新型超导体MgB2及其掺杂研究

MgB2是在2001年新发现的超导材料.它作为一种新型超导体材料备受关注且发展迅速,但其较低的不可逆场和较小的高磁场临界电流密度已成为阻碍其发展的关键.化学掺杂由于具有方便快速、能均匀改性等优点而成为当前提高MgB2超导性能的研究热点.重点评述了有关MgB2的元素或化合物掺杂研究的国内外最新进展,并从基础和应用的角度提出了MgB2超导材料需要深入研究的问题.     

SiC掺杂对MgB2/Fe超导线材临界电流密度和显微结构的影响

利用原位粉末套管法制备出SiC微粉掺杂的MgB2-x(SiC)x2／Fe(z=0．00、0．05、0．10、0．20)超导线材。在750℃,流通高纯氩气的条件下热处理1h后,大部分SiC没有参与取代B位的反应。随着x的增大,线材中非超导相SiC和Mg的含量增加,MgB2的平均晶粒尺寸变小,从而使可作为磁通钉扎中心的晶界的面积相应增加。在外加磁场中,MgB2超导线材的临界电流密度(Jc)随x增大逐步升高,至x=0．10时Jc性能最好,其在6K,5T时的Jc达到了8480A／cm^2,比未掺杂线材的Jc高出约70％。但是,当x=0．20时,Jc却有所下降。Jc的这种变化规律与SiC掺杂引起的MgB2晶粒变小,以及非超导相物质含量之间的相互平衡有关,其中MgB2晶粒变小是Jc提高的主要原因。     

分步反应法制备SiC掺杂MgB2超导线材的研究

以干燥的B粉和Mg粉为原料,采用分步反应法制备了SiC(40～45μm)掺杂的MgB2/Nb/Cu超导线材.通过X射线衍射仪(XRD)、扫描电子显微镜(SEM)研究了在650℃热处理温度下不同掺杂量对所制备样品的相组成、微观结构的影响.采用标准四引线法测定了样品的电阻温度曲线,结果表明,当该工艺第二步热处理温度为650℃时,反应不完全,应适当升高温度;同时高SiC掺杂量有利于在MgB2线材中引入更多B位C掺杂,表现为Tc略有降低,从而提高了其磁通钉扎特性.     

烧结方法对MgB2超导体结构和性能的影响

以Mg粉和B粉为主要原料,采用两种烧结方法制备出MgB2超导体.利用x射线衍射仪、扫描电子显微镜、阿基米德法和标准的直流四引线法等,分别研究了样品的物相组成、显微结构、密度和临界电流密度等.研究发现,MgB2块材的密度随Mg粉粒度的增加而降低.与常规烧结相比,快速烧结时MgB2块材的密度较低且含有更多的非超导相,如Mg和MgBx(x=4,6或12).快速烧结MgB2线材的临界电流密度低于常规烧结线材的.结果表明,快速烧结不利于获得高性能的MgB2超导体.     

提高MgB2超导体临界电流密度的研究进展

临界电流是超导体载流能力大小的重要表征,论述了制备工艺、元素掺杂和物理场对MgB2超导体临界电流密度的影响.使用非晶态高纯硼粉制备致密的MgB2试样有利于样品临界电流密度的提高,添加SiC或者Ti也能起到提高临界电流密度的作用,质子照射使MgB2试样在高磁场条件下的临界电流密度增加,强磁场下烧结则有利于提高MgB2样品临界的传输电流密度.     

掺杂和辐照对MgB2超导电性影响的研究进展

分别从掺杂和辐照两个方面论述了改善MgB2超导电性的研究进展.研究发现:虽然只有少数掺杂物可以提高MgB2的临界转变温度,但几乎所有的掺杂都会提高样品的临界电流密度Jc和不可逆场Hirr.在所有的掺杂物中,SiC掺杂取得了最好的效果.另外研究发现,通过一定程度的辐照也可以提高MgB2的超导电性,但辐照存在一个最佳的剂量,过量的辐照会产生破坏作用.     

超导体MgB2的高温电阻率及热重—差热分析

利用Mg扩散法制备出单相多晶的MgB2超导体，其超导转变的零电阻温度为38.4K左右，转变宽度小于1K。正常态电阻率温度关系为金属型，在270K-450K的高温范围内电阻率与温度成很好的线性关系。差热和热重分析表明在空气气氛中MgB2在900℃左右开始急剧氧化。     

Ti3SiC2材料中Ti3SiC与TiC的界面关系

用透射电子显微镜研究了Ｔｉ３ＳｉＣ２材料中Ｔｉ３ＳｉＣ２与ＴｉＣ的界面关系。结果表明ＴｉＣ和Ｔｉ３ＳｉＣ２颗粒都可能生长在另一相中,Ｔｉ３ＳｉＣ２中的ＴｉＣ颗粒与Ｔｉ３ＳｉＣ２没有明显的晶体学关系,而ＴｉＣ中的Ｔｉ３ＳｉＣ２与ＴｉＣ之间有下列晶体学关系,（１１１）ＴｉＣ／／（０００１）Ｔｉ３ＳｉＣ２,（００２）ＴｉＣ／／（１ １＾－０４）Ｔｉ３ＳｉＣ２,（１ １＾－０）ＴｉＣ／／「１１０」Ｔｉ２ＳｉＣ２。     

MgB2超导电性研究进展

2001年1月所发现的MgB2超导体具有39K的临界转变温度,是迄今为止转变温度最高的非铜氧化物超导体.它可能做为一种新型低成本高性能超导材料而受到广泛关注.本文简述了近期对MgB2超导体的研究工作,介绍了近期主要有关MgB2超导体电子结构研究和应用开发的工作,着重叙述了关于MgB2超导机制的研究.     

On the Magnetism of the Normal State in MgB2

The experimentally observed ferromagnetism in MgB₂ in the normal state is attributed to microphase-separated inclusions of iron. This magnetic character is also observed when the iron content of the samples is reduced below 20 g/g, however in these samples the diamagnetism of MgB₂ is apparent and is measured. It is found experimentally that the diamagnetic susceptibility at room temperature of B element, MgB₂, and MgB₄ is close to the ratio 1:2:4, suggesting that the diamagnetism in these borides is confined to the boron atoms. This observation supports a picture in which the two electrons of Mg are donated to B in MgB₂.     

Effects of Weak Links in the Nonlinear Microwave Response of MgB2 Superconductor

We report experimental results of second-harmonic (SH) response at microwave frequency in several ceramic MgB₂ samples, prepared by different methods. The SH signal has been investigated as a function of the temperature and DC magnetic field. The investigation has been carried out at low magnetic fields, where nonlinear processes arising from motion of Abrikosov fluxons are ineffective. We show that the low-temperature SH emission is ascribable to processes involving weak links. Comparison among the peculiarities of the SH signal radiated by the different samples shows that the presence of weak links strongly depends on the sample preparation method, as well as on the purity and morphology of the components used for the preparation.     

Effect of Heavy Al Doping on MgB2: A Point-Contact Study of Crystals and Polycrystals

We present the results of point-contact spectroscopy (PCS) measurements in single-phase Mg_1−x Al _x B₂ crystals and polycrystals with x up to 0.32, recently grown at ETH (Zurich) and University of Genova, respectively. The differential conductance curves of our “soft” point contacts were measured as a function of temperature from 4.2 K up to the Andreev critical temperature T _c ^A , at which the normal-state conductance is recovered. The gap amplitudes, Δ _σ and Δ _π , were obtained through a two-band BTK fit of the normalized conductance curves. The results extend previous data to the range of heavy Al doping and show that contrary to expectations, no gap merging is observed up to x=0.32 (i.e., down to T _c ^A =9 K). The analysis of the gap trends within the two-band Eliashberg theory shows that band filling is the main effect of Al doping, even though a small increase in interband scattering might be necessary to account for the experimental data in single crystals.     

Effect of CH4 and H2 on CVD of SiC and TiC for possible fabrication of SiC/TiC/C FGM

SiC and TiC coatings were deposited by CVD on graphite substrates and the effect of the variation of the methane (CH₄) and hydrogen (H₂) ratio on deposition was investigated. SiCl₄, TiCl₄ and CH₄ were used as sources of Si, Ti and C. In case of the SiC coatings, stoichiometric SiC was obtained when the ratios of CH₄/(SiCl₄ + CH₄)andH₂/(SiCl₄ + CH₄) are 0.4 and 10, respectively. Stoichiometric TiC was also obtained under similar conditions. In order to obtain non-stoichiometric materials for possible fabrication of functionally gradient materials (FGM), a change of microstructure and composition was observed with changes of the CH₄ and H₂ ratio. As a result, SiC, TiC and C contents were more easily controlled by a change of the H₂ ratio compared to the CH₄ ratio for SiC and TiC deposition. It has been verified that the change of the H₂ ratio is more desirable for possible manufacturing of SiC/TiC/C FGM.     

Fabrication of Bulk Targets of MgB2 with Stoichiometric and Nonstoichiometric Contents

Powder of magnesium diboride was obtained by solid phase reaction of mixture of magnesium （〉 99% pure） and amorphous boron （〉 99% pure） powders at 650-900 ℃ temperatures in inert atmosphere. During synthesis process main attention was paid. to removing oxide layer of surfaces of powder particles by organic solvents in Glovebox, where concentration of oxygen and water steam is less than 5 ppm. Homogenization and activation of powders were conducted in a planetary nano-mill by WC balls in an inert area. Pressing of the obtained powders was conducted in an argon atmosphere. MgB2 nonstoichiometric powders contained excess boron and magnesium, Magnesium hydride was used as source of excess boron, which is fragile compound and easy to grind in nano-mill. It decomposites with metallic magnesium and hydrogen up to 280 ℃ temperature. Commercial magnesium diboride powder （Aldrich, 〉 99%） was used for fabrication of MgB2 bulk targets. Powders systems of MgB2-Mg, MgB2-MgH2, MgB2-B homogenized by nano-mill in Glove box was used for fabrication of composites with nonstoichiometric contents. The targets were cylinders with diameters of 27-52 mm and height of 5-15 mm. Consolidation of pressed powdery composites was conducted in argon atmosphere. Synthesis of MgB2 from mixture of magnesium and amorphous boron powders and simultaneous consolidation were conducted by hot pressing （HP） method. Phase content of the obtained targets were established by XRD method after dry polishing. Superconducting characteristic of the obtained samples were measured by vibrational magnetometer. The superconducting transition with an onset at 39 K was observed in a good agreement with the results of the other groups obtained on samples prepared by conventional techniques. The phase exists near the nominal composition without a significant homogeneity range.     

泡沫碳化硅陶瓷的导电性能

采用高分子热解和反应烧结方法制备出泡沫碳化硅陶瓷，研究了泡沫碳化硅陶瓷的体积分数变化和钛的掺杂对泡沫碳化硅陶瓷骨架导电性能的影响．结果表明：随着泡沫碳化硅陶瓷的体积分数提高，泡沫碳化硅陶瓷的电阻率降低，这是泡沫碳化硅陶瓷筋中部碳化硅的面积增加所引起的；掺杂的钛转变成TiSi2导电相改善了泡沫碳化硅陶瓷的导电性能．TiSi2呈现离散和团聚两种形态分布，以不规则的形状位于碳化硅晶界之间，在碳化硅中作为施主杂质．泡沫碳化硅陶瓷表现出的正或负温度系数取决与掺杂的钛量的多少．     

Structure and superconducting properties of pure and variously doped bulk MgB2 obtained by uniaxial and isostatic hot pressing

The preparation of dense MgB₂ bodies, undoped and doped with different atomic species (Na, Ag, Y), was performed via reactive sintering by uniaxial and isostatic hot pressing, starting from the pure elements, and compared with undoped samples obtained by commercial MgB₂ powder. The superconducting characteristics of the obtained materials, namely critical temperature (T_c) and current (J_c), were obtained through ac susceptibility measurements and compared to their structural features, like phase purity and secondary phases formation and distribution in the MgB₂ matrix. Both the adopted hot pressing techniques gave rise to undoped MgB₂ pieces exhibiting phase purity in the range 85–95% and relative density above 80%; although in most cases the doped samples underwent higher extents of phase decomposition and lesser densification, they all exhibited higher critical temperature and current compared to the corresponding undoped material, indicating a net influence of the doping on the superconducting behaviour of MgB₂, particularly Ag and Y. An opportune quality factor was adopted, to obtain a more reliable comparison between the different MgB₂ samples and evaluation of the samples goodness, in relation to their superconducting characteristics. It was put in evidence that low amounts of doping can improve the superconducting behaviour of MgB₂ and that this influence can be addressed in terms of pinning centres, as there was no experimental evidence of an actual atomic substitutions in the MgB₂ crystal.     

The effects of annealing temperature on the in-field Jc and surface pinning in silicone oil doped MgB2 bulks and wires

The effects of sintering temperature on the lattice parameters, full width at half maximum (FWHM), strain, critical temperature (T_c), critical current density (J_c), irreversibility field (H_irr), upper critical field (H_c2), and resistivity (ρ) of 10 wt.% silicone oil doped MgB₂ bulk and wire samples are investigated in state of the art by this article. The a-lattice parameter of the silicone oil doped samples which were sintered at different temperatures was drastically reduced from 3.0864 Å to 3.0745 Å, compared to the un-doped samples, which indicates the substitution of the carbon (C) into the boron sites. It was found that sintered samples at the low temperature of 600 °C shows more lattice distortion by more C-substitution and higher strain, lower T_c, higher impurity scattering, and enhancement of both magnetic J_c and H_c2, compared to those sintered samples at high temperatures. The flux pinning mechanism has been analyzed based on the extended normalized pinning force density f_p = F_p/F_p,max scaled with b = B/B_max. Results show that surface pinning is the dominant pinning mechanism for the doped sample sintered at the low temperature of 600 °C, while point pinning is dominant for the un-doped sample. The powder in tube (PIT) MgB₂ wire was also fabricated by using of this liquid doping and found that both transport J_c and n-factor increased which proves this cheap and abundant silicone oil doping can be a good candidate for industrial application.