Synthesis of MnxZn（1-x）Fe2O4 Nanopartieles by Ball-milling Hydrothermal Method

SMnxZn1-xFe2O4 （x=1,0.9,0.8,0.7,0.6,0.5,0.25,0） nanoparticles were prepared by ball-milling hydrothermal and investigated by X-ray diffraction, DTG and TEM. Nanocrystallite grain size was determined by X-ray linewidth to be from 63 A to 274 A. The thermal properties indicate absorbed water still remain at low temperature, crystalline wate will be decomposed from 230 ℃ to 260 ℃, partial Mn^2＋ will be oxidized near 730 ℃. TEM shows the ferrite particles pocess a spherical morphology and uniform nanosize.     

Structure and stability of Li-Mn-Ni composite oxides as lithium ion sieve precursors in acidic medium

A series of spinel Li-Mn-Ni composite oxides with theoretical chemical formula of LiNixMn2-xO4 (0≤x≤1.0) were synthesized by liquid phase method. Their structure and morphology were characterized by X-ray diffractometry (XRD) and scanning electron microscopy (SEM),respectively. The stability of these Ni-substituted spinel oxides prepared at different temperatures was investigated in acidic medium as well. The results show that Ni can be brought into the spinel framework completely to form well-crystallized ...     

Theoretic Diffraction Research on the Order-Disorder Effect of Transition Metal in Li(Ni1/3Co1/3Mn1/3)O2

Li(Ni_1/3Co_1/3Mn_1/3)O₂的(3b)位有序-无序效应研究

曹春晖^1,2, 张建¹, 杨传铮¹, 夏保佳¹

（1.上海微系统与信息技术研究所,上海 200050;

2.中国科学院大学, 北京100049）

创新点说明：

提出了有序度的概念,通过理论模拟了过渡金属在3b位不同有序度下的衍射情况。

研究目的：

借助理论衍射研究镍钴锰在三元材料中的占位情况,为实际得到的衍射数据分析起指导作用。

研究方法和结果：

借助Powercell程序模拟不同结构下的衍射情况。结果表明：对于Li(Ni1/3Co1/3Mn1/3)O2,基体衍射线的强度不随有序度而变化,有序度增加时,超点阵衍射线强度增加,但是即使对于有序度最大时,超点阵线的相对强度只有0.225%和0.043%。

结论：

3b位的有序无序很难通过常规的衍射实验观测到,必须提高X射线源的强度才可能观测到。

关键词：Li(Ni1/3Co1/3Mn1/3)O2, 有序-无序,超结构,衍射

     

Preparation of high emissivity NiCr2O4 powders with a spinel structure by spray drying

Spray-drying was used to produce the high emissivity NiCr2O4 powders with a spinel structure. Preliminary investigations focused on fabricating the high emissivity powders for infrared radiation coatings and finding the relationship between microstructure and emissivity. The NiCr2O4 powders were characterized for composition, microstructure, and infrared emissivity by X-ray diffraction (XRD), scanning electron microscopy (SEM), infrared radiant instrument, and Fourier transform infrared spectra (FT-IR). Thermogravimetry and differential thermal analysis show that the appropriate baking temperature for NiCr2O4 powder preparation is about 1200?C. The emissivity measurement and FT-IR spectra show that, because of the special spinel structure, the NiCr2O4 powders have a high emissivity about 0.91. Spray-drying is a suitable method to produce the high emissivity ceramic powders.     

Effects of Excess Barium on the Structure and Electrical Properties of (Ba,Ca)TiO<Subscript>3</Subscript> Piezoelectric Ceramics with High Mechanical Quality Factors

Manganese-doped Ba_0.925Ca_0.075TiO₃ lead-free piezoelectric ceramics (abbreviated as BCT) with high mechanical quality factor were synthesized by conventional solid-state reaction method. The effects of excess Ba on the crystal structure, microstructure, and electrical properties of the ceramics were systematically investigated. X-ray diffraction and Raman spectra revealed that Ca²⁺ ions were pushed from Ba sites to Ti sites of BCT when 1.5 mol% extra Ba²⁺ ions were added after sintering. The grain size of the ceramics was decreased by adding extra Ba²⁺ ions. The mechanical quality factor and resistivity of the ceramics decreased dramatically when the excess Ba was more than 1.5 mol%. High piezoelectric coefficients ( d₃₃ = 150–190 pC/N ) and high mechanical quality factors ( Q_m = 1 000–1 200 ) were obtained in the ceramics when the excess of Ba was between 0.5 mol% and 1 mol%. These results indicated that the properties of BCT ceramics could be tailored by adjusting the content of Ba.     

Synthesis of NiCr2O4 spinel coatings with high emissivity by plasma spraying

Air plasma spraying(APS) was used to produce high emissivity coatings with a NiCr2O4 spinel structure.The relationship be-tween the emissivity and the crystal structure was investigated.X-ray diffraction(XRD) analyses show that NiCr2O4 spinel has been fabri-cated with the space group Fd3m.Scanning electron microscope(SEM) photographs show that the coating consists of a laminated structure with homogeneous grains and high porosity because of the unique feature of plasma spraying.The emissivity measurement and Fourier transformation infrared radiation(FT-IR) spectra show that NiCr2O4 has a high emissivity of about 0.91 because of its special spinel structure.APS is a suitable method to produce high emissivity coatings.     

Preparation of Ni/PZT core-shell nanoparticles and their electromagnetic properties

The Ni nanoparticles coated with Pb(Zr,Ti)O_3(PZT) were synthesized by a sol-gel method and in situ reaction. And their structure, oxidation resistance, and electromagnetic properties were investigated. The X-ray diffraction patterns(XRD) exhibited that a small amount of impure phase characterized to Ni(OH)_2 was detected from the ammonia-treated Ni nanoparticles and the ammonia-treated Ni nanoparticles coated with PZT. After being pre-treated with aqueous ammonia, the PZT coating layer was more uniform and about 10 nm in thickness. The oxidation resistance of the ammonia-treated Ni nanoparticles coated with PZT, compared with that of the non-treated ones, was improved by about 66 ℃. The PZT shell layer prepared by in-situ reaction can greatly reduce the dielectric constant and improve the natural resonance loss at high frequency, so as to obtain the optimal impedance matching performance of the electromagnetic wave transmission.     

A Modified Co-precipitation Method to Prepare Cu/ZnO/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Catalyst and Its Application in Low Temperature Water-gas Shift (LT-WGS) Reaction

A modified co-precipitation method for the production of Cu/ZnO/Al₂O₃ complex was studied. The modification was that part of Al was introduced by adding Al³⁺ into Cu²⁺/Zn²⁺ solution, and the rest of Al was added after co-precipitation step in the form of pseudo-boehmite. The prepared samples were characterized by different techniques such as X-ray diffraction, N₂ adsorption, H₂-N₂O titration, temperature programmed reduction and scanning electron microscopy. X-ray diffraction characterizations revealed that Al³⁺ can be doped in aurichalcite lattice, and the maximum doping amount of Al³⁺ was 5.0% of total Cu and Zn atoms. The Cu/ZnO/Al₂O₃ sample produced by the modified method, in which co-precipitated Al³⁺ was 2.5% of total Cu and Zn atoms showed much better activity and stability in water-gas shift reaction than commercial sample. The high Cu surface area (26.1 m²/g) obtained by decompositon of doped aurichalcite is believed to be responsible for the activity enhancement. The stability was enhanced mainly because of the support effect of γ-Al₂O₃, which was decomposed from pseudo-boehmite in the calcination step.     

Spontaneous Magnetic Transitions and Corresponding Magnetoelastic Properties of Intermetallic Compounds <Emphasis Type="Italic">R</Emphasis>Mn<Subscript>2</Subscript>Ge<Subscript>2</Subscript> (<Emphasis Type="Italic">R</Emphasis>=Gd,Tb and Dy)

The spontaneous magnetic transitions and corresponding magnetoelastic properties of intermetallic compounds RMn₂Ge₂ (R=Gd, Tb and Dy) were investigated by using the X-ray diffraction method and magnetic measurement. The results showed that the compounds experience two magnetic transitions, namely the second-order paramagnetic to antiferromagnetic transition at temperature T_N (T_N=368, 423 and 443 K for GdMn₂Ge₂, TbMn₂Ge₂ and DyMn₂Ge₂, respectively) and the first-order antiferromagnetic - ferrimagnetic transition at temperature T_t (T_t=96, 80 and 40 K for GdMn₂Ge₂, TbMn₂Ge₂ and DyMn₂Ge₂, respectively) as the temperature decreases. The temperature dependence of the lattice constant a(T) displays a negative magnetoelastic anomaly at the second-order transition point T_N and, at the first-order transition T_t, a increases abruptly for GdMn₂Ge₂ and TbMn₂Ge₂, Δa/a about 10^-3. Nevertheless, the lattice constant c almost does not change at these transition points indicating that such magnetoelastic anomalies are mainly contributed by the Mn-sublattice. The transitions of the magnetoelastic properties are also evidenced on the temperature dependence of magnetic susceptibility χ. The first-order transition behavior at T_t is explained by the Kittel mode of exchange inversion.     

锰氧化菌激活及生物氧化锰去除乙炔基雌二醇试验研究

利用污水厂好氧污泥进行锰氧化细菌的激活试验,探究pH值以及初始Mn2+浓度对激活效果的影响,采用高通量测序技术分析激活前后微生物群落变化,利用X射线衍射(X-ray diffraction,XRD)技术对产生的生物氧化锰进行表征,研究pH值和投加量对生物氧化锰去除乙炔基雌二醇(17α-ethinylestradiol,...     

Structural and electrical properties of high Curie temperature Aurivillius phase composite ceramics with largely enhanced piezoelectricity

High performance piezoelectric ceramics with high Curie temperatures(TC) are the bottle necks of relevant high temperature devices. In this study, the electrical performance and microstructure of Li and Mn codoped Aurivillius-type composite ceramics with a composition Ca_(0.99-x_Bi_(6.99+x)(Li Mn)_(0.01) Nb Ti_5O_(24)(x = 0–0.8) were systematically investigated. The results indicated that uniform intergrowth structure with a lattice similar to that of the end member CBT could be formed at a low x value(x 0.4). Phase separation occurred when more A-site Ca~(2+) ions were replaced by Bi~(3+) ions. Nevertheless, all composite samples showed d_(33) values about 2 to 3 times of that of the constituent phase Ca Bi_4Ti_4O_(15) and Bi_3 Ti NbO_9 with still a high depolarization temperature. The performance of the samples was found to be related to the density and larger lattice distortion along the polarization a axis. The results also demonstrated that formation of the compound system was an effective way in improving the performance of Aurivillius-type high TC piezoelectric ceramics.     

Structure and electrochemical properties of La, F dual-doped iLa0.01Mn1.99O3.99F0.01 cathode materials

The cathode materials LiMn₂O₄ and rare earth elements La-doped or La and F dual-doped spinel lithium manganese oxides were synthesized by the citric acid-assisted sol-gel method. The synthesized samples were investigated by differential thermal analysis (DTA) and thermogravimetry (TG) measurements, X-ray diffraction (XRD), scanning electronic microscope (SEM), cyclic voltammetry (CV), and charge-discharge test. XRD data shows that all the samples exhibit the same pure spinel phase, and the LiLa_0.01Mn_1.99O_3.99F_0.01 and LiLa_0.01Mn_1.99O₄ samples have smaller lattice parameters and unit cell volume than LiMn₂O₄. SEM indicates that LiLa_0.01Mn_1.99O_3.99F_0.01 has a slightly smaller particle size and a more regular morphology structure with narrow size distribution. The charge-discharge test reveals that the initial capacities of LiMn₂O₄, LiLa_0.01Mn_1.99O₄, and LiLa_0.01Mn_1.99O_3.99F_0.01 are 129.9, 122.8, and 126.4 mAh·g⁻¹, and the capacity losses of the initial values after 50 cycles are 14.5%, 7.6%, and 8.0%, respectively. The CVs show that the La and F dual-doped spinel displays a better reversibility than LiMn₂O₄.     

Microstructure and growth kinetics of silicide coatings for TiAl alloy

In order to improve the oxidation resistance of Ti Al alloy, silicide coatings were prepared by pack cementation method at 1273, 1323, and 1373 K for 1-3 hours. Scanning electron microscopy(SEM), energy dispersive spectrometry(EDS) and X-ray diffraction(XRD) were employed to investigate the microstructures and phase constitutions of the coatings. The experimental results show that all silicon deposition coatings have multi-layer structure. The microstructure and composition of silicide coatings strongly depend on siliconizing temperatures. In order to investigate the rate controlling step of pack siliconizing on Ti Al alloy, coating growth kinetics was analyzed by measuring the mass gains per unit area of silicided samples as a function of time and temperature. The results showed that the rate controlling step was gas-phase diffusion step and the growth rate constant(k) ranged from 1.53 mg~2/(cm~4·h~2) to 2.3 mg~2/(cm~4·h~2). Activation energy(Q) for the process was calculated as 109 k J/mol, determined by Arrhenius' equation: k = k0 exp[–Q/(RT)].     

Preparation and magnetic properties of Mn-Zn ferrites by the Co-precipitation method

Mn-Zn ferrites (Mn_1?x Zn _x Fe₂O₄) with different compositions were prepared by the coprecipitation method, and the influences of such synthesis conditions as pH value, composition and volume ratio (R) of the mixed solution and NH₄HCO₃ solution on their microstructures and magnetic properties were discussed. The samples were characterized by X-ray diffraction (XRD) and magnetization measurement instrument. Lattice parameters and average crystalline size of the synthesized materials were calculated from the corresponding XRD patterns with the related software Jade.5. For samples of different pH values, only one phase was found when pH values were 7.0, 8.0 and 9.0. The sample with pH value of 7.0 exhibited the highest saturation magnetic induction, the lowest coercive force, and crystallized best. For samples of different R values with pH value of 7.0, only one phase was observed in all samples, and the sample with R value of 2.3 exhibited the highest saturation magnetic induction and the lowest coercive force. The composition has mainly afected the magnetic properties, and the saturation magnetic induction increases with the increase of the content of Zn (x), but decreases when x is beyond 0.6. The trend of coercive force is on the contrary. However, no magnetism is exhibited when the x value is up to 0.8.     

Biomolecule-assisted solvothermal synthesis and enhanced visible light photocatalytic performance of Bi<Subscript>2</Subscript>S<Subscript>3</Subscript>/BiOCl composites

Novel Bi₂S₃/BiOCl photocatalysts were successfully synthesized via a facile biomolecule-assisted solvothermal method and biomolecule L-cysteine was used as the sulfur source. The structures, morphology, and optical properties of the synthesized samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, transmission electron microscopy (TEM), and UV-vis diffuse reflectance spectroscopy (DRS). The presence of Bi₂S₃ in the Bi₂S₃/BiOCl composites could not only improve the optical properties but also enhance the photocatalytic activities for the degradation of Rhodamine B (RhB) under visible-light irradiation (λ > 420 nm) as compared with single Bi₂S₃ and BiOCl. Especially, the sample displayed the best performance of the photodegradation when the feed molar ratio of BiCl3 and L-cysteine was 2.4:1, which was about 10 times greater than that of pure BiOCl. The enhanced photocatalytic activities could be ascribed to the effective separation of photoinduced electrons and holes and the photosensitization of dye. Moreover, the possible photodegradation mechanism was also proposed, and the results revealed that the active holes (h⁺) and superoxide radicals (?O₂ ^?) were the main reactive species during photocatalytic degradation.     

Structure and infrared radiation property of Co<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Zn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript> ferrites by XAFS analysis

Co_1−x Zn _x Fe₂O₄ ferrites were prepared by solid state reaction. The microstructure and performance were studied by X-ray diffraction, X-ray absorption fine-structure analysis and IRE-2 infrared radiant test. It is found that infrared radiance show a nonlinear change with x, exhibiting the infrared radiance of this material improved and the average radiance in the 8–14 μm waveband reached 0.91. The Co³⁺ and Zn²⁺ ions are found to occupy both tetrahedral and octahedral sites, and correspondingly, the fraction of Fe³⁺ ions in B-site decreases nonlinearly in ferrites. The lattice parameters are found to concern with Zn²⁺, and the activation energy deduces from crystal strain and crystal vibrate increases with content Zn²⁺. The redistribution of the Co³⁺ and Zn²⁺ ions between tetrahedral and octahedral sites is related to the providing a selective tetrahedral and octahedral sites infrared radiance of Co_1−x Zn _x Fe₂O₄ ceramics with increasing x.     

Influence of Ti^4＋ doping on hyperfine field parameters of Mg0.95Mn0.05Fe2-2xTizxO4 （0 ≤x ≤ 0.7）

The mixed spinel ferrite system Mg_0.95Mn_0.05Fe_2−2x Ti_2x O₄ (0⩽x⩽0.7) was synthesized by the conventional solid-state reaction technique. The effect of Ti⁴⁺ doping was studied by using the M?ssbauer spectroscopy measurements at room temperature. From the analysis of the M?ssbauer spectra, it is observed that s-electron density, electric field gradient (EFG), quadrupole coupling constant (QCC) and the net hyperfine magnetic fields acting on the M?ssbauer nuclei-Fe_A ³⁺ and Fe_B ³⁺ change with the increase of Ti⁴⁺ doping in Mg_0.95Mn_0.05Fe₂O₄. The hyperfine magnetic field decreases with the increase of Ti⁴⁺ doping.     

Vacuum degree effects on betavoltaics irradiated by <Superscript>63</Superscript>Ni with differently apparent activity densities

For many current betavoltaics, beta sources and PN junction energy conversion units are separated. The air gap between the two parts could stop part of decay beta particles, which results in inefficient performance of the betavoltaic. By employing ⁶³Ni with an apparent emission activity density of 7.26×10⁷ and 1.81×10⁸ Bq cm^?2, betavoltaic performance levels were calculated at a vacuum degree range of 1×10⁵ to 1×10^?1 Pa and measured at 1.0×10⁵ and 1.0×10⁴ Pa, respectively. Results show that betavoltaic performance levels improve significantly as the vacuum degree increases. The maximum output power (P _max) exhibits the largest change, followed by short-circuit current (I _sc), open-circuit voltage (V _oc), and fill factor. The vacuum degree effects on I _sc, V _oc, and P _max of the betavoltaic with low apparent activity density ⁶³Ni are more significant than those of the betavoltaic with high apparent activity density ⁶³Ni. Moreover, the improved efficiencies of the measured performances are larger than the calculated efficiencies because of the low ratio of I _sc and reverse saturation current (I ₀). The values of I ₀, ideality factor, and shunt resistance were estimated to modify the equivalent circuit model. The calculation results based on this model are closer to the measurement results. The results of this research can provide a theoretical foundation and experimental reference for the study of vacuum degree effects on betavoltaics of the same kind.     

Effects of annealing processes on Cu<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Si<Subscript>1-<Emphasis Type="Italic">x</Emphasis></Subscript> thin films

The Cu _x Si_1-x thin films have been grown by pulsed laser deposition (PLD) with in situ annealing on Si (001) and Si (111), respectively. The transformation of phase was detected by X-ray diffraction (XRD). The results showed that the as-deposited films were composed of Cu on both Si (001) and Si (111). The annealed thin films consisted of Cu + η”-Cu₃Si on Si (001) while Cu + η’-Cu₃Si on Si (111), respectively, at annealed temperature (T _a) = 300-600 °C. With the further increasing of T _a, at T _a= 700 °C, there was only one main phase, η”-Cu₃Si on Si (001) while η’-Cu₃Si on Si (111), respectively. The annealed thin films transformed from continuous dense structure to scattered-grain morphology with increasing T _a detected by field emission scanning electron microscope (FESEM). It was also showed that the grain size would enlarge with increasing annealing time (t _a).     

Overcharge performance of LiMn2O4/graphite battery with large capacity

The LiMn₂O₄/graphite battery was fabricated and its 3 C/10 V overcharge performance was studied. Spinel LiMn₂O₄ was synthesized by solid-state method and 325680-type size full battery was fabricated. The structure and morphology of the powders were characterized by XRD and SEM technique, respectively. The battery explodes after 3 C/10 V overcharged test, and surface temperature of the battery case arrives at 290 °C in 12 s after exploding. Black air is given out with blast. Carbon, MnO, and Li₂CO₃ are observed in the exploded powders. The cathode electrode remains spinel structure with 5.0 V charged. Cracks in the cathode electrode particles are detected with the increase of voltage by SEM technique. The 5.0 V charged electrode can decompose into Mn₃O₄ at 400 °C. It is demonstrated that the decomposition of 5.0 V charged electrode can be promoted and Mn⁴⁺ can be deoxidized to Mn²⁺ by carbon and electrolyte through the simulation of blast process.