固相法和共沉淀法制备La2/3Sr1/3MnO3∶Agx多晶材料性能比较

分别采用固相法和共沉淀法工艺制备了不同Ag掺杂量的La2/3Sru3MnO3∶ Agx(LSMO∶ Agx,x为摩尔百分比,x=0.00、0.10、0.20、0.30、0.40)多晶材料,通过XRD和R-T对Lav2/3Sr1/3MnO3∶ Agx材料的结构和性能进行测试分析.XRD分析结果表明,系列样品为正交菱面体结构,没有出现Ag元素的峰,这与Ag在高温烧结时的挥发有关;随着组分x的增加,固相法系列样品晶胞体积呈无规律膨胀,而共沉淀系列样品晶胞体积呈增大趋势,这可能是由于固相法系列样品的粒径较大且不均匀,导致LSMO:Agx晶格有较多的缺陷使晶胞体积发生膨胀,而共沉淀系列样品的粒径较小且均匀,Ag+进入晶格替代Ag位的La3+或Sr2+,引起晶胞体积发生微小膨胀.R-T分析结果表明,相对于同一组分x,共沉淀比固相法系列样品有更低的电阻率及更高的TCR值,Ag掺杂能有效改善LSMO材料的电阻率及TCR;共沉淀系列样品Ag掺杂对LSMO材料电阻率及TCR调制作用更明显.     

La_(2/3)Ba_(1/3)MnO_3∶Ag_x多晶靶材制备及其性能

采用化学共沉淀法制备了不同Ag掺杂量的La2/3Ba1/3MnO3∶Agx(x为摩尔分数,x=0.00、0.02、0.08、0.10、0.20)多晶靶材,通过XRD、SEM和R-T对La2/3Ba1/3MnO3∶Agx靶材的结构和性能进行测试分析,实验结果表明:所得样品为正交晶系钙钛矿结构;掺Ag(x=0.02、0.08、0.10、0.20)样品比未掺Ag样品的金属-绝缘转变温度Tp值低;随着烧结温度和Ag掺杂量的升高,金属-绝缘转变温度Tp随之增加;随着Ag掺杂量增加,电阻率归一化值先增大后减小。La、Ba、Mn元素的摩尔分数与理论设计的数值基本相同,O元素在烧结过程中缺失较严重,Ag元素的摩尔分数也较低,这与Ag在高温烧结时的挥发有关。     

La0.75Ca0.25MnO3多晶陶瓷与外延薄膜的结构和电学性能研究

采用溶胶-凝胶法制备了La0.75Ca0.25MnO3多晶靶材,并用紫外脉冲激光沉积法(PLD)在LaAlO3(100)单晶衬底上制备了La0.75Ca0.25MnO3外延薄膜。采用XRD测试了薄膜的晶体结构和生长取向,测试了薄膜(200)衍射峰摇摆曲线并分析了薄膜的结晶质量。利用原子力显微镜(AFM)表征了薄膜表面形貌,并利用四探针法测试了薄膜的电阻-温度(R-T)曲线。实验结果显示薄膜结晶质量较好,并沿c轴择优生长,且生长方式为层状生长。薄膜的绝缘体-金属转变温度(TIM)达到270 K以上,电阻温度系数(TCR)高达10%。     

稀土空位锰氧化物(La(1-x-y)Yy)2/3Ca1/3MnO3的磁热效应

采用固相反应法制备La(1.x)2/3Ca1/3MnO3(x=0.0,0.04)和(La0.7Y0.3)2/3Ca1/3MnO3系列样品,测量不同温度下的磁化强度-磁场曲线,计算样品的磁熵变,研究La空位掺杂和Y3 离子掺杂对磁热效应的影响.结果表明,La空位掺杂(x=0.04)的样品在居里温度附近磁熵变最大值为6.22 J/(kg.K),这比La2/3Ca1/3MnO3磁熵变最大值(6.26 J/(kg.K))稍有降低;而Y3 离子掺杂的样品在温度60 K时和磁场强度2 T下,其磁熵变最大值为0.568 J/(kg.K),并且磁熵变随温度变化有继续增大的趋势.这表明(La0.7Y0.3)2/3Ca1/3MnO3可以作为一定温区的磁致冷材料.     

La0.7Ca0.3MnO3薄膜的微结构研究

利用ＴＥＭ研究了脉冲激光法（ＰＬＤ）制备的外延生长Ｌａ０．７Ｃａ０．３ＭｎＯ３薄膜的显微结构。结果表明，在近衬底处薄膜具有单一取向，随薄膜礅度增加，出现大量的微畴结构，此外，结合衍射与高分辨像（ＨＲＥＭ）观察确定了薄膜的结构不同于体材料的正交结构，而是具有单斜结构。     

Structure and transport properties of （La1-x-yYy）2/3Cal/3MnO3 with La-site vacancies

Several samples of manganese oxides La（1-x）2/3Cal/3MnO3 （V-LCMO） and （La0.7-xY0.3）2/3Cal/3MnO3 （x〈0.15） （V-LYCMO） with vacancies at La-site （La-vacancy） were prepared by solid-state reaction method. The X-ray diffraction（XRD） patterns refined by Rietveld confirm that these compounds exhibit single phase structure with orthorhombic symmetry （Pnma）. The lattice parameters, Mn-O bond length and Mn—O—Mn bond angle vary with La-vacancy concentration, as an indication of the occurrence of the local Jahn-Teller effect. The measurement result of V-LCMO compounds shows that the maximum magnetoresistance（MR） is about 220% at TIM=268 K and La-vacancy content x=0.04. For V-LYCMO compounds, there exists metal-insulator transition at about 50 K, and a very large MR （over 106%） is observed at the temperature ranging from 40 K to 50 K.     

颗粒尺寸对多晶La2／3Ca1／3Mn1-xCuxO3低场磁电阻的影响

采用溶胶-凝胶法制备了不同颗粒尺寸的La2/3Ca1/33Mn1-xCuxO3(x=0.04)系列试样。X射线衍射实验说明Cu掺杂和不同温度烧结没有改变晶体的结构。电阻-温度实验曲线表明，随颗粒尺寸的减少，半导体-金属转变温度（Tp）向低温方向移动。磁电阻曲线显示，随颗粒尺寸的减少，与颗粒晶界有关的磁电阻在25K恒温、0.4T低场下由25%增加到了51%。实验结果表明，在La2/3Ca1/3MnO3中少量Cu掺杂和小颗粒尺寸可以实质性地提高与颗粒晶界有关的低场磁电阻效应。     

La、Ba的添加对Pd/Y2O3-ZrO2催化氧化CH4性能的影响

以浸渍法制备了1.0%Pd/Y2O3-ZrO2催化剂,考察了Pd负载过程中La和Ba的添加对Pd/Y-ZrO2催化氧化CH4性能的影响,用BET、XRD、CO脉冲、TEM和H2-TPR等方法对所制备的催化剂进行表征。结果表明,La和Ba的添加降低了Pd/Y2O3-ZrO2催化剂氧化CH4的活性。催化剂中活性金属的分散度及体相PdO的还原性影响催化剂对CH4的氧化活性,La、Ba的添加降低了Pd/Y2O3-ZrO2催化剂中活性金属Pd的分散性,使Pd在高温老化后更容易团聚,同时增强了PdO与载体的相互作用,使PdO不容易被还原。     

油酸对化学共沉淀法制备La0.7（Ca0．53Sr0．47）0.3MnO3多晶的电阻温度系数的影响

研究了化学共沉淀法制备La0.7(Ca0.53Sr0.47)0.3MnO3多晶过程中添加油酸作分散剂的工艺,用DTG/TA、XRD和R-T(电阻-温度)系统测试了所制样品的性能.结果表明:添加油酸,共沉淀法制备La0.7(Ca0.53Sr0.47)0.3MnO3多晶比不添加的烧结温度低,也比同相反应法低.油酸的用量为0.1～O.2L/mol能明显提高La0.7(Ca0.53Sr0.47)0.3MnO3的电阻一温度转变点和电阻温度系数.     

固相法制备La2/3Sr1/3MnO3∶Agx多晶材料及其性能研究

采用固相法合成制备La2/3Sr1/3MnO3∶Agx(LSMO∶Agx,其中x为Ag掺杂量的摩尔比,x=0.00、0.10、0.20、0.30、0.40)多晶材料.通过X射线衍射和R-T对LSMO∶Agx材料的结构和性能进行测试分析.结果表明:La2/3Sr1/3MnO3∶Agx(x=0.00,0.10,0.20,0.30,0.40)多晶样品,x=0.00样品研磨后的粉体粒度D50=6.66 μm,所有样品都具有正交菱面体结构,没有出现Ag元素的衍射峰,这与Ag在高温烧结时的挥发有关;随着Ag掺杂量从x=0.00增加到x=0.40,样品的晶胞体积在348.6～350.6(A),说明Ag并没有有效替位掺杂,主要以晶界析出为主;随着Ag掺杂量的增加,电阻率归一化值随之下降,样品电阻率降低;LSMO∶Agx多晶材料Tp值在253～298K,且随组分增加呈上升趋势.     

Elastic behavior of La0.67Ca0.33MnO3:ZrO2 composites

A series of Colossal Magneto Resistance materials, with compositional formula (1 − x) La_0.67Ca_0.33MnO₃ + xZrO₂ (where x = 0%, 10%, 20%, 40%, 60%, 80%) were prepared by sol–gel technique. When characterized structurally by X-ray diffraction they are found to have cubic structure. After measuring their bulk densities, the ultra sonic longitudinal (V_l) and shear velocities (V_s) were measured at room temperature using the pulse transmission technique. Using the ultrasonic data, the values of Young's and rigidity moduli along with Poisson's ratio and Debye temperatures have been calculated. As the materials are porous, zero porous elastic moduli have also been arrived at using a well-known model. The observed variation of elastic moduli with varying ZrO₂ concentration has been explained qualitatively.     

Magnetic held dependence of elastic modulus and resistance in La2/3Ca1/3MnO3

We have measured the magnetic field dependence of the anelastic modulus and the electric resistance of a ceramic sample of the magnetoresistant perovskite La_2/3Ca_1/3MnO₃ around the metal–insulator transition by the vibrating reed technique (2.5 KHz). Previous work [1] showed that the modulus becomes higher while the internal friction has a peak at the transition temperature (T_c=262 K). In this work, improvements made on the equipment allowed us to measure at constant deformations (<10⁻⁵) and magnetic fields up to 4500 Gauss. We made isothermal measurements of internal friction, modulus and resistance as a function of an applied magnetic field. We found that most of the changes induced by the magnetic field take place in a few degrees (almost 5 K) near the transition temperature where the changes in resistance are more important. Up to the highest magnetic field applied, we found 3% maximum variations of the modulus and no hysteresis while cycling the magnetic field. We suppose that the experiment is placed in the linear response of the inverse Wiedemann effect [2], due to the small deformations used, and that the ferromagnetic domain structure is responsible for the observed effects. Some additional measurements are needed (magnetic hysteresis loops) to be compared with our results.     

Size effects and interactions in La0.7Ca0.3MnO3 nanoparticles

La_0.7Ca_0.3MnO₃ (LCMO) nanoparticles with average diameter of 16-73 nm were prepared by reactive milling and thermal processing methods. Interaction and size effects on the magnetic properties of the LCMO nanoparticle samples were investigated. Phenomena related to the interparticle interaction, such as an un-overlapping of the M(H_ext,T)/M_S vs. H_ext/T scaling plots and a Curie-Weiss rather than Curie law behavior of the dc susceptibility at high temperatures were analyzed. The magnetization curves of interacting nanoparticles were well described by using the mean-field approximation. The dependence of the blocking temperature T_B on the strength of the interactions, magnetic anisotropy, as well as the thermal dependence of magnetization deviates from the expected Bloch law was also estimated.     

Magnetic and electrical transport properties of nanostructured La0.67Ca0.33MnO3 networks

Contiguously nanostructured networks of La_0.67Ca_0.33MnO₃ (LCMO) are fabricated successfully by pulsed electron deposition (PED) onto the surface of porous anodic alumina oxide (AAO). The Curie temperature (T_C) is about 250 K. The metal–insulator transition temperature (T_p) is about 145 K without the magnetic field. The magnetoresistance can reach 84% near the peak temperature, which suggesting a strong magnetic correlated electronic transportation process. Zero field cooling (ZFC) and field cooling (FC) are split below the paramagnetic–ferromagnetic transition. The ZFC curves exhibit a typical blocking process. The observed spin glass and weak localization phenomena are due to the size effect, and it is found that the resistance dependent temperature curve above metal–insulator transition temperature (T_p) is more suitable to small polaron hopping (SPH) model.     

Studies on La0.67Ca0.33MnO3-SrTiO3 composites using two-phase model

In this study we report the structural, electrical and magnetic properties of (1 − x)La_0.67Ca_0.33MnO₃ (LCMO)-(x)SrTiO₃(STO) composites. For this series we have observed a minute change in ferromagnetic (FM)-paramagnetic (PM) transition temperature with STO addition in LCMO matrix; however a reasonable change is observed in metal-insulator transition temperature, along with the occurrence of percolation threshold for x = 0.30 sample. Overall pattern for temperature dependence of resistivity for this series has been best-fitted using the formula 1/ρ = (1 − f)/ρ_PM + (f/ρ_FM), whereρ_PM and ρ_FM are the resistivities of the PM and FM contents in the sample and f is the volume fraction of FM phase in the sample. Investigations on magnetoresistance (MR) using magnetic field up to 3 T show enhancement of extrinsic MR in the composite samples which can be viewed in the light of spin polarized tunneling.     

A-site-disorder-dependent magnetocaloric properties in the mono-valent-metal doped La0.7Ca0.3MnO3 manganites

The influence of mono-valence-metal (Li, Na, and K) doping effect on the structural, resistivity, magnetic and magnetocaloric properties of La_0.7Ca_0.3MnO₃ polycrystalline samples is studied for a fixed (5% at Ca site) dopant concentration. All the samples crystallize in orthorhombic structure and the lattice parameters increase continuously as the dopant atoms changes from Li to Na and then K. Paramagnetic-ferromagnetic phase transition at T_C and insulator-metal phase transition at T_p are observed for all studied samples. The transition temperature decreases as Ca atoms is replaced by Li, while the transition temperature shifts to higher values as Ca is substituted by Na or K. In addition, the maximum magnetic entropy change of the K-doped sample is much smaller than that of the free- and Na-doped samples. The results are discussed according to the change of A-site-disorder effect caused by the systematic variations of A-site average ionic radius 〈r_A〉 and A-site-cation mismatch σ².     

La1-xKxMnO3的微波吸收特性

用溶胶-凝胶法制备La1-xKxMnO3粉晶,用X射线衍射仪和扫描电镜表征样品的晶体结构和微观形貌,用微波矢量网络分析仪测试了该样品在2~18 GHz微波频率范围的复介电常数和复磁导率,并计算损耗角正切及微波反射率,分析K掺杂量和样品厚度对体系微波吸收性能的影响及微波损耗机制。结果表明:晶体结构为钙钛矿型,颗粒形貌为不规则椭球状或短棒状;当样品厚度为2.40 mm、x=0.3时,吸收峰值为27.1 dB,10 dB以上有效吸收频带宽度达10.6 GHz。纳米La1-xKxMnO3兼具介电损耗和磁损耗,介电损耗相对较强。磁损耗因子和介电损耗因子随微波频率的变化相反,是基体中铁磁与反铁磁团簇在微波电磁场作用下相互转变引起。     

溶胶-凝胶法制备La1-xSrxMnO3及其电磁性能研究

采用溶胶凝胶法,制备了La_1-xSr_xMnO₃(LSMO)纳米微粉。探究了Sr^₂₊的掺杂量对LSMO晶体结构、磁学性质、电磁特性和微波吸收性能的影响。结果表明,随Sr^₂₊含量的升高,样品的晶格常数和Mn-O-Mn键角增大,平均晶粒尺寸逐渐下降,样品出现从反铁磁性向铁磁性的转变,复介电常数呈先增大后减小的趋势。在2~18GHz内,x=0的样品在厚度为2mm时有最佳吸波效果,反射率小于-10dB对应的有效吸波频段为12.5~18GHz;Sr^₂₊的掺杂可使吸波频段有效的向低频移动,在X波段内,x=0.2的样品在厚度为2.3mm时的有效带宽达2.6GHz,证明LSMO是一种性能优异的介电损耗型吸波材料。     

SiO_2含量对激光熔覆含La_2O_3生物陶瓷涂层性能的影响

采用激光熔覆技术,利用CaHPO_4·2H_2O,CaCO_3,La_2O_3,SiO_2粉末和Ti粉在医用钛合金Ti-6Al-4V表面制备掺杂的质量分数分别为0%,5%,10%,15%SiO2的含La2O3梯度生物陶瓷涂层,并研究了SiO_2含量对涂层性能的影响。利用金相显微镜、扫描电镜、能谱仪、X射线分析仪分别对涂层进行显微结构、表面元素、物相组成分析,利用MTT细胞活性检测法对涂层上种植的小鼠破骨前体细胞(RAW264.7)进行细胞活性分析。结果显示:掺杂10%~15%的SiO_2后,涂层的裂纹明显减少,且厚度变均匀。涂层在模拟体液(SBF)中浸泡2周后,羟基磷灰石(HA)在掺杂10%SiO_2涂层表面的沉积量最多,涂层表面的金属元素含量稀少,这表明含10%SiO_2涂层在SBF中具备更加优良的沉积HA的能力,同时有效的阻碍了基体中重金属离子的析出。MTT结果表明,掺杂SiO_2的涂层对破骨前体细胞的活性有更加明显的抑制作用。     

Post annealing effect on transport properties of La0.67Ca0.33MnO3 films grown on vicinal cut substrates

La_0.67Ca_0.33MnO₃ thin films have been grown on 10°, 15°, and 20° vicinal cut SrTiO₃ (1 0 0) substrates by pulse laser deposition. The single phase and the least textured growth have been studied by X-ray diffraction analysis. The post annealing effect with high temperature and high oxygen pressure on the transport properties of films has been investigated by resistance versus temperature measurements. Films with post annealing show large enhancement of metal-insulator transition temperature T_p about 20-30 K towards higher temperature and obvious decrease of resistance, which is attributed to the refilling of oxygen, the change of Mn-O-Mn angle and the improvement of crystallinity by the post annealing effect. Specially, film on 20° vicinal cut substrate exhibits the biggest range gap of peak resistance drop, which may originate from more defects caused by steps at this tilt angle and many of these defects are removed after post annealing.