Spark plasma sintering of MgAl2O4–YCr0.5Mn0.5O3 composite NTC ceramics

New high temperature negative temperature coefficient (NTC) thermistor ceramics based on a xMgAl₂O₄–(1 − x)YCr_0.5Mn_0.5O₃ (x = 0.1, 0.4, 0.6) composite system have been successfully fabricated through spark plasma sintering (SPS) with a low sintering temperature and a short sintering period. The X-ray diffraction analysis indicates that the SPS-sintered composite ceramics consist of a cubic spinel MgAl₂O₄ phase and an orthorhombic perovskite YCr_0.5Mn_0.5O₃ phase isomorphic to YCrO₃. The SPS-sintered composite ceramics have high relative density ranging from 94.1 to 97.4% of the theoretical density. X-ray photoelectron spectroscopy analysis corroborates the presence of Cr³⁺, Cr⁴⁺, Mn³⁺, and Mn⁴⁺ ions on lattice sites, which may result in the hopping conduction. The obtained ρ₂₅, B_25–150, and B_700–1000 of the SPS-sintered composite NTC thermistors are in the range of 1.53 × 10⁶–9.92 × 10⁹ Ω cm, 3380–5172 K, and 7239–9543 K, respectively. These values can be tuned by adjusting the MgAl₂O₄ concentration.     

Influence of Bi2O3 flux in the structural and photoluminescence properties of SrAl2O4:Eu2+ phosphors

SrAl₂O₄:Eu²⁺ phosphors with various content of Bi₂O₃ flux were synthesized and analyzed. It was observed that the crystallinity and the particle size of the phosphors were increased with the addition of Bi₂O₃ flux. These phenomena are considered to be caused via the melting of the Bi₂O₃ flux particles during the synthesis of the phosphors. The melted Bi₂O₃ flux increased the mobility and homogeneity of solid reactants, thereby enhancing the photoluminescence intensity of the phosphors. SrAl₂O₄:Eu²⁺ phosphors with Bi₂O₃ as the flux exhibited a broad green emission with a peak at 520 nm. The highest photoluminescence emission intensity was observed when 5 mol% Bi₂O₃ flux was added into the phosphors. The emission is due to 4f⁶5d→4f⁷ (⁸S_7/2) transitions of the Eu²⁺ ions. Moreover, Bi₂O₃ flux extended the application of the ultraviolet excited phosphors toward the blue-light excited phosphors. Nevertheless, the influence of Bi₂O₃ on the afterglow and the emission color of SrAl₂O₄:Eu²⁺ phosphors were not significant. This research indicated that Bi₂O₃ flux is effective flux for synthesizing SrAl₂O₄:Eu²⁺ phosphors.     

Mn2+在Zn2SiO4中的发光

利用Sol-gel法制备掺Mn^2 的Zn2SiO4的前驱体，并将前躯体在弱氧化气氛下在1000℃煅烧2h，得到掺Mn^2 的Zn2SiO4试样。X射线衍射分析确定试样为α-Zn2SiO4晶相。荧光分析测定试样的激发光谱和发射光谱。结果显示Mn^2 掺杂的α-Zn2SiO4可发蓝色和绿色荧光，这一结果显然不同于以前的文献报道。同时，我们讨论了Mn^2 在Zn2SiO4中产生这一新型发光性质的机理。     

Mn掺杂BaTi4O9陶瓷结构和介电性能

用电子陶瓷工艺制备主晶相为BaTiO9(BT4)的介电陶瓷,研究用锰掺杂的BaTi4O9陶瓷的结构和介电性能。XRD研究表明BaTiO9属正交晶系,空间群Pmmn,晶格常数为a=1.453nm,b=0.379nm,c=0.629nm,每个原胞有两个分子,钛原子位于变形的氧八面体之中。这种氧八面体的极化类似于或大于在BaTiO3和PbTiO3铁电相观察到的极化。锰掺杂极大地增强了Q值,在1MHz下测得的Q值为12500。而没有掺杂的陶瓷有高的损耗,这可能是由于在空气中烧结时形成的Ti^3 ,显然锰的作用是在缺陷平衡中作为一种补偿剂,依据反应：Mn^3 Ti^3 →Mn^2 Ti^4 ,可能有助于Ti^4 的形成,BaTi4O9陶瓷具有优良的介电性能;低介质损耗、中等介电常数和介电常数温度系数。此种陶瓷造成多层陶瓷电容器开拓了一种新的应用领域。     

非均相沉淀法制备Ba3MgSi2O8:Eu2+,Mn2+荧光粉

用非均相沉淀法首次合成了名义化学式为Ba2.88MgSi2O8:0.02Eu2+,0.1Mn2+的Eu2+、Mn2+共掺杂Ba3MgSi2O8荧光粉.用XRD、SEM和荧光光谱进行表征,并与相同条件下用高温固相法合成的荧光粉作对比.研究沉淀反应温度、金属离子浓度对非均相沉淀法制备荧光粉相纯度和发光性能的影响.结果表明:相对于高温固相法,非均相沉淀法可在更低的温度下合成相纯度高的荧光粉,且粉末颗粒呈近球状,粒径均匀,粉末基本无团聚;沉淀反应温度为40℃,在此温度下,金属离子溶液滴加完毕后,继续搅拌2h,并在室温下陈化24h,金属离子浓度为0.30mol/L左右时为最宜.     

Mn2+对掺Ce3+BiB3O6纳米材料发光强度的影响

采用溶胶-凝胶的方法合成了一系列掺杂Mn2+,Ce3+的BiB3O6纳米发光材料.通过激发光谱和发射光谱研究了其发光性质,并探讨了Mn2+对Ce3+发光性能的影响.BiB3O6:Ce3+的发射光谱有位于370nm和405nm处的2个发射峰,由于Mn2+对Ce3+的敏化作用,Ce3+在BiB3O6:Ce3+,Mn2+中的发光强度有了显著的增强.     

Catalytic Oxidation of CO Gas over Nanocrystallite Cu x Mn1−x Fe2O4

The catalytic oxidation of CO over nanocrystallite Cu _x Mn_(1−x)Fe₂O₄ powders was studied using advanced quadruple mass gas analyzer system. The oxidation of CO to CO₂ was investigated as a function of reactants ratio and firing temperature of ferrite powders. The maximum CO conversion was observed for ferrite powders which have equal amount of Cu²⁺ and Mn²⁺ (Cu_0.5Mn_0.5Fe₂O₄). The high catalytic activity of Cu_0.5Mn_0.5Fe₂O₄ can be attributed to the changes of the valence state of catalytically active components of the ferrite powders. The firing temperature plays insignificant role in the catalytic activity of CO over nanocrystallite copper manganese ferrites. The mechanism of catalytic oxidation reactions was studied. It was found that the CO catalytic oxidation reactions on the surface of the Cu _x Mn_1−x Fe₂O₄ was done by the reduction of the ferrite by CO to the oxygen deficient lower oxide then re-oxidation of this phase to the saturated oxygen metal ferrite again.     

Dispersion–precipitation synthesis of nanorod Mn3O4 with high reducibility and the catalytic complete oxidation of air pollutants

Manganese oxide catalyst was prepared by a novel dispersion–precipitation method, which involved synthesis of stable aqueous dispersion of manganese oxide nanoparticles and the subsequent precipitation by dilution-induced destabilization. The characterizations indicated that the thus prepared catalyst was composed of nanorod particles with a Hausmannite structure of Mn₃O₄, and had a high reducibility. In comparison to the catalysts prepared by alkaline-salt reaction or calcination of manganese acetate, this catalyst prepared by the new method showed much better performance in the catalytic complete oxidation of airborne carbon monoxide and toluene, which is possibly attributed to the smaller particle sizes and higher oxygen mobility.     

(en)Mn2(V2O7): A 3D manganese vanadate built by Mn–O layers and two types of pillars of V2O7 and en bridges

An unexpected 3D manganese vanadate (en)Mn₂(V₂O₇) (1) (en = ethylenediamine) has been hydrothermally obtained by H₂E₂Ge₂O₃ (E = ? CH₂CH₂COO^?) ligands and well-prepared mixture of V–Mn-amine and characterized by IR spectroscopy, elemental analysis, thermal stability and powder X-ray diffraction. Single-crystal X-ray diffraction analysis reveals that the structure is a novel pillared-layer, in which MnO₅N octahedra are corner-linked to form an infinite sheet with 4-membered rings (MRs) and further condensed to the 3D framework. The most prominent feature of 1 is the connection between the sheets via double bridges, namely, inorganic V₂O₇ dimeric units and organic en molecules. It is noteworthy that inorganic and organic double bridges between sheets have not been seen in manganese vanadates.     

多孔球状Mn3O4的制备及电容特性研究

通过精确控制葡萄糖的摩尔反应比,采用水热结合低温烧结法制备了多孔球状黑锰矿结构Mn3O4.当高锰酸钾与葡萄糖比例为1∶3(MNO-3)时,具有最优性能.SEM结果显示最优样品具有多孔球状结构,粒径大小均匀,约为1 ～4 μm.运用恒流充放电、交流阻抗、循环伏安等电化学测试方法研究其电容特性和电化学性能.结果 表明:在6 mol·L-1KOH电解质溶液中,电流密度为1A·g-1的条件下MNO-3样品具有最高比容量321.7 F·g-1,循环400圈后,其比容量保持率为97.15％.     

聚合物辅助法合成LiNi0.5Mn1.5O4的研究

采用聚合物辅助方法合成了纳米级的LiNi0.5Mn1.5O4颗粒.通过XRD测试,扫描电镜观察和充放电测试表征了材料的晶体结构、形貌和电化学性能.结果表明烧结温度对于颗粒的尺寸形貌和结晶度具有重要的影响作用,并影响其放电能力,800℃烧结获得的LiNi0.5Mn15O4具有更好的结晶性并且展示出更好的电性能.     

Synthesis and characterization of monodispersed BaSO4/Y2O3:Eu3+ core–shell submicrospheres

Spherical BaSO₄ particles have been coated with Y₂O₃:Eu³⁺ phosphor layers (BaSO₄/Y₂O₃:Eu³⁺) by the wet chemical method. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dipersive spectroscopy (EDS), photoluminescence spectra were utilized to characterize the BaSO₄/Y₂O₃:Eu³⁺ core–shell-structured phosphor particles. The obtained core–shell phosphors consist of well dispersed submicron spherical particles with narrow size distribution. XRD result shows that no reaction occurred between the BaSO₄ cores and the Y₂O₃:Eu³⁺ shells even after annealing at 1400 °C. TEM and EDS results show that BaSO₄ particles are well coated with the shell of Y₂O₃:Eu³⁺. The BaSO₄/Y₂O₃:Eu³⁺ core–shell particles show a red emission corresponding to ⁵D₀?⁷F₂ of Eu³⁺ under the excitation of ultraviolet.     

Investigation of cation distribution and magnetocrystalline anisotropy of NixCu0.1Zn0.9−xFe2O4 nanoferrites: Role of constant mole percent of Cu2+ dopant in place of Zn2+

Co-precipitated and 800 °C heat treated Ni-Cu-Zn nanoferrites with chemical formula Ni_xCu_0.1Zn_0.9-xFe₂O₄ (x=0.5, 0.6, 0.7) were prepared because of their potential use as multilayer chip inductors in electromagnetic applications. Their structural, magnetic properties and phase formation were studied using X-ray diffractometer (XRD), field emission scanning electron microscope (FE–SEM), vibrating sample magnetometer (VSM), Mössbauer spectrometer, thermogravimetric analyzer (TGA) and differential scanning calorimeter (DSC). The XRD patterns confirm the cubic spinel structure of the ferrite phase belonging to Fd3m space group. Lattice parameters and cation distributions were obtained by Rietveld refinement of the XRD patterns. The lattice parameter decreases with increase in Ni²⁺ ion concentration. Rietveld analysis indicates that Cu²⁺ ions predominantly occupy the B-sites and Ni²⁺ ions partly going into B-sites but predominantly into A-sites. An excellent agreement is observed between the experimental lattice parameters and lattice parameters theoretically calculated using this cation redistribution. The inversion parameter (λ) observed for Fe³⁺ ions by Mössbauer spectroscopy is different from that of Rietveld analysis. Magnetization and Mössbauer spectroscopic measurements indicate that the ferrite nanoparticles are mostly superparamagnetic. The cation redistribution is supposed to alter the magnetocrystalline anisotropy which in turn affects the magnetic parameters of the present ferrite samples. The reduced magnetization is attributed to core-shell interactions and possible canting of A- and B-shell magnetizations. TGA-DSC studies indicate that ferrite formation in the 800 °C heat treated samples is completed but grain growth increases as the particles are subject to the increased temperature.     

The Electrical Properties of Polyaniline (PANI)–Co0.5Mn0.5Fe2O4 Nanocomposite

Polyaniline (PANI)/cobalt-manganese ferrite, PANI/Co_0.5Mn_0.5Fe₂O₄, nanocomposite was synthesized by oxidative chemical polymerization of aniline in the presence of ammonium peroxydisulfate. Microwave assisted synthesis method was used for the fabrication of core Co_0.5Mn_0.5Fe₂O₄ nanoparticles. The presence of PANI on the surface of the Co_0.5Mn_0.5Fe₂O₄ NPs was confirmed by infrared spectroscopy and thermal gravimetric analysis. The crystallite size was calculated with line profile fitting method as 20 ± 9 nm. The spherical morphology of the product was presented by Scanning electron microscopy and transmission electron microscopy. The electrical characterizations showed that ac conductivity is found to be independent of frequency and increases with increase of temperatures. However, imaginary component of dielectric function obey the power law of frequency while it is almost independent of temperature. This can be attributed to the molecular interatomic interaction between Co_0.5Mn_0.5Fe₂O₄ nanoballs and PANI shells.     

纳米片状Mn2O3@α-Fe3O4活化过碳酸盐降解偶氮染料

过碳酸钠是过氧化氢与碳酸钠的加成化合物,具有在存储、运输和使用过程中安全稳定的优点。本文采用共沉淀-高温煅烧法制备纳米片状Mn₂O₃@α-Fe₃O₄,活化过碳酸钠（SPC）产生自由基氧化降解偶氮染料活性黑5（RBK5）。采用透射电子显微镜（TEM）、X射线粉末衍射仪（XRD）、扫描电子显微镜（SEM）、傅里叶变换红外光谱仪（FTIR）、X射线光电子能谱（XPS）及比表面积测试（BET）表征制备的纳米片状Mn₂O₃@α-Fe₃O₄催化剂,分别探究催化剂投加量、过碳酸钠浓度、初始pH及RBK5溶液浓度对降解效率的影响。当催化剂投加量为0.3g/L、过碳酸钠浓度为1.0mmol/L、初始pH为3、反应时间为90min时,RBK5的降解效率达88%,反应过程符合拟一级动力学（R²＞0.9）。Mn₂O₃@α-Fe₃O₄/过碳酸钠体系中起氧化降解作用的活性物种为·OH、CO{}_{\mathrm{3}}^{-}·、O{}_{\mathrm{2}}^{-}·和¹O₂,其中·OH占据主导地位,XPS反映了铁锰元素存在价态以及双金属间的协同作用,依据猝灭实验及XPS分析降解机理。     

机械力化学法制备LiNi0.5Mn1.5O4粉体的研究

以Li2CO3,MnO2和Ni(OH)2·H2O为原料,采用机械力化学法制备锂离子层状结构正极材料LiNi0.5Mn1.5O4,采用X射线衍射,扫描电镜对其结构和形貌进行了表征.结果表明粉磨6 h可制备能在较低温度下发生固相反应的前驱体;前驱体于800℃煅烧6 h制备得到具有α-NaFeO2型层状有序结构的单相LiNi0.5Mn1.5O4.样品的首次放电容量为80 mAh·g-1.     

Electrical properties of CaBi4Ti4O15–Bi4Ti3O12 piezoelectric ceramics

CaBi₄Ti₄O₁₅–Bi₄Ti₃O₁₂ (CBT–BIT) ceramics were synthesized using a solid state reaction method. The X-ray diffraction (XRD) analysis revealed the existence of bismuth layered perovskite phase with orthorhombic crystal structure. High-resolution transmission electron microscopy (HRTEM) confirmed the alternate arrangement of CBT part and BIT part along c axis in the intergrowth structure. CBT–BIT ceramics showed excellent thermal stability of the dielectric loss (tan δ), but the relaxation of dielectric loss in the 100 Hz to 1 MHz frequency range had been observed. Meanwhile, an enhanced piezoelectric constant (d₃₃) value of 15 pC/N was observed without degradation even the temperature up to 650 °C. The dc resistivity (ρ_dc) of CBT–BIT performed a high value of 5.68×10¹⁴ (Ω cm) at room temperature (RT). In addition, the ρ_dc values of CBT–BIT within the temperature range of 100–450 °C were close to those of CBT and kept almost one hundred times higher than those of BIT.     

高电压LiNi0.5Mn1.5O4正极材料现状及展望

LiNi0.5Mn1.5O4正极材料具有高能量密度、三维的锂离子传输通道、无毒、安全性高等优势,成为近些年来锂离子电池领域中最具有研究前景的材料之一.介绍了LiNi05Mn15O4正极材料的结构,综述了LiNi05Mn15O4材料常见的制备和改性方法,着重介绍了LiNi05Mn1.5O4微米级单晶形貌对材料性能的影响,并结合当前研究进展对LiNi0.5Mn1.5O4材料未来的发展趋势进行展望.