高矫顽力的C0（70）Cu（30）合金纳米线阵列的制备及磁性研究

利用直流电化学沉积法,在多孔阳极氧化铝模板中首次制备出了具有[220]取向的单晶面心立方结构的CoCu固溶体合金纳米线阵列,其Co含量高达70%.透射电子显微镜显示纳米线均匀连续,具有较高的长径比,约为300.磁性测量表明所制备的Co（70）Cu（30）合金纳米线具有超高的矫顽力Hc//=2438 Oe（1 Oe=79.5775 A/m）和较高的矩形比S//=0.76,远高于以往报道的CoCu合金纳米线的磁性,分析表明磁性好的主要原因是由于较高Co含量和高形状各向异性.通过磁性测量和模型计算,得到Co（70）Cu（30）合金纳米线阵列在反磁化过程中遵从对称扇型转动的球链模型,并从结构的角度分析了Co（70）Cu（30）合金纳米线阵列的反磁化行为.     

FeCo二元合金纳米线阵列的磁化反转

利用交流电化学沉积方法在氧化铝模板中制备了一维结构的Fe_xCo_1-x(0 ≤ x ≤ 0.51)二元合金纳米线阵列.X射线衍射结果显示,单质Co纳米线为(100)择优取向的hcp结构,FeCo合金纳米线则呈现(110)择优取向的bcc结构,而且衍射峰随纳米线中Fe含量的增加向低角度偏移.室温磁性测量结果显示, FeCo合金纳米线具有较好的磁特性.与Co纳米线相比,Fe的引入改善了Co纳米线的磁性能,使其呈现出较大的矫顽力和较高的矩形比.采用一致转动模型和对称扇形机理的球链模型分别计算了FeCo合金纳米线的矫顽力, 发现其磁化反转机理与对称扇形机理的球链模型相符合.     

海胆状CoCu双金属纳米复合材料的合成及其在甘油氢解制丙二醇中的催化性能

以Ru为多相成核剂和硬脂酸为表面活性剂,在多元醇溶液中合成了CoCu双金属纳米复合物,并在甘油选择性氢解制丙二醇中评价了其催化性能．结果表明,硬脂酸作为结构导向剂可诱使Co纳米晶沿着一维方向生长,形成纳米线．当Co²⁺和Cu²⁺共存于多元醇溶液中,由于Cu²⁺较高的氧化还原电位,首先被还原成Cu⁰,进而增长成100～300 nm的球形粒子．在Cu粒子表面,Co²⁺被还原成核,在表面活性剂的结构导向作用下生长为长度为100～500 nm的纳米棒,从而形成海胆状CoCu双金属纳米复合结构．在甘油选择性氢解制丙二醇反应中,海胆状CoCu双金属复合催化剂的单位表面活性与丙二醇选择性均明显高于单金属Co纳米线和Cu球形粒子,在Co₉₀Cu₁₀催化剂上获得33%的丙二醇收率．这可能是由于Co和Cu界面的协同效应促进了甘油的转化所致．     

Ni70Co30/Cu磁性金属多层膜界面元素分布的X射线异常散射研究

应用X射线异常散射技术研究了[Ni₇₀Co₃₀(25A)/Cu(20A)]₂₀多层膜的界面结构, 结果表明, 退火前后Cu/Ni₇₀Co₃₀和Ni₇₀Co₃₀/Cu界面的温度行为不同.对于制备态样品, 界面结构是非对称的, 在Cu/Ni₇₀Co₃₀界面, 存在一个8A厚的CuNi₃过渡层和一个4A厚的NiCo层. 然而, Ni₇₀Co₃₀/Cu界面却不存在任何扩散. 285\textcelsius 2h退火后,Ni₇₀Co₃₀/Cu界面开始发生扩散, 产生了一个12A厚的CuNi₂Co过渡层. X射线能量分别在Co, Ni, Cu K吸收边附近的X射线漫散射实验, 揭示了在Ni₇₀Co₃₀/Cu多层膜的界面处, Cu与Ni和Co具有不同的横向关联长度, 显示了不均匀的横向分布.     

Co掺杂对铁磁金属La0.8Sr0.2MnO3磁电阻影响机理

通过对La_0.8Sr_0.2Mn_1-yCo_yO₃(y≤02)饱和磁矩和输运的测量,研究了Co对La_0.8Sr_0.2MnO₃的磁电阻影响机制.结果表明,在La_0.8Sr_0.2Mn_1-yCo_yO₃（y≤02）中Co³⁺离子是低自旋态.由于Mn³⁺—O—Co³⁺—O—Mn³⁺类型的磁交换与Mn³⁺-Mn⁴⁺离子间双交换作用相比较弱,Curie温度T_C附近的磁电阻随着Co掺杂量的增加而降低.与此相反,由于Co²⁺离子与e_g巡游电子的反铁磁交换耦合作用,低温区间的磁电阻随着Co掺杂量的增加而升高.     

固相反应法制备的CoxZn1-xO磁性能的研究

采用固相反应烧结法制备了Co掺杂ZnO的粉末和压片样品. XRD衍射表明样品中Co²⁺离子取代Zn²⁺离子进入了ZnO晶格中. 在室温下样品均表现为顺磁性, 利用密度泛函理论(DFT+U)方法计算得到的Co₂Zn₁₄O₁₆体系反铁磁基态更稳定, 并通过Co, O原子电子迁移变化, 表明了CoZnO体系中磁性机理更倾向于Co²⁺—O^2-—Co²⁺成键的间接交换作用模型. 改进了安德森模型中的直接交换积分J_pd公式. 提出两个可能的途径来实现具有本征铁磁性氧化物半导体.     

铁基Heusler合金Fe2Co1-xCrxSi的结构、磁性和输运性质的研究

基于多种实验手段和能带计算的方法, 对四元合金Fe₂Co_1-xCr_xSi的晶体结构、 磁性、输运性质及能带结构进行了研究. 研究发现, 随着Cr的增加, 合金Fe₂Co_1-xCr_xSi保持了高度有序结构, 逐渐从Hg₂CuTi结构的Fe₂CoSi 过渡到L2₁结构的Fe₂CrSi; 由于次晶格网络的破坏, 居里温度逐渐下降; 系列合金的分子磁矩呈现线性下降, 符合半金属特性; 剩余电阻比率与原子占位有序程度密切相关, 呈现两端大、 中间小的特点. 在Cr替代Co的过程中, 材料半金属能隙逐渐打开, 表现半金属特征. 同时费米能级从Fe₂CoSi半金属能隙的价带顶上移至Fe₂CrSi能隙的导带底. 最大的能隙宽度出现在x= 0.75处, 这表明四元合金有可能成为具有更高自旋极化率和更强抗干扰能力的自旋电子学材料.     

多自旋态离子Co替代诱导La2/3Ca1/3MnO3体系的输运反常

利用具有多自旋态的Co离子进行Mn位替代，制备了La_2/3Ca_1/3Mn_1-xCo_xO₃ (0≤x≤0.15) 系列样品并研究了体系的结构和输运特性.结果表明，在替代范围内，样品呈现很好的单相结构，各晶格参数随替代量的增大而减小；Co替代导致体系出现电输运反常，具体表现为在居里温度T_C以下电阻-温度曲线的二次金属-绝缘转     

Gd,Co共掺杂对BiFeO3陶瓷电输运和铁磁特性的影响

采用快速液相烧结法制备BiFeO₃和Bi_0.95Gd_0.05Fe_1-xCo_xO₃ (x= 0, 0.05, 0.1, 0.15, 0.2)陶瓷样品,研究Gd, Co共掺杂对BiFeO₃微观结构, 介电性能和铁磁性的影响. X射线衍射谱表明:所有样品的主衍射峰与纯相BiFeO₃相符合且 具有良好的晶体结构,随着Co³⁺掺杂量x的增大, Bi_0.95Gd_0.05Fe_1-xCo_xO₃样品的主衍射峰(104)与(110)逐渐相互重叠, 当x大于0.1时, 样品呈现正方晶系结构; J-V特性显示Gd³⁺, Co³⁺共掺杂有效地降低BiFeO₃陶瓷的漏导电流,其降低幅度为1-2个数量级; 当f=10³ Hz时, Bi_0.95Gd_0.05Fe_0.8Co_0.2O₃的介电常数是BiFeO₃的6倍, 而Bi_0.95Gd_0.05Fe_0.95Co_0.05O₃和 Bi_0.95Gd_0.05Fe_0.85Co_0.15O₃样品的介电损耗最小,均为0.01.室温下, Bi_0.95Gd_0.05Fe_1-xCo_xO₃样品磁性与BiFeO₃相比显著增强. 在磁场为30 kOe的作用下,Bi_0.95Gd_0.05Fe_1-xCo_xO₃ (x= 0, 0.05, 0.1, 0.15, 0.2)的剩余磁化强度M_r分别是BiFeO₃的34, 60, 105, 103, 180倍.样品磁性增强的主要原因是Gd, Co掺杂使BiFeO₃的晶格结构发生变化导致BiFeO₃自身储存的磁性能被释放, Gd³⁺的4f电子与Fe³⁺或Co³⁺的3d电子自旋相互作用及样品中存在局域的 Fe-O-Co磁耦合三者共同作用的结果.     

Cu对Ni50Mn36In14相变和磁性的影响

文章研究了Cu替代部分Ni对铁磁性形状记忆合金Ni₅₀Mn₃₆In₁₄相变和磁性的影响规律. 研究表明,在Ni_50-xCu_xMn₃₆In₁₄中,随着Cu含量的增加,相变温度逐渐降低. Cu含量低于5%时,奥氏体的磁性强于马氏体的磁性, 母相和马氏体相的饱和磁化强度的差值ΔM随着Cu含量的增加而增大. 当Cu含量x=4.5时, ΔM迅速增加到80 emu/g, 并在该材料中观察到了磁场驱动的马氏体到奥氏体的转变,显示了该材料作为磁驱动磁电阻材料的潜在应用前景.当Cu含量高于5%时,奥氏体保持铁磁状态, 马氏体相由反铁磁状态变为铁磁状态,马氏体的磁性强于奥氏体的磁性, ΔM大大削弱,磁场驱动性质消失.     

Controlled Cu content of electrodeposited CoCu nanowires through pulse features and investigations of microstructures and magnetic properties

CoCu alloy nanowire arrays embedded in anodic alumina template were fabricated by ac pulse electrodeposition. Different off-times between pulses in an electrolyte with constant concentration of Co⁺² and Cu⁺² and acidity of 4 were employed. The effect of deposition parameters on the alloy contents, microstructures and magnetic properties of Co_xCu_1−x nanowires were studied. It is shown that Co content decreased by increasing the off-time between pulses in a wide range (x = 0.53-0.07). These results are in consistence with saturation magnetization, which was reduced with increase in the off-time between pulses. It was also found that by optimizing the off-times, it is possible to fabricate CoCu nanowires with mixed phase of hcp Co, fcc Cu and fcc CoCu crystal phase.     

CoxCu1-x复相纳米线阵列的制备及其磁性的研究

利用电化学沉积方法在同一种富Co²⁺溶液Co²⁺/Cu²⁺=10∶1中,利用不同的沉积电位成功地制备了一系列不同成分(x=0.38—0.87)和复合相结构的Co_xCu_1-x纳米线阵列.发现随着纳米线中Cu含量的变化,Co_xCu_1-x纳米线的复相结构随之发生规律的变化,最终导致纳米线的磁性也随之规律的变化.随着纳米线中Cu含量的不断增加,一部分Cu与Co形成面心立方结构(fcc)的CoCu固溶体,减弱了磁晶各向异性与形状各向异性的竞争,从而提高样品的方形度;一部分Cu以fcc结构的Cu单质的形式存在于纳米线中,并随着Cu颗粒大小的不同分别起到破坏磁晶各向异性和钉扎畴壁的作用,从而增加纳米线的方形度和矫顽力.对比不同成分的样品,发现Co_xCu_1-x纳米线的方形度和矫顽力的最大值分别出现在Co₇₅Cu₂₅和Co₆₀Cu₄₀中,并且由于其特殊的复相结构致使它们的值要好于相同直径的单相结构的结果. 关键词： 纳米线 电化学沉积 磁性     

Effects of annealing temperature on structure and magnetic properties of amorphous Fe61Co27P12 nanowire arrays

Arrays of Fe₆₁Co₂₇P₁₂ nanowire with an aspect ratio about 70 were prepared in anodic aluminum oxide templates by electrodeposition. The influences of annealing temperature on structure and magnetic properties of Fe₆₁Co₂₇P₁₂ nanowires were studied. When the specimens were annealed below 400 °C, there are no obvious changes in structure except relaxation. With the annealing temperature increasing from 400 to 600 °C, the Fe-Co phase is detected by X-ray diffraction and Mössbauer spectra. The crystalline fraction and hyperfine field can be derived from Mössbauer spectra. The room temperature magnetic hysteresis loops show that the coercivity and squareness of the nanowire arrays in parallel to the wire axis increase with the increasing of annealing temperature, which mainly attributes to the strengthening of anisotropy.     

Thermally activated magnetization reversal process of self-assembled Fe55Co45 nanowire arrays

We have investigated the temperature dependence of the magnetic properties and the magnetic relaxation of the Fe₅₅Co₄₅ nanowire arrays electrodeposited into self-assembled porous alumina templates with the diameter about 10 nm. X-ray diffraction (XRD) pattern indicates that the nanowire arrays are BCC structure with [1 1 0] orientation along the nanowire axes. Owing to the strong shape anisotropy, the nanowire arrays exhibit uniaxial magnetic anisotropy with the easy magnetization direction along the nanowire axes. The coercivity at 5 K can be explained by the sphere chains of the symmetric fanning mechanism. The temperature dependence of coercivity can be interpreted by thermally activated reversal mechanism as being the localized nucleation reversal mechanism with the activation volume much smaller than the wire volume. Strong field and temperature-dependent magnetic viscosity effects were also observed.     

Magnetic domain structure in small diameter magnetic nanowire arrays

Fe_0.3Co_0.7 alloy nanowire arrays were prepared by ac electrodepositing Fe²⁺ and Co²⁺ into a porous anodic aluminum oxide (PAO) template with diameter about 50 nm. The surface of the samples were polished by 100 nm diamond particle then chemical polishing to give a very smooth surface (below ±10 nm/μm²). The morphology properties were characterized by SEM and AFM. The bulk magnetic properties and domain structure of nanowire arrays were investigated by VSM and MFM respectively. We found that such alloy arrays showed strong perpendicular magnetic anisotropy with easy axis parallel to nanowire arrays. Each nanowire was in single domain structure with several opposite single domains surrounding it. Additionally, we investigated the domain structure with a variable external magnetic field applied parallel to the nanowire arrays. The MFM results showed a good agreement with our magnetic hysteresis loop.     

Fabrication and magnetic properties of CoxPd1−x composite nanowire

A series of Co_xPd_1−x   (x=0.37–0.85$x=0.37–0.85$) nanowire arrays have been successfully deposited in a single Co²⁺/ Pd²⁺=20:1 solution by applying the various depositing potentials. We found that the nanowires are the composites of CoPd alloy with some Co and Pd clusters, but the overall structure of the composite wires followed the binary phase relation of Pd–Co. The existence of Pd content makes the nanowires structured in FCC phase, except for Co_0.85Pd_0.15 sample in which some HCP Co phase coexists with the dominating FCC phase. Between Co-rich and Pd-rich nanowires, we found that the optimized composition for Co_xPd_1−x nanowire is around Co_0.73Pd_0.27 in which the coercivity (H_c) and squareness (M_r/M_s) have their maximum values consistently.     

Superparamagnetic properties of La1−xBaxCoO3 (0.0<x<0.18)

The static and dynamic magnetic properties of La_1−xBa_xCoO₃ (0<x<0.18) (LBCO) have been investigated by the dc and ac susceptibility measurements systematically. The spin-glass-like characteristics of magnetic behavior, which are always considered as an evidence of spin glasses for La_1−xSr_xCoO₃ (0<x<0.18) (LSCO), have been observed. However, just like that of LSCO, some magnetic behaviors, which are different from the canonical spin-glass characteristics, for example, the difference far above peak temperature T_p of zero-field-cooled curve between field-cooled magnetization (FCM) and zero-FCM (ZFCM) and the very broad peaks in the samples for x>0.10, are also observed simultaneously. Based on the comparisons with canonical spin-glass Au₉₆Fe₄ alloy and conventional superparamagnetic (SPM) Cu₉₇Co₃ alloy, the nature of the magnetic behaviors in LBCO is ascribed to the superparamagnetic cluster rather than spin glass. Though the magnetic properties behave as SPM, LBCO has one critical point different from that of the conventional SPM Cu₉₇Co₃ alloy. The segregated Co nanoparticles in the Cu₉₇Co₃ alloy are isolated by nonmagnetic background while the clusters in LBCO are embedded in an antiferromagnetic matrix. The SPM behavior of LBCO can only exist at low temperature because the antiferromagnetic matrix transfers to paramagnetic phase at Neél temperature T_N and the SPM cluster turns into ferromagnetic (FM) above T_N.     

Pulse electrodeposition of Co1−xZnx nanowire arrays: Magnetic improvement through electrolyte concentration,off-time between pulses and annealing

Using different electrolyte compositions and varying the off-time between pulses, Co_1xZn_x nanowire arrays were fabricated by ac pulse electrodeposition. The effect of deposition parameters on alloy contents was investigated by studying the microstructures and magnetic properties of as-deposited and annealed Co_1xZn_x nanowires. It is shown that Zn content in CoZn nanowires exponentially increases by increasing the zinc ions in the electrolyte. The Zn content initially increases to a maximum by increase in off-time between pulses and then falls off. Adding a certain amount of Zn to Co led to form amorphous CoZn nanowires. A significant increase in magnetization, coercivity and squareness of CoZn nanowires was observed after annealing. The rate of increase in magnetization of annealed samples was seen to be inversely proportional to their initial magnetization. Improvement of magnetic properties of annealed samples may be caused by magnetic cluster formation and pinning effect.     

Effects of nickel on the crystallization of Zr70Cu20Ni10 amorphous alloy

Differential scanning calorimetry (DSC) and x-ray diffraction (XRD) are employed to investigate the effects of nickel on the crystallization of the amorphous Zr₇₀Cu₂₀Ni₁₀ alloy. We have found that the crystallization process of the amorphous Zr₇₀Cu₂₀Ni₁₀ alloy is strongly influenced by the addition of nickel. Addition of 10 at% Ni to the Zr₇₀Cu₃₀ amorphous alloy makes the crystallization process proceed from a single-stage mode to a double-stage mode. The activation energy for crystallization of the amorphous Zr₇₀Cu₂₀Ni₁₀ alloy is calculated to be about 388kJ·mol^-1 on the basis of the Kissinger equation. The effects of nickel on the crystallization of the amorphous Zr₇₀Cu₂₀Ni₁₀ alloy are discussed in terms of the genetics of metals.     

Synthesis and characteristics of Co100−xSnx nanowire arrays

Co_100?xSn_x alloy nanowires were fabricated by electrodeposition of Co²⁺ and Sn²⁺ into anodic aluminum oxide (AAO) templates. X-ray diffraction results indicate that the crystal structures of the nanowires changed from polycrystal to amorphism, and then to polycrystal again with the increase of Sn content in the nanowires. Transmission electron microscopy result shows that the nanowires are about 50 nm in diameter and the aspect ratio is approximately 75. The magnetic response of the arrays was measured using vibrating sample magnetometry at room temperature. The results show that the coercivity and squareness with the magnetic field along the nanowire arrays decrease with the increase of the Sn content. Nanowires exhibit obviously uniaxial magnetic anisotropy, and the easy magnetizing axis is parallel to the nanowires owing to the large shape anisotropy.