俄罗斯：合成特殊的准单晶物质

莫斯科钢与合金研究所利用机械一化学合成法成功合成一种特殊的准单晶物质，在工业领域有广泛应用前景。在这种物质中，铁、铜、铝三种原子的排列不像普通单晶那样具有相同的晶格，但仍具有严格的顺序，呈现出几何排列。以橡胶和聚合物为底基，辅以这种准单晶物质制成的复合材料具有金属和陶瓷的双重特性，像金刚石一样坚硬，摩擦系数小于金属，化学稳定性和耐摩性很高。

Mechanochemical redox-based synthesis of highly porous CoxMn1-xOy catalysts for total oxidation

A mechanochemical redox reaction between KMnO4 and CoCl2 was developed to obtain a CoxMn1-xOy catalyst with a specific surface area of 479 m^2 g^-1,which was higher than that obtained using a co-precipitation(CP)method(34 m2 g^-1),sol-gel(SG)method(72 m^2 g^-1),or solution redox process(131 m^2 g^-1).During catalytic combustion,this CoxMn1-xOy catalyst exhibited better activity(T100 for propylene=~200℃)than the control catalysts obtained using the SG(325℃)or CP(450℃)methods.The mechanical action,mainly in the form of kinetic energy and frictional heating,may generate a high degree of interstitial porosity,while the redox reaction could contribute to good dispersion of cobalt and manganese species.Moreover,the as-prepared CoxMn1-xOy catalyst worked well in the presence of water vapor(H2O 4.2%,>60 h)or SO2(100 ppm)and at high temperature(400℃,>60 h).The structure MnO2·(CoOOH)2.93 was suggested for the current CoxMn1-xOy catalyst.This catalyst could be extended to the total oxidation of other typical hydrocarbons(T90=150°C for ethanol,T90=225°C for acetone,T90=250℃for toluene,T90=120℃for CO,and T90=540℃for CH4).Scale-up of the synthesis of CoxMn1-xOy catalyst(1 kg)can be achieved via ball milling,which may provide a potential strategy for real world catalysis.

Structural insights of mechanically induced aluminum-doped hydroxyapatite nanoparticles by Rietveld refinement

Aluminum doped hydroxyapatite （HA：AI3 ＋） nanopowders were successfully prepared via a simple and efficient one-pot mechanochemical route. The effects of dopant loading on phase compositions and structural features were assessed by Rietveld analysis. The XRD-Rietveld refinement revealed the stabilization of HA in hexagonal structure for all the samples. The sharpness and intensity of the apatite-derived XRD peaks decreased as the dopant content increased to 10% due to the increase in lattice imperfections and mechanically induced amorphization. The incorpo- ration of A13 ＋ into the HA lattice decreased the unit cell parameters. From the FfiR measurements, the representing bands of apatite were identified in all cases. The mechanosynthesized nanopowders consisted of nanospheroids with an average size of 44 - 20 nm and therefore are promising for bone tissue regeneration.

Synthesis of Crystalline Hydroxyapatite from CaCO_3 and CaHPO_4·2H_2O by Mechanochemical Method

The mixture of CaHPO 4·2H 2O and CaCO 3 was ground in an aqueous system under appropriate conditions to investigate the mechanochemical reaction for the synthesis of crystalline hydroxyapatite (HA) powder. Hydroxyapatite of high crystallinity powder including trace Ca 10 (PO 4) 6CO 3(OH) and Ca 9HPO 4(PO 4) 6OH can be synthesized by mechanical activation without further thermal treatment at a high temperature. The synthesis reaction during the grinding process was almost completed within 1h. The as-ground powder exhibits a particle distribution of 20-100nm in size with a spherical or rodlike morphology. The composition and degree of crystallinity of the mechanochemical synthesized hydroxyapatite powders were coincident with the cement-type hydroxyapatite.

特殊准单晶物质

俄罗斯利用机械-化学合成法成功合成一种特殊的准单晶物质，在工业领域有广泛应用前景。这种物质中的铁、铜、铝三种原子排列不像普通单晶具有相同的晶格，但有严格的顺序，呈几何排列。以橡胶和聚合物为底基．辅以这种准单晶物质制成的复合材料，具有金属和陶瓷的双重特性．像金刚石般坚硬．摩擦系数小于金属．化学稳定性和耐磨性很高。

Synthesis of niobium borides by powder metallurgy methods using Nb_(2)O_(5), B_(2)O_(3) and Mg blends

Niobium boride powders having NbB, NbB2 and Nb3B4 phases in various amounts and single phase NbB powders were successfully synthesized by using powder metallurgy methods from related metal oxide raw materials in the presence of a strong reducing agent. Nb2O5, B2O3 and Mg powder blends were milled at room temperature by a high-energy ball mill for different time. Subsequently, undesired MgO phase was removed from the milled powders by HCl leaching to constitute NbB?NbB2?Nb3B4 as final products and they were subjected to an annealing process at 1500 °C for 4 h to observe probable boride transformation. Characterization was carried out by XRD, DSC, PSA, SEM/EDX, TEM and VSM. The effects of milling time (up to 9 h) on the formation, microstructure and thermal behavior of the final products were investigated. Reduction reaction took place after milling stoichiometric powder blends for 2 h. Nano-sized NbB?NbB2?Nb3B4 powders in high purity were obtained in the absence of any secondary phase and any impurity via mechanochemistry by milling for 5 h and leaching with 4 mol/L HCl. After annealing, pure and nano-sized NbB?NbB2?Nb3B4 powders transformed to a single NbB phase without leaving behind NbB2 and Nb3B4 phases.

Exchange Interactions at the Interface FMIAFM Nanocomposite Obtained by Mechanochemical Synthesis

This paper presents a study of the relationship between the magnetic properties and microstructure of nanocomposite Ni/MnO, Ni/CoO, Co/MnO, Co/CoO. The objective is to understand how the coupling interface FM/AFM （ferromagnetic/anti-ferromagnetic） manifests itself in magnetic response of these materials to an applied field. Sample preparation was performed using mechanochemical synthesis by means of a ball mill planetary type high power at normal atmosphere. The characterization was done by XRD （X-ray diffraction）, SEM （scanning electron microscopy） and VSM （vibrating sample magnetometry）. Analyzing the XRD peaks of the samples studied, there was a decrease in the average particle diameter with increasing milling time, which is important in the magnetic interactions of the atoms of the surface. In addition, the diffraction pattern showed formation of new phases by oxidation interfering with the magnetic measurements. Analyses by SEM show chipboard multiform nano- and micrometer-sized grains on the surface of the clusters being responsible for the interaction. The magnetic measurements show a strong coupling between the phases present in nanocomposites showing once again that the MS （mechanosynthesis） is a powerful technique for this kind of purpose. The effect of the decrease in crystallite size leads to large variations of magnetic properties of the material which have been specifically observed changes in HC （coercive field） in the RM （remanent magnetization） and SM （saturation magnetization）. The decrease in crystallite size in the course of grinding intensifies the effects that depend on the surface-to-volume ratio of the material. M vs. T measures were taken for different values of applied field and found a jump in the moment of the sample near the N6el temperature of the antiferromagnetic.

Unraveling the mechanochemical synthesis and luminescence in MnⅡ-based two-dimensional hybrid perovskite（C4H9NH3）2PbCl4

The mechanochemical route is a facile and fast way and has received much attention for developing versatile advanced functional materials. Herein, we reported a mechanochemical synthesis for incorporating divalent manganese ions (Mn^Ⅱ) into a two-dimensional (2D) hybrid perovskite (C4H9NH3)2PbCl4. The mild external stimuli originating from the grinding at room temperature enabled the formation of Mn^Ⅱ-doped 2D hybrid perovskites, and rapidly changed the luminescence characteristics. The photoluminescence analyses show that the violet and orange emissions are attributed to (C4H9NH3)2Pb1-xMnxCl4 band-edge emission and the T1→^6A1 transition of Mn^2+ resulting from an efficient energy transfer process, respectively. Site preference and distribution of the doped Mn^2+ cations on the locations of Pb^2+ were analyzed. The formation energy calculated by the density functional theory (DFT) indicates that the Mn^2+ ions can rapidly enter the crystal lattice due to the unique 2D crystal structure of the hybrid perovskite. Such a case of mechanochemical synthesis for the 2D hybrid perovskite motivates many novel emerging materials and the related applications.