystal structure of Mg2Ni and form relevant oxides by combination with oxygen existed in argon atmosphere.     

Kinetics of Glass Transition and Crystallization in Carbon Nanotube Reinforced Mg-Cu-Gd Bulk Metallic Glass

Mg65Cu25Gd10 bulk metallic glass and its carbon nanotube reinforced composite were prepared. Differential scanning calorimeter （DSC） was used to investigate the kinetics of glass transition and crystallization processes. The influence of CNTs addition to the glass matrix on the glass transition and crystallization kinetics was studied. It is shown that the kinetic effect on glass transition and crystallization are preserved for both the monothetic glass and its glass composite. Adding CNTs in to the glass matrix reduces the influence of the heating rate on the crystallization process. In addition, the CNTs increase the energetic barrier for the glass transition. This results in the decrease of GFA. The mechanism of the GFA decrease was also discussed.     

La0.65RE0.10Mg0.25Ni3.5Si0.15(RE=La,Ce,Pr,Nd,Sm)储氢合金的电化学性能及EIS分析

通过感应熔炼制备La0.65RE0.10Mg0.25Ni3.55i0.15(RE =La,Ce,Pr,Nd,Sm)合金.采用X射线衍射方法分析了合金的相结构,研究了其电化学性能,并采用电化学阻抗谱分析了合金电极的放氢动力学特性.研究结果表明,合金是以LaNi5、LaNi3为主相的多相结构,同时合金中少量的Si元素与Mg和Ni元素形成了少量的Mg2 Si相和Ni2Si相.Ce,Pr,Nd,Sm部分替代La以后,合金的放电容量下降,Ce的替代使合金容量大幅度降低.对于本系列合金,La被其他稀土元素部分替代后,合金经过100次循环后的容量保持率略有下降,但除了Pr元素以外,变化值均较小.合金电极的电化学阻抗谱分析表明,中低频区的容抗弧半径依次为Ce ＞La＞ Nd ＞Sm ＞Pr,这表明采用Nd、Sm、Pr替代La后合金电极在碱液中放电过程电荷传递电阻Rct减小,即合金表面活性增加,但Ce替代却导致Ret急剧增大,这可能与Ce在碱液中易形成氧化物降低了合金的表面活性有关.     

Impression Creep Behavior of an Mg–Zn–RE Alloy at Elevated Temperatures

Mg–Zn–RE alloys are promising candidates for automotive and aerospace applications as, among magnesium alloys, they have better corrosion and creep resistance abilities at elevated temperatures. This study evaluates the high-temperature creep behavior of ZE41 magnesium alloy, belonging to the Mg–Zn–RE family, using impression test. Impression tests were performed under a constant temperature and stress with a flat-ended cylindrical punch. Power law and Eyring relationships were used to analyze the creep mechanism. By applying the power-law relationship, it was found that the creep exponent decreased from 7.5 to 4 in the temperature range of 493 K to 593 K. Activation energy increased from 78.5 to 107.1 kJ/mol in the applied stress range of 350 to 500 MPa (normalized stress: 0.024 ≤ σ_imp/G ≥ 0.034). Using the Eyring relationship, a single activation energy of 25 kJ/mol for the entire stress and temperature range was obtained. Based on the creep exponent and activation energy, it is proposed that pipe-diffusion-controlled dislocation climb is the dominant mechanism, but grain boundary sliding also contributes at higher stresses.

     

On the Unavailability of Universal Glass Forming Ability Criterion

The present work examines different glass forming ability criteria (GFA), which distribute into four major categories based on different theories for glassy alloys. Four major categories are based on (i) characteristics transformation temperatures, (ii) Miedema approach, (iii) internal atomic configuration, and (iv) kinetic constraints (viscosity, diffusivity, etc.). Twelve alloys of widely different origin and nature (with respect to number of constituent elements, base element, critical casting thickness, etc.) have been selected for studying the applicability of different GFA criteria of different categories. The experimentally determined critical casting thickness (Z_max) of each alloy has been taken to be the measure of GFA. The best criterion of each category has been identified. Finally, it has been observed that no single criterion of any category alone shows satisfactory correlation with Z_max. However, two criteria of two different categories do not simultaneously fail. It has been concluded that to determine GFA of any random glass forming material, two different criteria of two different categories should be checked. If both results do not indicate similarity in them, GFA must be checked with third criteria of third category.     

Study on Rare Earth Electrolyte of Ce_(0.9)RE_(0.1)O_(2-δ) (RE=Pr, Nd, Sm, Gd, Dy)

Thesolidelectrolyteisakeycomponentofsolidoxidefuelcell (SOFC) .Dopedceriaisoneofpromis inghigh conductingsolidelectrolyteinSOFC[1,2 ] .Butitiswell knownthatitisdifficulttosinterdopedceriabysolidstatereactioninair .TheCe0 .9RE0 .1O2 -δelectrolytematerialswerepreparedbythesol gelmethod .Thesinteringtemperatureofthesamplescandecreasetoabout 4 0 0K .Theionicconductivityandlinearthermalexpansionpropertiesofsol gelpreparedCe0 .9RE0 .1O2 -δinawidetemperaturerangewerein vestigated .Thepowder…     

Synthesis, Structure and Bonding Feature of New Metallic Zintl Phases RE 3Cu 3Sb 4(RE=Nd, Sm, Tb, Dy, Ho)

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Preparation and Structure of Mg2-xRExNi （RE = La, Ce, Pr, Nd, Y） Ternary Alloys

A series of Mg2-xNdxNi (x =0.05, 0.1, 0.2, 0.3) alloys and Mg1.95RE0.05Ni (RE= La, Ce, Pr, Nd, Y)ternary alloys were prepared by ball milling of mixted powder of Mg, Ni, RE and sintering under the protection of argon. XRD analysis shows that Mg2-xNdxNi (x = 0.05, 0.1 ) and Mg1.95RE0.05Ni consist of single phase with the same crystal structure as Mg2Ni. While three-phase alloys including Mg2Ni, NdNi and NdMgNi4 were formed in Mg1.8Nd0.2Ni and Mg1.7Nd0.3Ni alloys respectively. The lattice constants of Mg2Ni in those ternary alloys were calculated. The decomposition of Mg2Ni occurs in the milling process of Mg2Ni and Mg1.95RE0.05Ni alloys respectively. For the latter, another earlier reaction occurs in milling process, which means that atoms of RE are separated from crystal structure of Mg2Ni and form relevant oxides by combination with oxygen existed in argon atmosphere.     

多品种重稀土硅铁合金的试生产

阐述了用钇基重稀土硅铁合金为原料，分别添中铜、镁、铝等金属在中频熔炼中炼制多品种重稀土硅铁合金产品的生产工艺。     

稀土硅铁孕育对高铬合金白口铸铁性能的影响

本文对稀土硅铁、钒铁、钛铁的不同加入量对高铬合金白口铸铁性能的影响进行了实验研究。结果表明，当稀土硅铁的加入量为１．２～１．５％时，冲击韧性达到最大值，硬度也有提高。稀土硅铁孕育可以显著改善碳化物的形态和分布，细化基体组织。当加入量为０．９～１．５％时，大部分碳化物断网，呈孤立状态分布。钒铁的加入量为０．２％时，即可起到明显的孕育作用，机械性能得到提高。