Gd0.6Tb0.4-xCox合金的磁热效应研究

研究了Gd0．6Tb0．4-xCox系列稀土合金在261～290K温区范围的磁熵变,发现这种合金具有较大的磁熵变值,适合作为中低磁场(1～2T)下的室温磁制冷材料。     

通过拟合磁化强度函数计算磁熵变

用振动样品磁强计测量DyCo2化合物的磁化曲线,采用二元函数在矩形区域的双一次插值逼近拟合出M (T, H )的二元函数表达式,然后根据磁熵变的热力学公式,计算出它的磁熵变值。通过计算得到DyCo2合金的居里温度为142 K,在外磁场变化为1 T时,最大磁熵变为5.45 J/kg·K,因而DyCo2合金是良好的磁制冷材料。计算结果表明这种计算磁熵变的方法可行,能够得到比较准确的结果。     

GdDyFe、GdTbFe合金的磁熵研究

研究了Gd0.5Td0.5-xFex,Gd0.5Dy0.5-yFey(x=0.1,0.2,0.3,0.4；y=0.1,0.2,0.3,0.4)系列稀土合金在245～320K温区范围的磁熵变，发现这二种系列合金均具有较大的磁熵变值，适合作为中等磁场（1～2T）下的室温磁制冷材料。     

Sr掺杂对La_（0.77-x）Ca_（0.2）Sr_xMnO_3系列材料的相结构和居里温度的影响

以存在La空位的钙钛矿材料La0.77Ca0.2MnO3为母体,用溶胶-凝胶法制备了La0.77-xCa0.2SrxMnO3（x=0.00,0.02,0.06,0.08,0.10）系列样品,研究表明,该系列材料均为单相钙钛矿结构,且随Sr2＋含量的增加,该系列材料的晶格发生畸变,同时居里温度单调递增,由236K增高至300K,覆盖整个室温区,这对材料的实际应用有重要意义。     

通过拟合磁化强度函数计算磁熵变

用振动样品磁强计测量DyCo2化合物的磁化曲线,采用二元函数在矩形区域的双一次插值逼近拟合出M（T,H）的二元函数表达式,然后根据磁熵变的热力学公式,计算出它的磁熵变值。     

Mn1.2Fe0.8P0.48Six化合物的结构和磁热效应

对Mn1.2Fe0.8P0.48Si0.52和非化学计量比Mn1.2Fe0.8P0.48Si0.49化合物的物相与磁热效应(MCE)进行了研究。结果表明:两种化合物均为Fe2P型六角结构(空间群为P-62m),化合物中含有少量的(Fe,Mn)3Si第二相。当Si的含量x由0.52降到0.49时,化合物的居里温度由268K升到282K,而Si含量的变化对化合物的热滞没有明显的影响。Mn1.2Fe0.8P0.48Si0.52和Mn1.2Fe0.8P0.48Si0.49化合物在外磁场变化为0~1.5T下的最大磁熵变分别为11.7J/kg·K和9.0J/kg·K。低成本的原料、较大的磁熵变使得Mn1.2Fe0.8P0.48Six化合物成为一种理想的室温磁致冷材料。     

LaMn2Ge2室温附近的磁相变与磁热性能

用非自耗真空电弧炉制备LaMn2Ge2合金,采用X射线衍射研究了合金的结构,LaMn2Ge2在常温下具有ThCr2Si2-型晶体结构,空间群为I4/mmm.利用振动样品磁强计测量合金的磁性能,根据升降温的磁化曲线所确定的合金发生反铁磁-铁磁相变温度有4.3 K的滞后,居里温度约320 K,具有一级相变的典型特征.通过不同温度的磁化曲线结果,计算得LaMn2Ge2在1.43×106A/m外场变化下居里温度附近的最大磁熵变为1.42 J/kg·K.     

Na^＋掺杂对钙钛矿La0．7Sr0．3-xNaxMnO3的结构及磁熵变的影响

采用溶胶-凝胶法制备了钙钛矿La0.7Sr0.3-xNa xMnO3(0.05≤x≤0.3)系列样品.结果表明:由于Na+离子半径(0.102 nm)小于Sr2+离子半径(0.127 nm),导致La0.7Sr0.3-xNaxMnO3(0.05≤x≤0.3)样品的结构随着Na+离子掺杂量的增加由正交向单斜转变.样品的晶胞参数a随x的增大而增大,而c随x的增大而减小,c/a随x的增加而减小;样品的形貌呈现不规则的颗粒状,中间还夹杂着棒状物;随着Mn4+与Mn3+摩尔比的增加,A位的平均离子半径减小及A位离子失配效应减小的共同影响下,当x≤0.2时,居里温度随着Na+离子掺杂量的增加而增加;当x＞0.2时,居里温度随着Na+离子掺杂量的增加而下降;由于Na+离子掺杂引起的容差因子的减小,晶格收缩、铁磁耦合变小,导致居里温度附近的最大磁熵变随x增加而减小.     

SPS制备Mn1.2Fe0.8P0.76Ge0.24室温磁制冷材料

利用机械合金化和放电等离子烧结技术制备Mn1.2Fe0.8P0.76Ge0.24室温磁制冷材料。采用XRD、SEM分析烧结样品的相结构和显微组织,发现烧结样品显微组织均匀致密,但是存在少量MnO、Fe3Mn4Ge6杂质相。利用DSC测试样品的热流对温度的变化曲线,并计算出熵变随温度的变化关系。结果显示,Mn1.2Fe0.8P0.76Ge0.24的居里温度TC在–10 ℃左右,在–7 ℃的时磁熵变为23 J/(kg·K)     

LaFe11.9-xCoxSi1.1B0.2(x=0.7,0.8,0.9)合金的磁热效应

使用电弧熔炼法制备了LaFe11.9-xCoxSi1.1B0.2(x=0.7,0.8,0.9)系列合金.XRD分析表明该系列合金除微量的α-Fe相外,均由NaZn13型立方结构单相组成.晶格常数随着Co含量的增加而增大,分别为1.1487,1.1496,1.1498nm;磁性测量表明该系列合金的Curie温度在室温附近,并且也随着Co含量的增加而分别增加到270,290,300 K.在外场变化△B=1.5 T时,该系列合金的最大磁熵变均为金属Gd的2倍左右,相对制冷能力与金属Gd基本相同.     

纳米氧化物La0.8Sr0.2MnO3的制备研究

用添加表面活性剂的苹果酸溶胶凝胶法制备出纳米钙钛石型氧化物La0.8Sr0.2MnO3。通过差热热失重分析,确定了氧化物的焙烧制度。XRD分析表明,所烧制的氧化物样品特征衍射峰明显,杂峰少,晶形完整,其物相为钙钛石结构。表面活性剂因其亲油基团和亲水基团与胶体粒子可以发生复杂的相互作用,形成胶束和胶团,保护了胶体粒子不长大,从而有效地减小氧化物粉料的颗粒粒径,并且在纳米材料的制备过程中能显著降低纳米微粒的表面张力,从而可防止原生粒子团聚,所以在溶胶的制备过程中添加了表面活性剂聚乙烯醇(PVA)。根据谢乐公式计算得出,添加了PVA后,氧化物粉料的粒径约为17nm。TEM分析表明,聚乙烯醇可以作为纳米氧化物粉体La0.8Sr0.2MnO3的分散剂,添加适量的PVA可使纳米粒子的团聚现象得到了明显改善。     

La_（0.85）K_（0.15）MnO_3多晶纳米颗粒磁制冷材料的制备

采用非晶态多核配合的方法在800℃制备出La0.85K0.15MnO3纳米颗粒,用XRD、HRTEM和PPMS等手段对纳米颗粒的微观结构和磁性能进行研究。XRD和ED分析表明,所有样品都具有单相钙钛矿结构;样品的M-T曲线研究结果表明,La0.85K0.15MnO3纳米颗粒的居里温度TC为242.65 K。     

Microwave absorbing properties of La0.8Ba0.2MnO3 nano-particles

La0.8Ba0.2MnO3 nano-particles were synthesized by sol-gel process, and the crystal structure and morphology＇ were characterized by XRD and SEM, respectively. The complex permittivity and permeability were determined by microwave vector network analyzer in the frequency range of 2-18 GHz. The relationship between reflection coefficient and microwave frequency of La0.8Ba0.2 MnO3 was calculated based on measured data. The results show that the average diameter of La0.8Ba0.2MnO3 crystal powders is about 80 nm and the crystal structure is perovskite when being calcined at 800 ℃ for 2 h. The microwave absorbing peak is 13 dB at 6.7 GHz and the effective absorbing bandwidth above 10 dB reaches 1.8 GHz for the sample with the thickness of 2.6 mm. The microwave absorption can be attributed to both the dielectric loss and the magnetic loss from the loss tangents of the sample, but the former is greater than the latter.     

螯合物-凝胶法制备La0.8Sr0.2MnO3粉体

以La(NO3)3·6H2O,Sr(NO3)2和Mn(NO3)3·6H2O为起始原料,采用螯合物-凝胶法制备出La0.8Sr0.2MnO3粉体.首先在混合盐溶液中入柠檬酸形成螯合的柠檬酸盐,然后加入单体和交联剂,在引发剂和催化剂的作用下形成湿凝胶.干燥后的前驱体为无定形的,DTA和XRD测试表明晶化温度在400℃～500℃.在500℃～1 200℃范围内煅烧,颗粒尺寸由500℃时的约38 nm 长大到1 200℃时的500 nm.     

Synthesis of nano-structured La0.8Ba0.2MnO3 perovskite via a mechano-thermal route

In this study, barium-doped lanthanum manganite, La_0.8Ba_0.2MnO₃, was synthesized via a mechano-thermal route employing high energy ball milling and subsequent heat treatment. The structural evolution, morphology and thermal behaviour of the powders were evaluated using XRD, FESEM, and DTA/TGA, respectively. DTA/TGA results showed that the calcination temperature of the carbonates significantly decreased by increasing the milling time. The results revealed that single phase perovskite was formed at 900 °C in a milled sample for 2 h and this temperature decreased to 600 °C by increasing the milling time to 30 h. The mean crystallite size also decreased from 32 to 20 nm by increasing the milling time from 2 to 30 h. The reaction sequence of La_0.8Ba_0.2MnO₃ formation via the mechano-thermal route is proposed using XRD and DTA/TGA results. FESEM micrographs showed that the mean particle size of the perovskite phase is increased slightly from 30 to 40 nm by increasing the heat treatment temperature from 600 to 900 °C.     

Molten salt synthesis of La0.8Sr0.2MnO3 powders for SOFC cathode electrode

For La_0.8Sr_0.2MnO₃ (LSM) perovskite, used as the cathode material for solid oxide fuel cells (SOFC), it is known that the formation of a triple-phase-boundary is restrained due to the formation of a second phase at the YSZ/electrode interface at high temperature. To decrease the 2^nd phase, lowering the sintering temperature has been used. LSM powder was synthesized by molten salt synthesis method to control its particle size, shape, and agglomeration. We have characterized the phase formation, particle size, shape, and sintering behavior of LSM in the synthesis using the variation of KCl, LiCl, KF and its mixed salts as raw materials. In the case of KCl and KCl-KF salts, the particle size and shape of the LSM was well controlled and synthesized. However, in the case of LiCl and KCl-LiCl salts, LiMnO_x as 2^nd phase and LSM were synthesized simultaneously. In the case of the mixed salt of KCl-KF, the growth mechanism of the LSM particle was changed from ‘diffusion-controlled’ to ‘reaction-controlled’ according to the amount of mixed salt. The sintering temperature can be decreased below 1000 °C by using the synthesized LSM powder.     

Gd_3Al_(2-x)Ga_x合金的磁热效应研究

以Gd3Al2作为母相,在其中少量添加Ga元素替代部分Al元素,使其形成Gd3Al2-xGax(x=0.1,x=0.2,x=0.3)系列合金,经过热处理后,通过X射线衍射、扫描电镜、振动样品磁强计测量及直接测量等方法进行研究,实验结果表明:Gd3Al2-xGax(x=0.1,x=0.2,x=0.3)系列合金的晶体结构均为Zr3Al2型,主相为Gd3Al2,还有少量的Gd2Al相和Gd Al相。当x=0.2时,Gd3Al2-xGax合金的绝热温变值为2.7 K,比Gd3Al2高0.7 K,居里温度为277 K。少量添加Ga对磁熵变的提高有一定帮助,但对提高居里温度的作用不明显。     

La0.8Sr0.2 Mn1-yFeyO3微波电磁特性与损耗机制

用溶胶凝胶法制备La0.8Sr0.2Mn1-yFeyO3(y=0.10,0.12,0.14,0.16)样品,测试并分析该样品在2~18 GHz微波频率范围的复介电常数、复磁导率、损耗角正切及微波吸收系数与频率的关系,发现y=0.12,0.14时吸波的效果最好。样品厚度为2 mm、y为0.12时,有2个吸收峰,吸收峰值最高达22 dB,10 dB以上吸收频带宽度达6.2 GHz;厚度2.21 mm样品8 dB以上的吸收频宽达8.5 GHz。初步探讨了该材料的电磁损耗机理,电磁特性参数在频率为12.4 GHz位置发生阶跃式变化,在小于12.4 GHz频率范围以介电损耗为主,在大于12.4 GHz频率范围以磁损耗为主,这与Fe对Mn3 —O—Mn4 之间的影响有关。电导率测试表明在室温范围内电导在半导体范围内,有利于降低微波在氧化物表面的反射率。     

Preparation and magnetic properties of nanosized （La0. 47Gd0. 2 ） Sr0. 33 MnO3

1INTRODUCTION Themagneticpropertyandcrystalstructureof perovskite typelanthanummanganeseoxideswere firststudiedbyJonkerandVanSantenin1950[1].Thesematerialswereofconsiderableinterestinthe lastdecadeduetotheircolossalmagnetoresistance(CMR)effect[24].Recentlyaseriesofhole dopedperovskitemanganeseoxideswerereportedtodis playalargemagnetocaloriceffect(MCE)inthevic inityoftheferromagneticCurietemperature(Tc)[516],whichmaybeexploitedtobeappliedin magneticrefrigeratorandheatpumps[17].Idealmag…