Hydrogen storage properties of (Ti0.85Zr0.15)1.05Mn1.2Cr0.6V0.1M0.1 (M=Ni, Fe, Cu) alloys easily activated at room temperature

The(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)M_(0.1)(M=Ni, Fe, Cu) alloys with a single C14-type Laves phase have been fabricated by arc melting. They are able to be easily activated by one hydrogen absorption and desorption cycle under 4 MPa hydrogen pressure and vacuum at room temperature. Partial substitution of M for Mn results in the increase of hydrogenation and dehydrogenation capacities in an order of Ni Fe Cu. M elements increase the absorption and desorption plateau pressure in an order of(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Cu_(0.1)(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Fe_(0.1)(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Ni_(0.1). The(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Cu_(0.1) alloy has reversible hydrogen capacities of 1.81 wt% at 273 K and 1.58 wt% at 318 K with formation enthalpy(ΔH_(ab)) of-20.66 kJ mol~(-1) and decomposition enthalpy(ΔH_(de)) of 27.37 kJ mol~(-1). The differences in the hydrogen storage properties can be attributed to the increase of the interstitial size for hydrogen accommodation caused by the increase of unit cell volumes in the order of(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Ni_(0.1)(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Fe_(0.1)(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Cu_(0.1).     

Effect of TRT process on GFA, mechanical properties and microstructure of Zr-based bulk metallic glass

The effect of yttrium addition on the glass-forming ability(GFA) and mechanical properties of the Zr-based (Zr_(0.525)Al_(0.1)Ti_(0.05)Cu_(0.179)Ni_(0.146))_(100-x)Y_x and(Zr_(0.55)Al_(0.15)Ni_(0.1)Cu_(0.2))_(100-x)Y_x(x=0,0.2,0.4 0.6,1,2) alloys was studied.Micro-alloying of 0.6%yttrium enhances the room temperature ductility as well as the GFA of the Zr-based alloys.The mechanism of enhancing the GFA and room temperature ductility was analyzed.It is indicated that proper yttrium addition stabilizes the...     

Micro-alloying of yttrium in Zr-based bulk metallic glasses

The effect of yttrium addition on the glass-forming ability(GFA) and mechanical properties of the Zr-based (Zr_(0.525)Al_(0.1)Ti_(0.05)Cu_(0.179)Ni_(0.146))_(100-x)Y_x and(Zr_(0.55)Al_(0.15)Ni_(0.1)Cu_(0.2))_(100-x)Y_x(x=0,0.2,0.4 0.6,1,2) alloys was studied.Micro-alloying of 0.6%yttrium enhances the room temperature ductility as well as the GFA of the Zr-based alloys.The mechanism of enhancing the GFA and room temperature ductility was analyzed.It is indicated that proper yttrium addition stabilizes the...     

锂离子电池核壳G@Cu_(0.85)Sn_(0.15)@C负极材料的改性

针对锡负极材料充放电过程中的体积效应,综合采用组分改性与结构改性的研究方法,合成Cu_(0.85)Sn_(0.15)合金负极材料,研究Cu的掺入对Sn电化学稳定性的影响,同时基于优化改性的Cu_(0.85)Sn_(0.15)合金开展核壳结构设计,研究最佳核壳结构构造工艺.结果表明,掺入Cu能在一定程度上改善Sn的循环稳定性,Cu_(0.85)Sn_(0.15)样品的容量在60次循环后趋于稳定,库伦效率较高;核壳结构处理能大幅提升Cu_(0.85)Sn_(0.15)合金负极材料的循环稳定性,采用球形改性天然石墨作为内核的G@Cu_(0.85)Sn_(0.15)@C负极材料首次放电比容量接近800 m Ah/g,充电比容量最大值超过了500 m Ah/g,100次容量保持率大于85%.核壳结构能将Cu_(0.85)Sn_(0.15)合金的体积效应控制在"囚笼"式结构内,利于材料容量的发挥及循环稳定性的提升.核壳结构的可控制备对实现锡基合金负极材料的产业化具有重要的作用.     

用孤子模型计算Y_(1-x)Ca_xBa_2Cu_(2-x)M_xO_(7-δ)体系的转变温度

本文利用形变材料中的孤子阐明高温超导现象,导出转变温度T_c与能隙△的表达式并求出2△/k_BT_c的值。另外,利用Y_(1-x)Ca_xBa_2Cu_(2-x)M_xO_(7-δ)(M=Fe,Ni)体系的有关物理常数,计算出的T_c理论值与实验值符合得相当好。     

Sm_(1+x)Ba_(2-x)Cu_3O_y固溶体

用X射线衍射及氧含量分析法测定了Sm_(1+x)Ba_(2-x)Cu_3O_y固溶区域为0≤x≤0.4。当x<0.25时,Sm_(1+x)Ba_(2-x)Cu_3O_y属正交晶系;x=0.25时,发生从正交到四方的相变;在整个固溶区域内,T_c随x的增加而下降,直至淬灭。同时探讨了Sm_(1+x)Ba_(2-x)Cu_3O_y化合物在不同的淬火温度、氧含量与晶体结构、超导电性的关系。     

晶界偏析对CaCu_3Ti_4O_(12)陶瓷介电性能的影响

采用溶胶凝胶法制备Ca Cu_3Ti_4O_(12),通过球磨对陶瓷样品进行处理,探究此处理方法对Ca Cu_3Ti_4O_(12)介电性能的影响.研究结果表明,球磨对Ca Cu_3Ti_4O_(12)陶瓷样品的介电常数有较大影响.随着球磨时间的增加,样品介电常数显著增加,当球磨时间为4 h,其室温下介电常数可达10~6量级,比未经球磨处理的样品高2个数量级,且随温度升高,介电常数显著增大.温度上升100 K,介电常数约提高一个数量级.同时SEM分析表明,球磨处理Ca Cu_3Ti_4O_(12)样品介电常数的增大与其晶界偏析有较大的关系,特别是晶界处析出的Cu O二次相可极大地提升Ca Cu_3Ti_4O_(12)的极化率,可提高约2个数量级.     

Ba_(4.2)Nd_(9.2)Ti_(18-x)Zr_xO_(54)(x=0、0.25、0.5、1、1.5)微波介质陶瓷的结构与介电性能

采用传统固相反应法制备Ba_(4.2)Nd_(9.2)Ti_(18-x)Zr_xO_(54)(x=0、0.25、0.5、1、1.5)(BNTZ)微波介质陶瓷。运用X线衍射仪(XRD)和扫描电子显微镜(SEM)表征BNTZ陶瓷的相组成和微观结构。结果表明:BNTZ陶瓷的主晶相为Ba Nd2Ti4O12(JCPDS No.44-0061),随着掺杂量的增加,出现微量的Nd2Ti2O7烧绿石相。当x增加时,陶瓷的体积密度、介电常数(εr)和谐振频率温度系数(τf)均降低。而BNTZ微波介质陶瓷的Qf(Q为品质因子,f为频率)值先增加后降低,并且当x≥1时,陶瓷的Qf下降剧烈。当x=0.25时,Ba_(4.2)Nd_(9.2)Ti_(18-x)Zr_xO_(54)陶瓷样品在1 300℃下烧结2h,具有优良的微波介电性能,εr=82.83,Qf=9.009 THz,τf=56.7×10-6℃-1。     

La_(2-x)Sr_xCu_(0.94)Ti_(0.06)O_4体系的超导重现

为了探索高温材料的超导机制,采用固相反应法在最佳掺杂的La_(2-x)Sr_xCu_(0.94)Ti_(0.06)O_4体系中用Ti(4+)取代6%的Cu~(2+),使材料的超导电性完全消失,再向体系中注入空穴,成功合成了La_(2-x)Sr_xCu_(0.94)Ti_(0.06)O_4(0.15≤x≤0.39)系列多晶样品.采用X衍射、物理性质测量系统、超导量子干涉仪、红外光谱和拉曼散射光谱等检测手段对材料的晶体结构、超导电性、磁性质、光学性质和正常态输运性质进行了系统研究.结果表明:通过在La位掺入Sr,向体系提供空穴,并将空穴注入到CuO_2面上,可补偿因高价态Ti掺杂而引入的电子,这种补偿效应可使那些被近邻杂质局域化的空穴重新获得巡游性,变成载流子而凝聚配对,使材料的超导电性重现.     

Mo部分替代Ti对V_(40)Ti_(50)Fe_(10)合金储氢性能的影响

为了考察Mo部分替代Ti对高容量V_(40)Ti_(50)Fe_(10)合金储氢性能的影响,采用电弧熔炼制备了V_(40)Ti_(50-x)Mo_xFe_(10)(x=0～30)合金,系统地研究了该系列合金的结构和储氢性能随Mo替代Ti含量的变化规律,并探讨合金储氢容量的衰退机制。研究表明:该系列合金均由主相体心立方(BCC)固溶体和少量的C14型Laves第2相组成;Mo取代Ti并未改变合金的主相结构,但Laves第2相的含量明显降低,合金整体均匀性增加;随着Mo含量的增加,BCC相的晶胞体积逐渐减小,合金的放氢量总体呈现下降趋势但中间出现波动状态,而放氢平台压则持续上升;在这一系列合金中,V_(40)Ti_(40)Mo_(10)Fe_(10)合金的储氢性能较优,具有相对宽泛且平坦的放氢压力平台,可逆储氢量较高,且室温下吸放氢过程均可在5 min内完成。循环测试表明,合金氢化物在吸放氢过程中会形成难以活化的TiFe相,导致合金出现成分分离,影响合金的稳定性,从而造成储氢容量衰退。     

Cu_60Zr_20Ti_20块体金属玻璃在不同应变速率轧制时的组织变化

利用X射线衍射仪、差示扫描量热仪和高分辨电镜对Cu_60Zr_20Ti_20块体金属玻璃在低温轧制过程中的结构变化进行了研究.结果表明,应变速率对Cu_60Zr_20Ti_20金属玻璃塑性变形过程中相变产物具有决定性的影响.随着应变速率从1.0×10~(-4)增大到5.0×10~(-1)s~(-1),大塑性变形后的Cu_60Zr_20Ti_20金属玻璃从不发生相变到产生相分离、再到同时发生相分离和纳米晶化转变,发生相变的临界应变量则不断减小.     

硼氢化物(BHn)(n=1~5)稳定性与红外光谱

采用密度泛函(DFT)中的B3P86方法,结合Dunning的相关一致基组cc-PVTZ,优化计算硼氢化物(BHn)(n=1～5)可能的几何构型,得出最稳定构型的几何参数、电子结构和红外光谱等性质参数,给出了最稳定结构的总能量(ET)、结合能(EBT)、平均结合能(Eav)、电离势(EIP)、能隙(Eg)、费米能级(EF)和氢原子差分吸附能(Bdiff)等.结果表明硼氢化物基态稳定结构的电子态分别为:n为奇数为单重态1∑和1 A,n为偶数为双重态2A;由于B原子属于缺电子原子,能与等电子原子H化合,通过氢端或桥键形成氢化物,本文优化计算发现,硼氢化物最稳定的构型都存在氢端或桥键,且n为奇数的氢化物的氢端或桥键作用比相邻偶数的氢化物强.最后计算了硼氢化物最稳定结构的红外光谱、平均结合能、电离势、能隙和费米能级等动力学电子特性,分析得出(BHn)(n=1～5)氢化物中BH3的电离势和能隙最大,说明该氢化物最稳定,氢原子差分吸附能也最大.     

高温超导体YBa_2Cu_3O_(7-x)的结构、形貌和性质

本文研究了高温超导体YBa_2Cu_3O_(7-x)的结构、形貌和性质。使用SEM,TEM,EDS和SAED等探讨了化合物成分、结构、形貌。测量了样品的电阻与温度、磁化率与温度的关系,得到零电阻温度T_(C0)≈91K,完全抗磁性温度88K。并对超导化合物YBa_2Cu_3O_(7-x)的性质作了初步分析。     

氧含量分析法确定Sm_(1+x)Ba_(2-x)Cu_3O_n的固溶区

基于碘量法测定高温超导氧化物氧含量的方法,总结出固溶化合物Sm_(1+x)Ba_(2-x)Cu_3O_n的氧含量n随固溶度x变化的规律性;从理论分析和实验测定得出在固溶区域内,Sm_(1+x)Ba_(2-x)Cu_3O_n的氧含量n与替代程度x呈线性关系,超出固溶极限x_0,直线斜率将发生明显变化,此结果与X射线粉末衍射结果基本一致。关键词:碘量法,氧化物高温超导体,氧含量,固溶体。 稀土氧化物高温超导体123相合成过程中常伴有少量杂相产生,少量杂质对超导体的超导电性影响很大,在含La、Nd、Sm、Eu等体系中,123相常形成如R_(1+x)Ba_(2-x)Cu_3O_n替代或固溶体,准确测定固溶体极限x_0,对此类超导单晶的制备工艺和理论研究十分重要。 中子衍射表明,在R_(1+x) 、Ba_(2-x)Cu_3O_n固溶体中,稀土离子R代替Ba离子,其作用结果之一是固溶体化合物氧含量的变化呈一定的规律性。 本文采用无机分析化学中的碘量法,测定固溶体化合物Sm_(1+x)Ba_(2-x)Cu_3O_n的氧含量,从理论和实验分析高温超导体氧含量n随固溶度x变化的规律,从而确定固溶体极限X_0。     

Ba_(1-x)Ca_xZr_(0.2)Ti_(0.8)O_3陶瓷的晶体结构、储能性能及其极化机理

采用柠檬酸盐法制备名义组成为Ba_(1-x)Ca_xZr_(0.2)Ti_(0.8)O_3(x=0、0.05、0.10)的陶瓷材料,分析了不同钙含量对陶瓷样品结构及储能性能的影响。结果表明,x=0和x=0.05的陶瓷材料显微结构均呈现出双峰式晶粒尺寸分布,而x=0.10的陶瓷样品晶粒大小分布均匀;随着钙含量增加,Ba_(1-x)Ca_xZr_(0.2)Ti_(0.8)O_3晶格常数逐渐减小,晶体结构呈现单一钙钛矿相,当x=0.10时,陶瓷样品储能性能恶化;陶瓷材料储能性能与缺陷偶极子诱导的极化团簇转向行为有关。通过分析介电常数、介电损耗和交流电导率随测试频率的变化规律,证实了样品中极化实体的极化行为与氧空位跃迁存在关联。     

Improvements of dielectric properties of Cu doped LaTiO_(3+δ)

The ceramic composites of Cu-doped La_(1-x )Cu_x TiO_(3+δ)(x=0.05, 0.15, 0.3, 0.5) were synthesized by conventional solid-state reaction. The complex dielectric properties of the composites were investigated as a function of temperature(77 K ≤T≤ 320 K) and frequency(100 Hz ≤ f ≤1 MHz) separately. In all composites, the dielectric constants increase monotonously and the dielectric loss undulates with temperature. And it is clearly observed that extraordinarily high low-frequency dielectric constant(～10~4)appear at room temperature in La_0.5Cu_0.5TiO_(3+δ), which is 100 times larger than that of La_0.95Cu_0.05 TiO_(3+δ). Interestingly, the dielectric constants increase remarkably with the doped Cu contents, meanwhile the dielectric loss for all samples is ideal lower than 1 at room temperature in the measured frequency range. By means of complex impedance analysis, the improvements of dielectric properties are attributed to both bulk contribution and grain boundary effect, in which the bulk polaronic relaxation and the Maxwell–Wagner relaxation due to grain boundary response are heightened remarkably with the high doped Cu contents.     

(MnFe)_(1.9-x)V_xP_(0.5)Si_(0.5)化合物磁性和磁热性能

采用机械合金化和固相烧结技术,制备了V掺杂的Mn_(1.0)Fe_(0.9-x)V_xP_(0.5)Si_(0.5)(x=0,0.02,0.06,0.10,0.14,0.16)和Mn_(1.0)Fe_(0.9-x)V_xP_(0.5)Si_(0.5)(x=0,0.02,0.06,0.10,0.12)系列化合物.利用X射线衍射和磁性测量技术研究了材料的晶体结构、磁性和磁热效应.研究结果表明:两个系列化合物均结晶为Fe2P型六角结构;调整掺杂元素V的含量,可以将居里温度控制在188-375K范围;化合物的最大磁熵变随V含量增加而减少,化合物的热滞随V含量增加而减小,最小值为1K.     

自旋玻璃CuMn和CuMnT(T=Ti,Pd,Pt)的磁感生各向异性

本文是文献[1]的补充,除补充了一些典型特性外,还通过一些Cu_(93.4)Mn_(6.6)及含有λ_d不同的微量添加元素Ti,Pd,Pt的Cu_(95.1)Mn_(2.0)Ti_(2.9),Cu_(96.7)Mn_(2.1)Pd_(1.2),Cu_(97.2)Mn_(2.1)Pt_(0.7)的实验结果,介绍了Mn含量对磁各向异性特性及这些微量添加元素对2％Mn-Cu有关特性的影响。本文的实验条件同文[1]。     

pH对改进Pechini法制备Ba_(0.92)Sr_(0.08)Ti_(1-x)Zr_xO_3纳米粉体结构的影响

通过对Pechini法改进,在不同pH和锆离子掺杂量下制备了Ba_(0.92)Sr_(0.08)Ti_(1-x)Zr_xO_3(x=0~0.12,BSTZx)纳米粉体.通过物相结构的表征得到在锆离子掺杂量为0.03时,BSTZx纳米粉体具有较高的结晶度.通过XRD、SEM和激光粒度仪分别表征不同pH下BSTZ0.03纳米粉体的物相结构、形貌和粒径分布.结果表明,pH为6.5时制备的BSTZ0.03纳米粉体粒不易团聚、粒径分布窄且结晶度高.     

影响BiSr_1Ca_1Cu_2O_x及Y_1Ba_2Cu_sO_(7-x)超导相形成的几个重要因素

目前,已有大量不同的所谓高温超导体,其可分为两类。第一类是以La_(2-x)Sr_xCuO_(4-x)为代表,T_c=30～40K,晶体是K_2NiF_4结构;第二类是以YBa_2Cu_3O_(7-x)为代表,T_c=90K左右,晶体是缺氧钙钛矿结构,即所谓“123”结构。新高温超导体都是混合含氧化物,显示出陶瓷的机械和物理性能。新材料性能的关键在于化学键合在一起的铜(Cu)和氧(O)原子构成的原子平面,铜-氧化学键合的特殊性质使得材料在某些方向能很好地传导电流,这与大多数陶瓷为绝缘体形成对照。目前,人们在BiSrCaCuO系中以微量Pb取代部分Sr已可获得160K的高临界温度。作者利用化学纯原料成功地研制出零电阻温度达125K的Bi_1Ca_1Cu_2O_x系超导体和T_c在90K以上的Y_1Ba_2Cu_3O_(7-x)高温超导陶瓷。在研制过程中发现Y_1Ba_2Cu_3O_(7-x)超导相的形成过程中,氧环境及退火降温速度对其形成起十分重要的作用,而原料中的微量杂质对其形成不起关键作用;BiSrCaCuO系对微量杂质不敏感,而对退火温度要求甚高。