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.

Mechanochemical decomposition of pentachlorophenol by ball milling

The mechanochemical dechlorination of pentachlorophenol （PCP） was studied using CaO and SiO2 powder as additives. The effects of the milling time and additives on the dechlorination rate were investigated. The resulting product was characterized by X-ray diffraction （XRD）, Fourier transform infrared spectra （FT-IR）, thermogravimetric analysis （TG） and ion chromatography （IC）. It is found that grinding operation could dechlorinate PCP, with the formation of inorganic chloride and amorphous carbon. The addition of quartz to the grinding mixture facilitated dechlorination. On the basis of the experimental results, the decomposition mechanism was proposed. Decomposition predominantly proceeds through rupture of C-Cl bond in PCP molecule, followed by the formation of inorganic chlorides.

Hydrodesulfurization activities of NiMo catalysts supported on mechanochemically prepared Al-Ce mixed oxides

Al2O3-CeO2 supports containing 1-10 wt%Ce were prepared mechanochemically by milling aluminum and/or cerium nitrates with NH4HCO3.Heteropolymolybdate,（NH4）4NiMo6O（24）,was used as the precursor of the Ni and Mo to prepare NiMo6/Al2O3-CeO2 components in catalysts by impregnation method.The physicochemical properties of the catalysts were determined using chemical analysis,X-ray diffraction,temperature-programmed H2 reduction,temperature-programmed NH3 desorption,X-ray photoelectron spectroscopy（XPS）,and the Brunauer-Emmett-Teller method.The catalyst acidity decreased with increasing Ce concentration in the support.XPS showed that the NiS/MoS ratio decreased two-fold for the Ce-modified alumina support.NiMo6/Al2O3,which had the highest acidity,showed the highest activity in hydrodesulfurization of 1-benzothiophene（normalized per weight of catalyst）.The concentration of surface MoOxSy species（which is equal to the concentration of Mo^（5＋）） gradually decreased to zero for catalysts with Ce concentrations 10 wt%.However,the activities of all the catalysts prepared mechanochemically from Al2O3 and Al2O3-CeO2supports significantly exceeded that of a reference NiMo6/Al2O3 catalyst prepared by impregnation method using the same precursor and with the same composition.

Mechanochemical sulfidization of a mixed oxide-sulphide copper ore by co-grinding with sulfur and its effect on the flotation efficiency

Mechanochemical sulfidization of a mixed sulfide/oxide copper ore by co-grinding with sulfur and additives including Mg(NO3)2 and Fe(NO3)3 salts and iron,aluminum and magnesium powders was investigated for the first time.Also,the influence of sulfidization during the wet-milling process was examined on the separation efficiency and recovery of copper in detail.The results demonstrated that co-grinding with sulfur solely had the best flotation performance at the value of 0.5 wt.%and it was attributed to the possible existence of S\\O bonding on copper oxides surfaces.In addition,adding magnesium nitrate salt,magnesium powder,iron nitrate salt and aluminum powder as additive associated with 0.5 wt%sulfur into ball milling caused the flotation improvement at the amounts of 0.2 wt%,0.2 wt%,0.5 wt%and 0.5 wt%,respectively.Also,the effect of grinding time and sulfidization pH with 0.5 wt%sulfur solely was determined and pH s of 7.5 to 8.5 gave the best results.The highest recovery(75.76%)and separation efficiency(63.44%)were achieved at pH of 7.5 and 8.5,respectively.

Isothermal kinetics of mechanochemically and thermally synthesized Ag from Ag_2O

The kinetics of isothermal reduction of Ag2O with graphite under argon atmosphere for a non-activated sample and mechanically activated sample was investigated.It is found that Johnson-Mehl-Avrami model appropriately explained the thermal and mechanochemical synthesis of Ag from Ag2O＋ghraphite mixture.The process kinetics was investigated using the same approach for milled and unmilled samples.The results show that the Avrami exponent of mechanochemical reduction is higher than that of high temperature thermal reduction.Also,the mechanisms of nuclei growth in thermal and mechanochemical reduction are diffusion controlled and interface controlled,respectively.

Mechanochemical Dispersion of Nanodiamond Aggregates in Aqueous Media

A technology of mechanochemical treatment (MCT) is introduced to modify nanodiamond (ND) surface aiming to obtaining a stable suspension with well-dispersed ND particles in aqueous medium. ND investigated in this paper is a purified product of nanometer-sized diamond synthesized by explosive detonation. As obvious aggregation and sediment were observed when the sample was added into deionized water, it is crucial to conduct deaggregation and dispersion investigations. Amid a series of mechanical treatments, i.e. grinding, stirring, ultrasonic and classification, some reagents are introduced to modify the newly created surface during aggregates comminution. For the co-effects of mechanical forces and surfactants, the mean size of particles was reduced and a stable system containing ND with narrow size distribution was prepared. Mechanism of surface reaction and modification are discussed, while AFM, Zetasizer3000HS, XRD, XPS and FTIR are utilized for the analysis. The functional chemical structure of ND particle surface and surface electrical property changed during the modification processes, and the dispersion character and stability of suspension can consequently be improved.

Enhancement of leaching of cobalt and lithium from spent lithium-ion batteries by mechanochemical process

A mechanochemical method with SiO_(2)as the grinding aid was used to enhance the leaching efficiencies of Co and Li from spent lithium batteries(LIBs).Experiment results show that the optimal leaching efficiencies of 94.91%for Co and 97.22%for Li were obtained under the parameters of SiO_(2)/LiCoO_(2)mass ratio of 1:1,grinding speed of 500 r/min and grinding time of 30 min in citric acid.Characterization results indicate that the surficial properties of LiCoO_(2)were changed after mechanochemical grinding treatment due to the newly generated surfaces on LiCoO_(2).Meanwhile,the incompletely coordinated atomic structure and defective lattice structure lead to the activation of LiCoO_(2).The reduction effect of carbon black on Co^(3+)under the action of mechanical forces increases its leaching efficiencies in the citric acid solution.The proposed process was found efficiently to recover Co and Li from LiCoO_(2).

Preparation of nanostructure silver powders by mechanical decomposing and mechanochemical reduction of silver oxide

The mechanical decomposing and mechanochemical reductions of silver oxide for preparation of nanocrystalline silver powders by high planetary ball mill was investigated. XRD and HRSEM techniques were used to characterize the structural evolution and morphological changes of products. The results show that the nanostructured silver with an average crystallite size of 14 nm and internal strain of 0.75% is synthesized by mechanical decomposing of Ag2O after 95 h milling. While, the product of mechanochemical reduction of silver oxide using graphite after 22 h milling is nanostructured silver with an average crystallite size of 28 nm and internal strain of 0.44%.

Mechanochemical leaching of chalcopyrite concentrate by sulfuric acid

This study aimed to introduce a new cost-effective methodology for increasing the leaching efficiency of chalcopyrite concentrates at ambient temperature and pressure. Mechanical activation was employed during the leaching（mechanochemical leaching） of chalcopyrite concentrates in a sulfuric acid medium at room temperature and atmospheric pressure. High energy ball milling process was used during the leaching to provide the mechanochemical leaching condition, and atomic absorption spectroscopy and cyclic voltammetry were used to determine the leaching behavior of chalcopyrite. Moreover, X-ray diffraction and scanning electron microscopy were used to characterize the chalcopyrite powder before and after leaching. The results demonstrated that mechanochemical leaching was effective; the extraction of copper increased significantly and continuously. Although the leaching efficiency of chalcopyrite was very low at ambient temperature, the percentages of copper dissolved in the presence of hydrogen peroxide（H2O2） and ferric sulfate（Fe2（SO4）3） after 20 h of mechanochemical leaching reached 28% and 33%, respectively. Given the efficiency of the developed method and the facts that it does not require the use of an autoclave and can be conducted at room temperature and atmospheric pressure, it represents an economical and easy-to-use method for the leaching industry.

Characterization of carbon fibers recovered through mechanochemical-enhanced recycling of waste carbon fiber reinforced plastics

In this study,we present the characterization of the carbon fibers recovered from the mechanochemical-enhanced recycling of carbon fiber reinforced fibers.The objectives of the study were to investigate the effect of our modified recycling method on the interfacial properties of recovered fibers.The reinforced plastics were recycled;the recycling efficiency was determined and the recovered fibers were sized using 1 wt%and 3 wt%concentration of(3-aminopropyl)triethoxysilane.We characterized the morphologies utilizing the electron spectroscopy for chemical analysis(ESCA),atomic force microscopy(AFM),FTIR-attenuated total reflection(ATR)spectroscopy and scanning electron microscopy(SEM).Although the surface of the fibers had no cracks,there was evidence of contaminations which affected the interfacial properties and the quality of the fibers.Results showed that the trends in the recovered and virgin fibers were similar with an increase in sizing concentration.The results highlighted the perspectives of increasing the quality of recovered fibers after the recycling process.

Mechanochemical Reaction of Lanthanum Carbonate with Sodium Hydroxide and Preparation of Lanthanum Oxide Nanoparticle

The preparation of nano sized La 2O 3 powder by mechanochemical reaction of lanthanum carbonate with sodium hydroxide and subsequent heat treatment was studied using X ray diffraction, differential thermal and thermo gravimetric analysis and transmission electron microscopy. It was found that the mechanochemical reaction process can be divided into two steps: the first step is the multi phases mechanochemical reaction of lanthanum carbonate with NaOH to form amorphous lanthanum basic carbonate and lanthanum hydroxide, and the second step is the crystallization of basic lanthanum carbonate with the formula of La 2(OH) 2(CO 3) 2·H 2O under a quasi hydrothermal synthesis condition caused by the mechanical ball milling. The synthesized La 2O 3 powder appears clearly separated spherical like monodisperse nano size particles in which particle size ranges from 30 to 50 nm.

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.

Mechanochemical Synthesis of Visible-light Induced Photocatalyst with Nitrogen and Carbon Doping

Nitrogen and/or carbon doped titania photocatalysts were prepared by a novel mechanochemical method. The prepared powders possessed two absorption edges around 400 and 540 nm wavelengths and showed excellent photocatalytic ability for nitrogen monoxide oxidation under visible light irradiation. Under the irradiation of visible light of wavelength >510 nm,37% of nitrogen monoxide could be continuously removed by the carbon and nitrogen co-doped titania prepared by planetary ball milling of P-25 titania–10% hexamethylenetetramine mixture followed by calcination in air at 400-C.

Preparation of Well Dispersed and Ultra-Fine Ce(Zr)O_2 Mixed Oxide by Mechanochemical Processing

Ultra-fine CeO_2-ZrO_2 mixed oxide was successfully synthesized by wet-solid phase mechanochemical processing, Ce_2(CO_3)_3·8H_2O, ZrOCl_2·xH_2O and ammonia were used as reactants. It is found that the crystalline Ce_2(CO_3)_3·8H_2O and ZrOCl_2·xH_2O are changed to amorphous cerium and zirconium hydroxide precursor after milling with ammonia, and Ce_(0.15)Zr_(0.85)O_2 mixed oxide with pure tetragonal phase structure and medium particle size(D_(50))less than 1μm is formed by calcining precursor over 673 K. The XRD patterns indicate that the crystal unite size increases with rising calcining temperature due to crystal growth. However, the particle size and BET surface area of the Ce(Zr)O_2 mixed oxide decreases with rising calcining temperature, which may be attributed to the contract of particles and the vanish of holes inside grains.

Mechanosynthesis and mechanochemical treatment of bismuth-doped vanadium phosphorus oxide catalysts for the partial oxidation of n-butane to maleic anhydride

Three Bi-doped vanadyl pyrophosphate catalysts were prepared via dihydrate route （VPD method）, which consisted of different preparation methods including mechanosynthesis, mechanochemical treatment, and the conventional reflux method. The catalysts produced by the above three methods were characterized by x-ray diffraction （XRD）, scanning electron microscopy （SEM）, and temperature programmed reduction （TPR）. Catalytic evaluation for the partial oxidation of n-butane to maleic anhydride （MA） was also carried out. The XRD patterns of all the Bi-doped catalysts showed the main peaks of pyrophosphate phase. Lower intensity peaks were observed for the mechanochemically treated Bi-doped catalyst （VPDBiMill） with two additional small peaks corresponding to the presence of a small amount of V5＋ phase. The TPR profiles showed that the highest amount of active oxygen species, i.e, V4＋–O- pair, responsible for n-butane activation, was removed from VPDBiMill. Furthermore, from the catalytic test results, the graph of selectivity to MA as a function of the conversion of n-butane demonstrated that VPDBiMill was the most selective catalyst. This suggests that the mechanochemical treatment of vanadium phosphate catalyst （VPDBiMill） is a potential method to improve the catalytic properties for the partial oxidation of n-butane to maleic anhydride.

Preparation of Compound Ultrafine CeO2 by Wet-Solid-Phase Mechanochemical Modification

To satisfy practical requirements from industrial applications, an alternate route for synthesis compound ultrafine CeO2 powders by wet-solid-phase mechanochemical modification using industrial grade hydrated cerium carbonate as raw material was proposed.The effect of modifier reaction percentage, reaction time, calcining temperature and modifier amount on particle size, density, suspensibility, and hardness of compound CeO2 powder was investigated.The phase evolutions of preparation process were characterized by XRD.SEM micrograph of the final product shows that compound CeO2 powders obtained are well-dispersed, spherically-shaped, uniformly-sized and submicron-sized particles.The method is readily available in raw material, low in cost, simple in process, and has great potential for industrialization.The compound CeO2 powders of different physical properties can be synthesized by controlling the above-mentioned influence factors in preparation process.

Ultramicro molybdenum nitride powder prepared using high-energy mechanochemical method

Using the specially designed mechanochemical ball-mill equipment, ultramicro molybdenum nitride powders were prepared from pure molybdenum powders in ammonia atmosphere at room temperature by high-energy ball milling. The structure and the particle size of the powders were investigated by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, and transmission electron microscopy （TEM）. The results show that the mass ratio of grinding media to powder was 8：1, after milling for 30 h the Mo2N of fcc structure was obtained, and the average particle size of the powders was around 100 nm. It is found that the chemisorption of ammonia onto the fresh molybdenum surfaces created by milling was the predominant process during solid-gas reaction, and the energy input due to introduction of highly dense grain boundaries and lattice defects offered the activation energy for the transition from Mo-N chemisorption to molybdenum nitride. In addition, the change of Mo electronic undersaturation induced by the grain refining accelerated the bonding between Mo and N. The mechanism model of whole nitriding reaction was given, During the high-energy ball milling processing, the rotational speed of milling played a critical role in determining the overall reaction speed.

Mechanochemical model for myosinⅡdimer that can explain the spontaneous oscillatory contraction of muscle

The spontaneous oscillatory contraction（SPOC） of myofibrils is the essential property inherent to the contractile system of muscle. Muscle contraction results from cyclic interactions between actin filament and myosin II which is a dimeric motor protein with two heads. Taking the two heads of myosin II as an indivisible element and considering the effects of cooperative behavior between the two heads on rate constants in the mechanochemical cycle, the present work proposes the tenstate mechanochemical cycle model for myosin II dimer. The simulations of this model show that the proportion of myosin II in different states periodically changes with time, which results in the sustained oscillations of contractive tension, and serves as the primary factor for SPOC. The good fit of this model to experimental results suggests that the cooperative interaction between the two heads of myosin II dimer may be one of the underlying mechanisms for muscle contraction.

Effects of iron precursors on the structure and catalytic performance of iron molybdate prepared by mechanochemical route for methanol to formaldehyde

Mechanochemical synthesis has been applied for many novel material preparations and gained more and more attention due to green and high-efficiency recently. In order to explore the influences of iron precursors on structure and performance of iron molybdate catalyst prepared by mechanochemical route, three typical and cheap iron precursors have been used in preparation of iron molybdate catalyst. Many characterization methods have been employed to obtain the physical and chemical properties of iron molybdate catalyst. Results indicate that iron precursors have the significant impact on the phase composition, crystal morphology and catalytic performance in the conversion of methanol to formaldehyde. It is hard to regulate the phase composition by changing Mo/Fe mole ratios for Fe2(SO4)3 as iron precursor. In addition, as for Fe2(SO4)3, the formaldehyde yield is lower than that from iron molybdate catalyst prepared with Fe(NO3)3·9H2O due to the reduction in Fe2(MoO4)3 phase as active phase. Based on mechanochemical and coprecipitation method, the solvent water could be a key factor for the formation of MoO3 and Fe2(MoO4) for FeCl3·6H2O and Fe2(SO4)3 as precursors. Iron molybdate catalyst prepared with Fe(NO3)3·9H2O by mechanochemical route, shows the best methanol conversion and formaldehyde yield in this reaction.

Mechanochemically Metamorphosed Composites of Homogeneous Nanoscale Silicon and Silicate Oxides with Lithium and Metal Compounds

An active anode material for Li-ion batteries was synthesized using a simple mechanochemical process to minimize the large change in Si volume observed during charge-discharge operation and to compensate for the associated irreversible loss of Li or irreversible capacity loss, which are obstacles to achieve high-performance electrochemical properties during charge-discharge. The composite was mechanochemically milled with Si, lithium oxide, and copper oxide as raw materials;the composite contains Si nanoparticles, amorphous silicon monoxide, and Si-Li or Si-Cu alloy compounds, and it exhibits improved electrochemical properties. In particular, this composite achieved a better capacity retention, higher coulombic efficiency (over 100%), and longer cycling performance than Si alone, indicating considerable optimization of the electrical and ionic conductivity in the composite. The developed method allowed for control of the Li content to compensate for the lack of Li ions in the composite, and the cycling performance was optimized using the Cu alloy, oxide, and Li compounds within the composite.