A new approach to the kinetics of size reduction in ball milling

The rate of breakage of feed in ball milling is usually represented in the form of a first-order rate equation. The equation was developed by treating a simple batch test mill as a well mixed reactor. Several case of deviation from the rule have been reported in the literature. This is attributed to the fact that accumulated fines interfere with the feed material and breaking events are masked by these fines. In the present paper, a new rate equation is proposed which takes into account the retarding effect of fines during milling. For this purpose the analogy of diffusion of ions through permeable membranes is adopted, with suitable modifications. The validity of the model is cross checked with the data obtained in batch grinding of ?850/+600 ?m size quartz. The proposed equation enables calculation of the rate of breakage of the feed at any instant of time.

The effect of crack closure on the grain size dependence of fatigue crack growth threshold

Recent studies (I-7) clearly indicate a strong dependence of fatigue threshold parameter, A K on grain size in several alloy systems. Attempts to explain these observations on the basis of crat~tortuosity (1,8), fracture surface roughness (5,9) and crack closure (6) appear to present a fairly clear picture of the mechanisms that cause a reduction in crack growth rates at threshold. In general, it has been shown that coarse grained microstructures exhibit higher fatigue threshold in low carbon steels (1,5) aluminium alloys (7) and titanium alloys (6). In spite of these observations, there exists (10-1#) considerable uncertainity about the manner in which the AK~L depends on prior austenitic grain size in quenched and tempered steels. Studies in quenched and tempered steels demonstrating both an increase (3,12,14) as well as a decrease (11,12) in AKth with an increase in prior austenitic grain size can be sought to illustrate this point. Occasionally , the absence of any sensitivity of AKth to the variations in prior austenitJc grain size has also been reported (11,13). While a few investigators (5-7) comfortably rationalised the grain size effects on AK~L on the basis of crack closure by a comparison in terms of the closure-free component of the thresho~Ifc~, AK -f such an approach has yet to be extended to high strength steels, An attempt has been made in t~et ,pthrg sent study to explai. n the effect of pri, or austeniti.c grain size on &Kth on the basis of crack closure measurements in a high strength steel.

Studies on the reduction of hematite by carbon

Single pellet experiments have been carried out in a nitrogen atmosphere to study the reduction of hematite by graphite in the temperature range 925 to 1060°C. The effect of variables such as c/Fe2O3 molar ratio, pellet size, and so forth, has been investigated. Gas analysis data show a continuous decrease in CO2/CO ratio during reduction, the values being far away from Fe/FeO equilibrium for wustite reduction by CO. The activation energies associated with different degrees of reduction appear to be widely different suggesting a possible changeover in reaction mechanism during the progress of reduction. X-ray diffraction studies confirm the stepwise nature of hematite reduction.

Physical chemistry of the reduction of calcium oxide with aluminium in vacuum

The physical chemistry of "aluminothermic" reduction of calcium oxide in vacuum is analyzed. Basic thermodynamic data required for the analysis have been generated by a variety of experiments. These include activity measurements in liquid AI-Ca alloys and determination of the Gibbs energies of formation of calcium aluminates. These data have been correlated with phase relations in the Ca-AI-0 system at 1373 K. The various stages of reduction, the end products and the corresponding equilibrium partial pressures of calcium have been established from thermodynamic considerations. In principle, the recovery of calcium can be improved by reducing the pressure in the reactor. However,, the cost of a high vacuum system and the enhanced time for reduction needed to achieve higher yields makes such a practice uneconomic. Aluminum contamination of calcium also increases at low pressures. The best compromise is to carry the reduction up to the stage where 3CaO-Al,O, is formed as the product. This corresponds to an equilibrium calcium partial pressure of 31.3 Pa at 1373 K and 91.6 Pa at 1460 K. Calcium can be extracted at this pressure using mechanical pumps in approximately 8 to 15 hr, depending on the size and the fill ratio of the retort and porosity of the charge briquettes.

Facile hydrothermal synthesis of carbon nanoparticles and possible application as white light phosphors and catalysts for the reduction of nitrophenol

We report a simple hydrothermal synthesis of highly reproducible carbon nanoparticles in a size range between 2 and 7 nmfroma single precursor sucrose without either surface passivating agents or acids and bases. The carbon nanoparticles can be used as white light phosphors, especially for ultraviolet light emitting diodes and metal-free catalyst for the reduction of nitrophenol.

Effect of size reduction on magnetic ordering in Bi0.2Sr0.8MnO3

We present a comparative study of the temperature dependent magnetic properties and electron paramagnetic resonance parameters of nano and bulk samples of Bi0.2Sr0.8MnO3 (BSMO). Bulk BSMO is known to have a high T-N similar to 260K and robust charge ordering (T-CO similar to 360 K). We confirm that the bulk sample shows an antiferromagnetic transition around similar to 260K and a spin-glass transition similar to 40 K. For the nano sample, we see a clear ferromagnetic transition at around similar to 120 K. We conclude that spin glass state, which is present due to the co-existence of antiferromagnetic and ferromagnetic states in the bulk sample, is suppressed in the nano sample and ferromagnetism is induced instead. (C) 2014 AIP Publishing LLC.

Ferroelectric phase coexistence by crystallite size reduction in BiFeO3-PbTiO3

Size effect in ferroelectrics has been extensively investigated in the past with the general consensus that the long-range ferroelectric ordering gradually disappears with decreasing crystallite size, eventually leading to the paraelectric state. In this paper, we show that the compositions exhibiting giant tetragonality (c/a similar to 1.18) of the ferroelectric alloy system BiFeO3-PbTiO3 transform from a pure tetragonal phase to a state comprising tetragonal and rhombohedral phases as the average crystallite size is reduced from similar to 10 to similar to 1 mu m. It is argued that the increased surface energy in the smaller sized crystallites creates an equivalent compressive stress that drives the system towards tetragonal-rhombohedral criticality.

Mixture of Fuels Approach for the Synthesis of SrFeO3-delta Nanocatalyst and Its Impact on the Catalytic Reduction of Nitrobenzene

A modified solution combustion approach was applied in the synthesis of nanosize SrFeO3-delta (SFO) using single as well as mixture of citric acid, oxalic acid, and glycine as fuels with corresponding metal nitrates as precursors. The synthesized and calcined powders were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis and derivative thermogravimetric analysis (TG-DTG), scanning electron microscopy, transmission electron microscopy, N-2 physisorption methods, and acidic strength by n-butyl amine titration methods. The FT-IR spectra show the lower-frequency band at 599 cm(-1) corresponds to metal-oxygen bond (possible Fe-O stretching frequencies) vibrations for the perovskite-structure compound. TG-DTG confirms the formation temperature of SFO ranging between 850-900 degrees C. XRD results reveal that the use of mixture of fuels in the preparation has effect on the crystallite size of the resultant compound. The average particle size of the samples prepared from single fuels as determined from XRD was similar to 50-35 nm, whereas for samples obtained from mixture of fuels, particles with a size of 30-25 nm were obtained. Specifically, the combination of mixture of fuels for the synthesis of SFO catalysts prevents agglomeration of the particles, which in turn leads to decrease in crystallite size and increase in the surface area of the catalysts. It was also observed that the present approach also impacted the catalytic activity of the SFO in the catalytic reduction of nitrobenzene to azoxybenzene.

Effect of Size Reduction on Magnetic Ordering in Sm1-x Ca (x) MnO3 (x=0.35, 0.65 and 0.92) Manganites: Magnetic and EMR Studies

We have employed the highly sensitive electron magnetic resonance technique complimented by magnetization measurements to study the impact of size reduction on the magnetic ordering in nanosized Sm1-x Ca (x) MnO3 (x = 0.35, 0.65 and 0.92). In the bulk form, x = 0.35 sample shows a charge ordering transition at 235 K followed by a mixed magnetic phase, the sample with x = 0.65 exhibits charge order below 275 K and shows an antiferromagnetic insulator phase below 135 K while that with x = 0.92 has a ferromagnetic-cluster glass ground state. Thus, a comparative study of magnetic ground states of bulk and nanoparticles (diameter similar to 25 nm) enables us to investigate size-induced effects on different types of magnetic ordering. It is seen that in the bulk samples the temperature dependences of the EPR parameters are quite different from each other. This difference diminishes for the nanosamples where all the three samples show qualitatively similar behavior. The magnetization measurements corroborate this conclusion.

Use of microwaves for the synthesis and processing of materials

An overview of the synthesis of materials under microwave irradiation has been presented based on the work performed recently. A variety of reactions such as direct combination, carbothermal reduction, carbidation and nitridation have been described. Examples of microwave preparation of glasses are also presented. Great advantages of fast, clean and reduced reaction temperature of microwave methods are emphasized. The example of ZrO2-CeO2 ceramics has been used show the extraordinarily fast and effective sintering which occurs in microwave irradiation.

Calciothermic reduction of TiO2: A diagrammatic assessment of the thermodynamic limit of deoxidation

Calciothermic reduction of TiO2 provides a potentially low-cost route to titanium production. Presented in this article is a suitably designed diagram, useful for assessing the degree of reduction of TiO2 and residual oxygen contamination in metal as a function of reduction temperature and other process parameters. The oxygen chemical potential diagram à la Ellingham-Richardson-Jeffes is useful for visualization of the thermodynamics of reduction reactions at high temperatures. Although traditionally the diagram depicts oxygen potentials corresponding to the oxidation of different metals to their corresponding oxides or of lower oxides to higher oxides, oxygen potentials associated with solution phases at constant composition can be readily superimposed. The usefulness of the diagram for an insightful analysis of calciothermic reduction, either direct or through an electrochemical process, is discussed. Identified are possible process variations, modeling and optimization strategies.

Electrochemical Reduction of Oriented Graphene Oxide Films: An in Situ Raman Spectroelectrochemical Study

Graphene oxide (GO) is assembled on a gold substrate by a layer-by-layer technique using a self-assembled cystamine monolayer. The negatively charged GO platelets are attached to the positively charged cystamine monolayer through electrostatic interactions. Subsequently, it is shown that the GO can be reduced electrochemically using applied DC bias by scanning the potential from 0 to -1 V vs a saturated calomel electrode in an aqueous electrolyte. The GO and reduced graphene oxide (RGO) are characterized by Raman spectroscopy and atomic force microscopy (AFM). A clear shift of the G band from 1610 cm-1 of GO to 1585 cm-1 of RGO is observed. The electrochemical reduction is followed in situ by micro Raman spectroscopy by carrying out Raman spectroscopic studies during the application of DC bias. The GO and RGO films have been characterized by conductive AFM that shows an increase in the current flow by at least 3 orders of magnitude after reduction. The electrochemical method of reducing GO may open up another way of controlling the reduction of GO and the extent of reduction to obtain highly conducting graphene on electrode materials.

Vapor-Pressure Of Calcium Corresponding To The Reduction Of Calcia By Aluminum

The equilibrium pressure of calcium corresponding to the reduction reaction 6CaO (s) + 2Al (l) half-arrow-right-over-half-arrow-left 3CaO.Al2O3 (s) + 3Ca (g) has been measured by Knudsen effusion - mass loss analysis in the temperature range 1190 - 1500 K. The measured vapour pressure can be expressed as a function of temperature by the relation: log p(Ca) (Pa) = -10,670/T + 9.267 The calcium generated is partially absorbed by aluminium to form an alloy. The equilibrium composition of the alloy at 1373 K was found to be 22 mol% Ca - 78 mol% Al. The measured vapour pressure is in good agreement with that computed from thermodynamic data.

Size dependence of the bulk modulus of semiconductor nanocrystals from first-principles calculations

The variation in the bulk modulus of semiconductor nanoparticles has been studied within first-principles electronic-structure calculations using the local density approximation (LDA) for the exchange correlation. Quantum Monte Carlo calculations carried out for a silicon nanocrystal Si87H76 provided reasonable agreement with the LDA results. An enhancement was observed in the bulk modulus as the size of the nanoparticle was decreased, with modest enhancements being predicted for the largest nanoparticles studied here, a size just accessible in experiments. To access larger sizes, we fit our calculated bulk moduli to the same empirical law for all materials, the asymptote of which is the bulk value of the modulus. This was found to be within 2-10% of the independently calculated value. The origin of the enhancement has been discussed in terms of Cohen's empirical law M.L. Cohen, Phys. Rev. B 32, 7988 (1985)] as well as other possible scenarios.

Combustion synthesis and properties of the NASICON family of materials

The fine-particle NASICON family of materials, MZr2P3O12(where M = Na, K, ½Ca and ¼Zr) and NbZrP3O12, have been prepared by the combustion of aqueous heterogeneous mixtures of stoichiometric amounts of metal nitrate, zirconyl nitrate, niobium phosphate, diammonium hydrogen phosphate, ammonium perchlorate and carbohydrazide (CH) at 400 °C. The formation of NASICON materials was confirmed by powder X-ray diffraction (XRD), IR, solid-state (31P) NMR spectroscopy and thermal expansion coefficient measurements. The combustion-synthesized NASICON powders have an average agglomerate size of 9�13 µm with a specific surface area varying from 8 to 28 m2 g�1. The powders pelletized and sintered in the range 1100�1200 °C for 5 h achieved 95�97% theoretical density and showed fine-grain microstructure. The coefficient of thermal expansion of a sintered compact was measured up to 500 °C and ranged from �1.5 × 10�6°C�1 to 1.0 × 10�6°C�1 depending on the composition.