Direct ultrasonic-assisted synthesis of sphere-like nanocrystals of spinel Co3O4 and Mn3O4

A simple sonochemical method was developed to synthesize uniform sphere-like or cubic Co(3)O(4) and Mn(3)O(4) nanocrystals by using acetate salts and sodium hydroxide or tetramethylammonium hydroxide (TMAH) as precursors. Influence of some parameters such as time of reaction, alkali salts, and power of the ultrasound and the molar ratio of the starting materials on the size, morphology and degree of crystallinity of the products was studied. Powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), FTIR spectroscopy, Thermal gravimetry analysis and differential thermal analysis (TGA/DTA) were used to characterize the nanocrystals.     

Luminescence kinetics in silica gel doped with Tb3+ ions and ZnS:Mn2+ nanocrystals

Luminescence kinetics and time-resolved luminescence spectra of SiO₂, SiO₂ doped with ZnS:Mn²⁺ nanocrystals and SiO₂ doped with ZnS:Mn²⁺, and additionally co-doped with Tb³⁺, are presented. The purposes of the paper are the analysis of the kinetics of the Tb³⁺ and Mn²⁺ intra-shell luminescence and the elucidation of the energy-transfer mechanism between the ZnS:Mn²⁺ nanocrystals and the Tb³⁺ ions. We have found a blue luminescence related to defects in the ZnS nanocrystals and an intrinsic luminescence of the SiO₂ lattice, which decays in few ns. A yellow luminescence related to the Mn^{2+ 4}T₁(G)→⁶A₁ transition and yellow sharp lines related to the ⁵D₄→⁷F₆, ⁷F₅, ⁷F₄ and ⁷F₃ transitions in Tb³⁺ are found to decay in ms. A very effective energy transfer between ZnS:Mn²⁺ nanoparticles and Tb³⁺ ions has been observed.     

Antiferromagnetic phase transition in garnet-type AgCa2Mn2V3O12 and NaPb2Mn2V3O12

Ferrimagnetism has been extensively studied in garnets, whereas it is rare to find the antiferromagnet. Present work will demonstrate antiferromagnetism in the two Mn–V-garnets. Antiferromagnetic phase transition in AgCa₂Mn₂V₃O₁₂ and NaPb₂Mn₂V₃O₁₂ has been found, where the magnetic Mn²⁺ ions locate only on octahedral A site. The heat capacity shows sharp peak due to antiferromagnetic order with the Néel temperature T_N=23.8 K for AgCa₂Mn₂V₃O₁₂ and T_N=14.2 K for NaPb₂Mn₂V₃O₁₂. The magnetic entropy change over a temperature range 0–50 K is 13.9 J K^?1 mol-Mn²⁺-ions^?1 for AgCa₂Mn₂V₃O₁₂ and 13.6 J K^?1 mol-Mn²⁺-ions^?1 for NaPb₂Mn₂V₃O₁₂, which are in good agreement with calculated value of Mn²⁺ ion with spin S=5/2. The magnetic susceptibility shows the Curie–Weiss behavior over the range 29–350 K. The effective magnetic moment μ_eff and the Weiss constant θ are μ_eff=6.20 μ_B Mn²⁺-ion^?1 and θ=?34.1 K (antiferromagnetic sign) for AgCa₂Mn₂V₃O₁₂ and μ_eff=6.02 μ_B Mn²⁺-ion^?1 and θ=?20.8 K for NaPb₂Mn₂V₃O₁₂.     

A novel approach for the synthesis of superparamagnetic Mn3O4 nanocrystals by ultrasonic bath

In this study, the synthesis of Mn₃O₄ (husmannite) nanoparticles was carried out in two different alkali media under sonication by ultrasonic bath and conventional method. Manganese acetate was used as precursor, sodium hydroxide and hexamethylenetetramine (HMT) as basic reagents in this synthesis. An ultrasonic bath with low intensity was used for the preparation of nanomaterials. The as prepared samples were characterized with X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, transmission electron microscopy (HRTEM, TEM), energy-dispersive spectrum (EDS), and superconducting quantum interference device (SQUID) analysis. The XRD patterns exhibit the nanocrystals are in pure tetragonal phase. The chemical composition was obtained by EDS analysis and confirmed the presence of Mn and O in the sample. According to the TEM and HRTEM results, both nanorods and nanoparticles of Mn₃O₄ were obtained in the presence of ultrasonic irradiation. The average size of nanoparticles was 10 nm, and the size of nanorods was 12 nm in diameter and 100-900 nm in length for the samples prepared in basic medium with sodium hydroxide. In the conventional method with the same basic medium, the nanorod was not observed and the nearly cubic nanoparticles was appeared with an average size of 2.5 nm. The selected area electron diffraction (SAED) patterns revealed that the nanocrystals are polycrystalline in nature. When HMT was used as a basic reagent in the presence of ultrasonic irradiation, it was led to a higher size of nanoparticles and nanorods than when sodium hydroxide was used as a basic reagent. The average size of nanoparticles was about 15 nm and its shape was nearly cubic. The diameter for nanorods was 50 nm and the length was about a few micrometers.The magnetic measurements were carried out on the sample prepared in sodium hydroxide under ultrasonic irradiation. These measurements as a function of temperature and field strength showed a reduction in ferrimagnetic temperature (T_c = 40 K) as compared to those reported for the bulk (T_c = 43 K). The superparamagnetic behavior was observed at room temperature with no saturation magnetization and hysteresis in the region of measured field strength.     

Influence of grain size on the electrical properties of the double-layered LaSr2Mn2O7 manganite

The double-layered LaSr₂Mn₂O₇ manganite was synthesized by the sol–gel process. Two samples with the average grain size from ～150 nm to ～1 μm were prepared by controlling the sintering temperature. Both samples had a tetragonal structure, with a small fraction of impurity phase in the S-1250 sample. In order to investigate the probable influence of grain size on the conduction mechanism, resistivity of the samples was measured as a function of temperature, and the data obtained was analyzed by different conduction mechanisms. It was found that with increase in the grain size, resistivity decreased at all temperature ranges. The results show that the adiabatic small polaron hopping (SPH) model is probably responsible for conduction at high temperature range, and that the 3D variable range hopping (VRH) model shows a better correlation with the experimental data for low temperature range. These analyses indicate the influence of grain size on the parameters obtained from fitting the data by both models.     

Phonon kinetics in solid solutions of ceramics in the ZrO2-Y2O3-MgO-Al2O3 system

The propagation of weakly nonequilibrium phonons is studied in ceramics based on ZrO₂-Y₂O₃-MgO-Al₂O₃. Under the assumption of a large dispersion in the ceramic grain sizes, the characteristics of phonon scattering are studied as a function of the temperature and duration of isothermal annealing of the samples and the contribution of the intergrain boundaries to the phonon kinetics is isolated. Fiz. Tverd. Tela (St. Petersburg) 39, 1091–1093 (June 1997)     

Austenite grain growth kinetics and mechanism of grain growth in 12Cr ultra-super-critical rotor steel

ABSTRACT

In this paper, the austenite grain growth behaviour of 12Cr ultra-super-critical (USC) rotor steel was investigated by a series of heat treatments. The heat treatments at heating temperatures of 900°C–1250°C and holding time of 1?h–20?h were conducted in an electric box-type heating furnace. Experimental results showed that the sizes of austenite grain were affected by heating temperatures and holding time, and heating temperature was the dominant factor. In addition, the grain growth rate changed significantly before and after the turning points of 1050°C and 1250°C. Meanwhile, an austenite grain growth mathematical model was established at different heating temperature stages, and possession of the capability to accurately predict austenite grain size was confirmed. Furthermore, the microstructure of austenite grain in the heating process was observed by optical microscope (OM) and transmission electron microscopy (TEM), which revealed the mechanism of austenite grain growth. Analysis indicated that the change of quantity of precipitate particles with increasing heating temperature was the main reason for the difference in austenite grain growth.     

Engineering of YBa2Cu3O7–δ grain boundary Josephson junctions by Au nanocrystals

We prepared and investigated grain boundary Josephson junctions based on SrTiO₃ bicrystal substrates. During the deposition of YBa₂Cu₃O_7–δ (YBCO) gold nanocrystals forming from an intermediate gold layer can modify the crystalline structure and thus the properties of the YBCO grain boundaries. The variation of the film thickness of the Au seed layer changes the growth conditions of the YBCO film and the Au nanocrystals. The values of the characteristic I_CR_N product do not change whereas the values of the critical current I_C decrease.

     

Excitons and photoluminescence in ZnO and Zn0.99Mn0.01O nanocrystals

The photoluminescence and photoluminescence excitation spectra for Zn_1?x Mn _x O nanocrystals are presented. After annealing of powders in air, the intensity of the bands attributable to manganese decreases noticeably. This suggests that the oxygen vacancies affect the Zhang-Rice-like states appearing due to strong d-p-hybridization, which is confirmed by an increase in the band gap of Zn_1?x Mn _x O for low x. The origin of the 2.9-eV peak and the shape of its excitation spectrum are discussed qualitatively. For Zn_1?x Mn _x O nanocrystals, the shape of the excitation spectrum is as unusual as the intense absorption in the range (2.2–3.0) eV.     

Linear grain growth kinetics and rotation in nanocrystalline Ni

We report three-dimensional atomistic molecular dynamics studies of grain growth kinetics in nanocrystalline Ni. The results show the grain size increasing linearly with time, contrary to the square root of the time kinetics observed in coarse-grained structures. The average grain boundary energy per unit area decreases simultaneously with the decrease in total grain boundary area associated with grain growth. The average mobility of the boundaries increases as the grain size increases. The results can be explained by a model that considers a size effect in the boundary mobility.     

Y2O3:Er3+纳米晶anti-Stokes发光性质的研究

采用均相沉积法制备了不同Er3+离子浓度掺杂的Y2O3纳米晶,应用XRD,SEM和PL光谱对该体系材料进行了表征.在Y2O3:Er3+纳米材料体系中,观察和研究了Stokes及anti-StokesPL谱强度与Er3+离子摩尔浓度变化的关系,当Er3+离子浓度为2.0mol%时,anti-Stokes PL强度最强.粉末XRD和SEM照片分别表明:制备的Y2O3:Er3+纳米材料具有立方相结构,且粒径分布均匀.实验结果证明:anti-Stokes PL来自于这个体系中的双光子吸收过程.     

纳米晶Gd2O3：Eu^3＋的制备及发光性能

采用低温燃烧合成法制备了Gd2O3：Eu^3＋纳米晶。用X射线衍射仪（XRD）、高分辨透射电子显微镜（HRTEM）和荧光光谱仪分别对样品的结构、形貌和发光性能进行了研究。结果表明，改变甘氨酸与稀土离子的比例（G／M）、退火温度可以制备出不同结构和晶粒尺寸的Gd2O3：Eu^3＋纳米晶。在退火温度为800℃，G／M等于0．83和1．0时，均得到了纯立方相的Gd2O3：Eu^3＋纳米晶，随着G／M的增加，Gd2O3：Eu^3＋从立方相逐渐向单斜相转变。粉末的晶粒尺寸随着退火温度的增高而增大，晶粒尺寸在10-30nm之间。立方相的Gd2O3：Eu^3＋纳米晶主发射峰位置在612nm（^5D^0→^7F2跃迁），激发光谱中电荷迁移态发生了红移。     

Spin relaxation in the amorphous spin glass Al2Mn3Si3O12

Neutron scattering measurements on the amorphous spin glass Al₂Mn₃Si₃O₁₂ have been made using the time-of-flight method. The scattering lawS(Q, ) reveals a quasielastic line with temperature andQ-dependent linewidth and an elastic line with constant intensity between 15 and 294K. The linewidth of the quasielastic scattering diminishes with decreasing temperature following an Arrhenius law at least down to 15K. Deviations from this exponential form are strictly correlated with an increase of the elastic intensity below 15K. We favour the opinion that this effect is caused by the instrumental resolution rather than by the onset of spin glass freezing.     

Spin-polarized Mn2+ emission from Mn-doped colloidal nanocrystals

We report magnetophotoluminescence studies of strongly quantum-confined 0D diluted magnetic semiconductors (DMS), realized in Mn(2+)-doped ZnSe/CdSe core-shell colloidal nanocrystals. In marked contrast to their 3D (bulk), 2D (quantum well), 1D (quantum wire), and 0D (self-assembled quantum dot) DMS counterparts, the ubiquitous yellow emission band from internal d-d ((4)T(1)→(6)A(1)) transitions of the Mn(2+) ions in these nanocrystals is not suppressed in applied magnetic fields and does become circularly polarized. This polarization tracks the Mn(2+) magnetization, and is accompanied by a sizable energy splitting between right- and left-circular emission components that scales with the exciton-Mn sp-d coupling strength (which, in turn, is tunable with nanocrystal size). These data highlight the influence of strong quantum confinement on both the excitation and the emission mechanisms of magnetic ions in DMS nanomaterials.     

Nuclear magnetic resonance in noncollinear antiferromagnet Mn3Al2Ge3O12

The ⁵⁵Mn nuclear magnetic resonance spectrum of noncollinear 12-sublattice antiferromagnet Mn₃Al₂Ge₃O₁₂ has been studied in the frequency range of 200–640 MHz in the external magnetic field H ‖ [001] at T = 1.2 K. Three absorption lines have been observed in fields less than the field of the reorientation transition H _c at the polarization h ‖ H of the rf field. Two lines have been observed at H > H _c and h ⊥ H. The spectral parameters indicate that the magnetic structure of manganese garnet differs slightly from the exchange triangular 120-degree structure. The anisotropy of the spin reduction and (or) weak antiferromagnetism that are allowed by the crystal symmetry lead to the difference of ≈3% in the magnetization of sublattices in the field H < H _c. When the spin plane rotates from the orientation perpendicular to the C ₃ axis to the orientation perpendicular to the C ₄ axis, all magnetic moments of the electronic subsystem decrease by ≈2% from the average value in the zero field.     

Catalytic precursors: (Fe,Mn)3O4 and γ-(Fe,Mn)2O3

Iron-manganese oxide catalysts are known to influence the production of short chain hydrocarbons in the Fischer-Tropsch-synthesis process. XRD, XRF, gravity measurements and Mössbauer-effect spectroscopy has been used to study a catalytic precursor made by coprecipitation of iron and manganese oxides. The sample is characterized as a mixture of two compounds with the same iron to manganese ratio. The two compounds are cubic spinels with the same crystallographic parameters, however, one compound is a defect spinel while the other is not. In the Mössbauer studies the defect spinel shows superparamagnetic relaxation behavior—fluctuations of the magnetization vector along two opposite easy directions, while the non-defect spinel shows evidence of collective excitations—fluctuations of the magnetization vector in directions close to the easy direction. These properties are related to the particle sizes.     

Ag+掺杂的立方相Y2O3:Eu纳米晶体粉末发光强度研究

采用化学自燃烧法制备了不同Ag+掺杂浓度的Y2O3:Eu纳米晶体粉末样品([Y3+]:[Eu3+]:[Ag+]=99:1:X,X=0-3.5×10-2),以及通过退火处理得到了相应的体材料.根据X射线衍射谱确定所得纳米和体材料样品均为纯立方相.实验表明在纳米尺寸样品中随着Ag离子浓度的增加,荧光发射强度随之增加,当X=2×10-2时达到最大值,其发光强度比X=0时提高了近50%.当Ag离子浓度继续增加,样品发光强度保持不变.在相应的体材料样品中则没有观察到此现象.通过对各样品的发射光谱,激发光谱,X射线衍射图谱,透射电镜(TEM)照片和荧光衰减曲线的研究,分析了引起纳米样品荧光强度变化的原因是由于Ag离子与表面悬键氧结合,从而使这一无辐射通道阻断,使发光中心Eu3+的量子效率提高;Ag+的引入所带来的另一个效应是使激发更为有效.这两方面原因使发光效率得到了提高.     

Nonradiative energy transfer from Mn2+ to Eu3+ in K2CaP2O7:Mn2+,Eu3+ phosphor

A series of color tunable phosphors K₂Ca_1?x?yP₂O₇:xMn²⁺, yEu³⁺ are synthesized by solid state reaction method. The energy transfer phenomenon from Mn²⁺ to Eu³⁺ has been observed in the Mn²⁺/Eu³⁺ codoped non-magnetic K₂CaP₂O₇ host, which was confirmed by PL spectra and decay curves. The Mn²⁺→Eu³⁺ energy transfer is controlled by quadrupole–quadrupole interaction between sensitizer and activator. The maximum efficiency of energy transfer is estimated to be 33% with x=0.125 and y=0.03 in K₂Ca_1?x?yP₂O₇:xMn²⁺, yEu³⁺ phosphor. The phosphors can emit light from green to yellow and eventually to orange under 400 nm excitation by changing the Mn²⁺/Eu³⁺ content ratio, indicating that K₂CaP₂O₇: Mn²⁺, Eu³⁺ would be potential candidates for use in lighting and displays applications.