基于广义逆理论的步进应力加速寿命试验的最优设计

步进应力加速寿命试验的最优设计问题早在20世纪60年代就已提出.本文在应力个数和未知参数个数不相等的情况下,以MLE渐近方差最小为准则,运用广义加号逆的理论,解决指数分布时定数截尾寿命试验和定时截尾寿命试验的最优设计问题.通过理论推导,得出定数截尾寿命试验时的不同应力下失效产品数的安排,以及定时截尾寿命试验时的最优应力变换点.并且,对每一种情况进行了数据模拟,结果显示,这些理论和方法在实际运用中是可行的和有效的.     

一种对钯催化剂有害杂质的光谱鉴定

乙二醛和苄胺在甲酸的催化作用下,可以合成六苄基六氮杂异伍兹烷(HBIW),但是产物中含有的少量杂质会对HBIW氢解脱苄时使用的钯催化剂产生危害,致使氢解产率降低或失败.采用多次重结晶的方法提取了HBIW中的杂质,用常压制备色谱分离得到一种主要杂质晶体;应用FTIR,1H-NMR,ESI-MS,元素分析等方法分析鉴定了该杂质是N,N'-草酰二苄胺;按文献中的方法合成了N,N'-草酰二苄胺,用FTIR,1H-NMR,EI-MS进行了表征,其光谱分析图谱与分离杂质一致;在钯催化的HBIW氢解脱苄反应体系中,当加入其量的0.9%合成的N,N'-草酰二苄胺时钯催化剂将完全失效.     

典型磁性材料价电子结构研究面临的机遇与挑战

目前在磁性材料磁有序现象研究中广泛使用的交换作用、超交换作用和双交换作用模型形成于1950年代及其以前,这些模型都涉及材料中的价电子状态,但那时还没有充分的价电子状态实验依据.1970年代以来,有关价电子结构实验结果的报道越来越多,这些实验结果表明传统的磁有序模型需要改进.首先,大量电子谱实验表明,在氧化物中除存在负二价氧离子之外,还存在负一价氧离子,并且负一价氧离子的含量可达30%或更多.这说明以所有氧离子都是负二价离子为基本假设的超交换和双交换作用模型需要改进.其次,一些实验证明,铁、钴、镍自由原子的一部分4s电子在形成铁磁性金属的过程中变成了3d电子,这为探讨金属磁性与电输运性质的关系提供了依据.此外,即使在现代的密度泛函计算中,仍不能给出磁性交换作用能的函数表达式,只能采取各种不同模型进行模拟计算,从而使磁性材料的模拟计算遇到严重困难.寻求一个磁有序能的函数表达式可能是解决这个困难的途径.这些研究表明磁性材料价电子结构研究面临着重大的机遇与挑战.本文首先介绍一些典型的实验例证,然后介绍了基于这些实验结果的一套典型磁性材料的磁有序新模型,随后介绍了基于新模型的磁性材料价电子结构与旧模型的主要区别,最后指出了未来研究工作面临的挑战.     

Composition design for (PrNd-La-Ce)_2Fe_(14)B melt-spun magnets by machine learning technique

Data-driven technique is a powerful and efficient tool for guiding materials design,which could supply as an alternative to trial-and-error experiments.In order to accelerate composition design for low-cost rare-earth permanent magnets,an approach using composition to estimate coercivity(H_(cj)) and maximum magnetic energy product(BH)_(max) via machine learning has been applied to(PrNd–La–Ce)_2Fe_(14)B melt-spun magnets.A set of machine learning algorithms are employed to build property prediction models,in which the algorithm of Gradient Boosted Regression Trees is the best for predicting both H_(cj) and(BH)_(max),with high accuracies of R~2= 0.88 and 0.89,respectively.Using the best models,predicted datasets of H_(cj) or(BH)max in high-dimensional composition space can be constructed.Exploring these virtual datasets could provide efficient guidance for materials design,and facilitate the composition optimization of 2:14:1 structure melt-spun magnets.Combined with magnets' cost performance,the candidate cost-effective magnets with targeted properties can also be accurately and rapidly identified.Such data analytics,which involves property prediction and composition design,is of great time-saving and economical significance for the development and application of La Ce-containing melt-spun magnets.     

Machine learning technique for prediction of magnetocaloric effect in La(Fe,Si/Al)_(13)-based materials

Data-mining techniques using machine learning are powerful and efficient for materials design, possessing great potential for discovering new materials with good characteristics. Here, this technique has been used on composition design for La(Fe,Si/Al)_(13)-based materials, which are regarded as one of the most promising magnetic refrigerants in practice. Three prediction models are built by using a machine learning algorithm called gradient boosting regression tree(GBRT) to essentially find the correlation between the Curie temperature(T_C), maximum value of magnetic entropy change((?S_M)_(max)),and chemical composition, all of which yield high accuracy in the prediction of T_C and(?SM)_(max). The performance metric coefficient scores of determination(R~2) for the three models are 0.96, 0.87, and 0.91. These results suggest that all of the models are well-developed predictive models on the challenging issue of generalization ability for untrained data, which can not only provide us with suggestions for real experiments but also help us gain physical insights to find proper composition for further magnetic refrigeration applications.     

Ce2Fe16Al化合物在居里温度附近的磁性和磁熵变

研究了具有菱方Th2Zn17型结构的Ce2Fe16Al化合物在居里温度TC附近的磁性和磁熵变.实验结果表明，在居里温度附近样品的磁特性符合二级相变规律，样品的居里温度为2758K.通过磁化强度与磁场和温度关系的测量，计算出临界指数β=044±001，γ=130±001，δ＝383±001，临界指数β，γ，δ基本满足标度率方程γ＝β（δ-1)，但偏离三维Heisenberg模型的理论值.Ce2Fe16Al化合物的磁熵变在居里温度处达到峰值，2T外磁场下的最大磁熵变为195J/kg K. 关键词： Ce2Fe16Al化合物 临界指数 磁熵变     

非晶态Co_(70)Cr_(20)Zr_(10)合金在居里温度附近的磁性

本文研究非晶态Co_(70)Cr_(20)Zr(10)合金在居里温度附近的磁性,样品的磁特性符合二级相变规律。得到临界指数β=0.45±0.02,γ=1.9±0.1,δ=5.13±0.05。Co_(70)Cr_(20)Zr_(10)合金的居里温度为Tc=(186.7±0.2)K。临界指数β,γ,δ满足γ=β(δ-1)关系,但临界指数值都偏离三维Heisenberg模型的理论值,这种行为可能起源于非晶态合金磁的不均匀性。讨论了Kouvel-Fisher(K-F)参数γ(T)对温度T的依赖关系。     

磁热效应材料的研究进展

磁制冷技术的发展取决于具有大磁热效应磁制冷材料的研发进展.经过长期的工作积累,特别是近20年来的努力,许多新型磁制冷材料的探索和研究极大地促进了磁制冷技术的进步.本文介绍了磁热效应的基本原理和磁制冷研究的发展历史,系统综述了低温区和室温区具有大磁热效应的磁制冷材料的研究进展,重点介绍了一些受到较为关注的磁热效应材料的最新研究成果.低温区磁制冷材料主要包括具有低温相变的二元稀土基金属间化合物(RGa,RNi,RZn,RSi,R_3Co以及R_(12)Co_7)、稀土-过渡金属-主族金属三元化合物(RTSi,RTAl,RT_2Si_2,RCo_2B_2,RCo_3B_2)以及四元化合物RT_2B_2C等,其中R代表稀土元素,T代表过渡金属.这些材料一般都具有二级相变,具有良好的热、磁可逆性,也因其合金属性具有良好的导热性.室温区磁制冷材料主要包括Gd-Si-Ge,La-Fe-Si,Mn As基,Mn基Husler合金,Mn基反钙钛矿,Mn-Co-Ge,Fe-Rh以及钙钛矿氧化物等系列.这些材料一般都具有一级相变,多数在室温具有巨大的磁热效应而受到国内外的极大关注.其中,La-Fe-Si系列是国际上普遍认为具有重要应用前景的磁制冷工质之一,也是我国具有自主知识产权的材料.本文还对磁制冷材料的发展方向进行了展望.     

Magnetic entropy change involving martensitic transition in NiMn-based Heusler alloys

Our recent progress on magnetic entropy change (ΔS) involving martensitic transition in both conventional and metamagnetic NiMn-based Heusler alloys is reviewed. For the conventional alloys, where both martensite and austenite exhibit ferromagnetic (FM) behavior but show differentmagnetic anisotropies, a positive ΔS as large as 4.1 J·kg^-1·K^-1 under a field change of 0–0.9 T was first observed at martensitic transition temperature T_M ~ 197 K. Through adjusting the Ni:Mn:Ga ratio to affect valence electron concentration e/a, T_M was successfully tuned to room temperature, and a large negative ΔS was observed in a single crystal. The -ΔS attained 18.0 J·kg-1·K-1 under a field change of 0–5 T. We also focused on the metamagnetic alloys that show mechanisms different from the conventional ones. It was found that post-annealing in suitable conditions or introducing interstitial H atoms can shift the T_M across a wide temperature range while retaining the strong metamagnetic behavior, and hence, retaining large magnetocaloric effect (MCE) and magnetoresistance (MR). The melt-spun technique can disorder atoms and make the ribbons display a B2 structure, but the metamagnetic behavior, as well as the MCE, becomes weak due to the enhanced saturated magnetization of martensites. We also studied the effect of Fe/Co co-doping in Ni₄₅(Co_1-xFe_x)5Mn36.6In13.4 metamagnetic alloys. Introduction of Fe atoms can assist the conversion of the Mn–Mn coupling from antiferromagnetic to ferromagnetic, thus maintaining the strong metamagnetic behavior and large MCE and MR. Furthermore, a small thermal hysteresis but significant magnetic hysteresis was observed around T_M in Ni₅₁Mn_49-xIn_x metamagnetic systems, which must be related to different nucleation mechanisms of structural transition under different external perturbations.     

Magnetic properties and magnetocaloric effects in NaZn13-type La（Fe, Al）13-based compounds

In this article,our recent progress concerning the effects of atomic substitution,magnetic field,and temperature on the magnetic and magnetocaloric properties of the LaFe13-xAlx compounds are reviewed.With an increase of the aluminum content,the compounds exhibit successively an antiferromagnetic(AFM) state,a ferromagnetic(FM) state,and a mictomagnetic state.Furthermore,the AFM coupling of LaFe 13-xAlx can be converted to an FM one by substituting Si for Al,Co for Fe,and magnetic rare-earth R for La,or introducing interstitial C or H atoms.However,low doping levels lead to FM clusters embedded in an AFM matrix,and the resultant compounds can undergo,under appropriate applied fields,first an AFM-FM and then an FM-AFM phase transition while heated,with significant magnetic relaxation in the vicinity of the transition temperature.The Curie temperature of LaFe13-xAlx can be shifted to room temperature by choosing appropriate contents of Co,C,or H,and a strong magnetocaloric effect can be obtained around the transition temperature.For example,for the LaFe 11.5Al1.5C0.2H1.0 compound,the maximal entropy change reaches 13.8 J·kg-1 ·K-1 for a field change of 0-5 T,occurring around room temperature.It is 42% higher than that of Gd,and therefore,this compound is a promising room-temperature magnetic refrigerant.