Search Documents

By Don H. Baker

THE need for new or improved refractory materials has caused metal phosphides to be given renewed scrutiny. Some metal phosphides show high-temperature inertness, are exceptionally hard, and exhibit a marked resistance to chemical attack. Various metal phosphides have been prepared for study by direct combination of the elements,'-' by reaction of metal or metal compounds with phosphine or phosphorus trichloride,'"' by thermal decomposition of a metallic phosphate or phosphite,"-'8 and by molten salt electrolysis.19 Electrolytic preparation of phosphides of titanium, manganese, and chromium from their oxides is reported in this paper. An externally heated 3-in.-ID by 6-in.-deep graphite cell, that served as the anode as well as a container for the electrolyte, was used in these investigations, and a suspended, centrally positioned graphite rod served as the cathode. A closely fitting silicon carbide furnace liner minimized atmospheric oxidation of the crucible. Electrolyses were performed for predetermined periods and current settings. Preliminary research had indicated the more efficient current and potential settings that could be used. Upon completion of the deposition period, the deposit was hot-stripped from the cathode. The mass of crystalline deposit, plus occluded and adhering salt, was crushed to minus 10 mesh and hot-leached in dilute hydrochloric acid. The leached crystalline material was water-washed, dried, and sampled for analysis. Products were identified by X-ray diffraction and standard analytical procedures. Electrochemical studies were initiated to establish the optimum conditions necessary to produce manganese phosphide (MnP), titanium phosphide (Tip), and chromium phosphide (CrP). Among the factors studied were the operating temperature, the imposed current, and the electrolyte system. If the temperature, or imposed current, was too high, deposition of phosphorus resulted, and if either were too low, partially reduced lower oxides were deposited. The operating conditions established for repetitive high-quality production of metal phosphides of the MP structure are presented in Table I. The metal phosphide crystals varied in size, but all had a definite metallic appearance. Typical are the crystals of CrP shown in Fig. 1. Evaluation data and analysis of the crystals are presented in Table 11. Efforts to measure resistivity of these three compounds over the temperature ranges of 250o to 400°K were hampered by the small physical size of the crys-

Jan 1, 1968

By J. W. Fuller

During the last 20 years, experimenters have sought to utilize pulverized coal in boiler plants, but refractory and slag troubles have usually overbalanced any gains in efficiency that were obtained. These troubles were caused largely by lack of knowledge of the proper methods of coal preparation and lack of a furnace design that would be adaptable to pulverized-coal firing. When this information was obtained the results were so much more satisfactory that within the last 5 years approximately 80,000 boiler hp. have been installed in plants ranging from 1000 to 20,000 boiler hp. rated capacity, which are operating at an average of 174 per cent. of rating. The first commercial installation for burning pulverized coal under boilers was made at the Parsons shops of the M. K. & T. railroad in 1916. Of eight 250-hp. water-tube boilers thus fitted, six were operated continuously for 3 yr., when oil was obtained at such a low price as to warrant its use. Since then, this plant has been operating alternately on pulverized coal and oil, depending on prevailing prices. Recently gas has been discovered within 20 mi. of this plant, so that this fuel may also be used. No change in furnace design was made when changing from pulverized coal to oil or gas firing. One of the principal advantages of this method of firing is its ability to utilize, with maximum efficiency, all kinds of coal, irrespective of quality or physical characteristics. In fact, quite a number of the present pulverized-coal installations were made for the purpose of utilizing coal that could not be marketed or used in any other way. The Pacific Coast Coal Co., at Black Diamond, Wash., formerly hand fired the boilers, using approximately 125 tons of prepared steam-size coal daily. The Black Diamond steam coal is the best quality of coal for steaming purposes mined in that section of the country, and there is a market for all that can be produced. By installing a pulverizing plant, it was possible to substitute coal of a size and quality that had no commercial value, so that 125 tons daily of the best steam coal formerly used at the mines is now marketed. This company made a similar installation, at its New Castle, Wash., mine with approximately similar results. Each of these two plants has a

Jan 1, 1922

By William Conger, Greg Schick

Grinding media consumption is a major cost variable in industrial mineral comminution circuits. Specifically, industrial SAG media consumption results from a combination of surface abrasion wear, media breakage, surface spalling and rejection size from the mill. Three main consumption rates; weight of media consumed per time, per kWh and per weight of ore ground are defined and compared. Recent industrial data has provided an opportunity to relate consumption in terms of weight of media consumed to weight of ore ground (g/tonne) and weight of media consumed per kWh of energy consumed (g/kWh) with SAG specific grinding energy consumed (kWh/tonne). Using relationships developed from this data it is possible to project SAG media consumption in future mineral comminution circuits.

Jan 1, 2014

By T. Markus, K. Hilpert

Discharge vessels of advanced light sources are made of translucent polycrystalline Al2O3(PCA).These tubes contain salt mixtures, which essentially consist of metal halides. The salt mixture is present as a melt at the coldest spot of the vessel under operating conditions and vaporizes partly. The temperatures of the coldest spot range between 1200 K and 1300 K, depending on the lamp performance. The maximum wall temperatures range up to 1500 K and for special purposes up to1700 K. Important constituents of the melt are alkali halides AX (A = Na, Cs, X= Br, I) and rare earth metal halides LnX3(Ln = Dy, Ho, Tm). Severe corrosion attack on the wall material is observed in the PCA discharge vessels. The aim of this work is to elucidate the corrosion mechanism. Annealing experiments under well defined temperatures were carried out in order to understand the complex chemical corrosion processes. Two different annealing vessels were used, one for experiments under isothermal conditions with a temperature of 1473 K and one for experiments with a linear temperature gradient from 1450 K to 1600 K. The vessels were filled with salt mixtures of different compositions and annealed for 1000 h. The corrosion attack was characterised by XRD, analytical electron microscopy, high temperature mass spectrometry, and chemical analysis of the salt melts. The results of our investigations show that the corrosion attack is caused by vapour species and by the salt melt. The most severe corrosion is observed in vessels filled with mixtures of alkali halides and rare earth metal halides. No corrosion of the alumina is practically observed if pure alkali halides or pure rare earth metal halides are present in the annealing vessel. Keywords: thermodynamic, corrosion, lamps, metal halide salt

Jan 1, 2004

By Joan C. Biordi

[Composition profiles for atomic, radical, and stable species, as well as temperature and area expansion ratio profiles, have been determined for a nearly stoichiometric CH4-02-Ar flame and one to which 0.3 percent CF5Br inhibitor had been added. Net reaction rate profiles were calculated for all the observed species. For the normal flame, these and the mole fraction profiles gave rate coefficient information about the elementary reactions in the methane flame, for example, CH. + 0 4- H2CO 0 H, k4 = 1.05 X 1014CM3 mole-1sec-1 for 1,550§T 0,725' K; CO + OH 4 C02 + H, k6= 4.7 X 1011 for 1,350{T X1,750° K. Comparison between the inhibited and normal flame showed that A] and [CH3] were significantly reduced at the lower temperatures in the inhibited flame even though in the hot gas region the [E] [OH!, and [0] were essentially the same in both flames. The CF3Br disappears very early in the flame, relative to the fuel, and the reaction primarily responsible for its disappearance is H v CF3Br 4 HBr + CF3, where k7 is found to be 2.2 X 1014 exp(-9460/RT) for 700-1,550° K. Reaction of the inhibitor with methyl radicals provides for the relatively small amounts of CH3Br observed, but CH3 + Br2 - CHs Br + Br must also occur. The HBr formed reacts rapidly with H atoms to form H2 and Br, but the reaction is soon "balanced" in the flame as may be demonstrated by calculation of the equilibrium constant at various temperatures. The fluoro-carbon fragment produced in reaction (7) also reacts rapidly, in part with methyl radicals to give the observed elimination product CH2CF2 Later in the flame, above -1,400' K, F2CO is formed from the reaction CH2CF2 + 0 P F2CO + CH2 and k., -1.5 X 1013 at 1,600° K. The rather slow decay of carbonyl fluoride is attributed to reaction with H atoms according to the sequence F2CO I H - HF + FCO and FCO + H HF + CO.]

Jan 1, 1975

By Gordon A. R

The effect of various types of solid carbonaceOlls reductants on the rate of fuming of zinc from lead blast furnace slag was investigated at I250°C.The results of the laboratory experiments indicated that the rate of removal of zinc from slag depended primarily on the volatile matter contents of the reduclants. The effects of fixed carbon, moisture and ash contents were less significant.

Jan 1, 1992

By R. H. Derammelaere

With renewed interest in coal slurry pipelines in China, Indonesia, Australia and Canada for electric generation, it appears worthwhile to update the relative economics of transporting coal by slurry pipeline. Three slurry pipeline technologies are evaluated for the commercial transportation of 3.0, 6.0, and 9.0 million tonnes per year (MMT A) example cases, over distances of 250 km, 500 km and 1000 km.

Jan 1, 1998

By Shamsher Prakash

Equivalent spring constants for analysis of footings is a function of Young's modulus of pile material (Ep), shear modulus of soil (Gs), and geometry of the footing and/or piles. Shear modulus is strongly strain dependent in soils. Therefore, the spring constants are strain dependent, which is acceptable to the Geotechnical engineers. However, structural engineers prefer to use spring constants as a function of displacement, rather than strain. In order to develop these relationships, appropriate relationships between strain and displacement are needed. Also, modulus degradation with strain needs be built into these relationships. Description of spring constants kx , ky, and kz in x, y, and z direction and k?, k?, k?, about x, y, and z directions are relatively simple. However, description of kxø and ky?, the cross-coupling spring constants depend on 2 - components of displacement and rotation. Thus, there are 8 spring constants and likewise there are 8 damping constants. Approximate strain-displacement relationships on which displacement dependant k's and c's are based are presented with appropriate equations, and a numerical example is included illustrating k's and c's as functions of displacement.

Jan 1, 2002

By D. Walton

The effect of small solute additions of Cu on the activation energies for creep A1 single crystals were determined over the range from 78° to 850° K. Below 240°K and above 800°K activation energies were unchanged. Between 240°K and 400°K strain aging causes the creep rate to become vanishingly small and the flow stress was independent of the temperature. Between 500° and 50°K the activation energy was increased to 41,000 cal per mole. NUMEROUS investigationsL have shown that solid solution alloying invariably increases the flow stress. A typical example is documented in Fig. 1. Such increases in flow stress can arise from two general effects: Alloying can increase the long-range stress fields through which dislocations must move by causing appropriate clustering; modification of dislocation densities, and so forth. Alloying can also modify the short-range stress fields that determine the activation energies for thermally stimulated migration of dislocations, such as occurs in some solute atom pinning processes, and so forth. Actually both long- and short-range stress-field effects can occur simultaneously. It was the purpose of this investigation to evaluate the effect of alloying on the short-range stress fields by determining the effect of alloying on the activation energies for creep. The resulting observations also shed some light on the effect of long-range stress fields on dislocation processes. EXPERIMENTAL TECHNIQUE Single-crystal bars (6 in. long 3/8 in. wide and l/4 in. thick) of dilute solutions of Cu in A1 were seeded, so as to provide extensive single slip, with the pole of the tensile axis located in the standard stereographic projection as shown in Fig. 2. Each crystal was grown under an argon atmosphere in a graphite mold containing a large reservoir of molten alloy for the purpose of obtaining rather uniform composition of Cu along the length of the bar. The nominal compositions of the alloys which were produced from 99.99 pct Cu and high-purity A1 containing 0.001 pct Fe and 0.001 pct Si, are given in Table I. Strains, measured by linear variable transformers attached by quartz rods to a 3 in. gage section were sensitive to and the stresses were ap- plied by direct loading of the specimen. Temperatures were determined by thermocouples attached to the gage section of the specimens. Below 400°K the apparent activation energies for creep, Q, were determined by the effect of small, rapid changes in temperature of about + 10°K from T1 to T2 on the corresponding creep rates ?1 and ?2 during primary creep according to where R is the gas constant.' Above 400°K, Q was evaluated from Eq. [1] for the secondary creep rate using temperature changes of about ±20K. A typical set of results is shown in Fig. 3. RESULTS AND DISCUSSION The previously obtained effect of temperature on the apparent activation energy for creep of single crystals of high-purity A12 is shown by the broken curve of Fig. 4. The datum points on the same graph illustrate the effect of dilute a solid solution alloying with Cu on the activation energy between 600" and 750°K. Each plotted point is the average of not less than five independent test values between 600° and 750°K and not less than three at other tempera-

Jan 1, 1962

By G. Thodos, R. J. Smialek

A method has been developed that permits the correlations of Mehra and Thodos8 and Dastur and thodos2 for binary systems to be used for the prediction of the vapor-liquid equilibrium constants of the light and heavy constituents, Kland Kh, of a ternary hydrocarbon mixture. Furthermore, the unique relationship observed in this study, i.e., a plot of log Ke/Ki vs log Kp/K h is linear and passes through the origin, permits the calculation of the K-value for the intermediate component. This approach has been used to establish K-values for the constituents of the three ternary hydrocarbon systems used to develop this method and has also been applied to two additional ternary hydrocarbon systems to yield an average deviation of 7.7 per cent resulting from a total of 294 points for the five ternary systems considered. INTRODUCTION The rigorous calculation of vapor-liquid equilibrium constants for systems containing two or more components is a difficult problem and becomes extremely complex at elevated pressures and for conditions approaching the critical point. Although thermodynamic relationships can be developed to account for the vapor-liquid equilibrium behavior of simple systems, their use is limited because the necessary PVT data for these systems are not generally available. To establish a method for calculating K constants directly, without any recourse to the PVT behavior of a system, Mehra and Thodos8 applied the principle of corresponding states to the vapor-liquid equilibrium constants of binary hydrocarbon systems. They developed a series of charts which made possible the prediction of K-values for all binary hydrocarbon systems not containing methane. This work has been extended by Dastur and Thodos2 to include binary hydrocarbon systems containing methane. The charts developed in these two studies cover the high-pressure region and are applicable to conditions in the vicinity of the critical point. The ability of this approach to predict vapor-liquid equilibrium constants of binary hydrocarbon systems suggests that this method may be extended to the prediction of the K-values of the components of ternary hydrocarbon systems. In this investigation, the charts developed for both the methane and non - methane binary systems,2,8 together with mixture rules developed in this study, have been used to predict the K-values of the light and heavy components of a ternary hydrocarbon system. These calculated values are then used to establish the K-value of the intermediate component through the use of a novel relationship developed in the present study. DEVELOPMENT OF METHOD FOR PREDICTING K-VALUES OF TERNARY SYSTEMS The application of the corresponding state charts developed for binary hydrocarbon systems is restricted to those systems containing two components. The extension of these correlations to three-component systems requires that the ternary system be reduced to an equivalent binary, which can be treated in a manner consistent with the corresponding state development. To establish such an approach, the vapor-liquid equilibrium constant of the light component K is first calculated by assuming that the ternary mixture consists of the light component and a pseudo-heavy component of the intermediate and heavy constituents of the original ternary. To establish the vapor-liquid equilibrium constant of the heavy component Kh, the light and intermediate constituents of the ternary are combined to form a pseudo-light component of another equivalent binary system. The calculated values Kl and Kb are then utilized to calculate the vapor-liquid equilibrium constant of the intermediate component EQUILIBRIUM CONSTANT FOR LIGHT COMPONENT K To calculate the K value of the light (most

Jan 1, 1965

By Mery-Cecilia Gómez-Marroquín

O presente trabalho trata da formação da ferrita de zinco a partir da mistura e posterior reação solido-solido entre o óxido de zinco e óxido de ferro - Fe2O3 puros em proporções equimolares. A faixa de temperatura onde teve lugar a formação foi entre 1073 e 1373 K. Testes de redução da ferrita da zinco sintética-ZF e pós de aciaria elétrica–EAFD foram realizadas usando misturas de CO e CO2 que variaram entre 50 e 100% CO. Ambos os testes (formação e redução de ZF e EAFD) foram suportados usando técnicas de caracterização física, química, estrutural e microscópica. No caso da redução, foi observado que tanto a temperatura como a percentagem de CO, foram os fatores que, mais afetarem a redução de ferrita de zinco contida no EAFD. A máxima percentagem de redução da ZF foi 85%, para 100% CO, 1373K e 105 min, e 52%, para 50% CO, 1373K e 105 min. Por outro lado, atingiu o 100% para 100% CO, 1273K, em 80.75 min, 60%, para 50% CO a 1373K durante 105 min. no caso da redução do EAFD

Aug 17, 2017

By J. M. Stuve

Low-temperature heat capacities of chiolite (Na5Al3F14) were determined by adiabatic calorimetry in the temperature range 5.8 to 300 K. The derived standard entropy (S°, 298.15) was 115.6 ± 0.2 cal/deg-mole. High temperature enthalpies relative to 298.15 K were obtained by precision drop calorimetry up to 1,000 K. Tables of experimental data and related thermodynamic functions are given for the temperature range of experimental observations.

Jan 1, 1980

By Shadia J. Ikhmayies

In this work the equilibrium temperature-composition phase diagrams of the Si-O2 system were calculated using Thermo-Calc software in the temperature range 500–3000 K. Constituents of stable phases were obtained, and the amounts of certain phases where investigated with the variations in the composition of oxygen and temperature. It is found that quartz with silicon represent a stable phase in the temperature range 500–1150 K, while tridymite with silicon represent a stable phase in the temperature range 1150–1700 K. A liquid phase is found besides tridymite in the temperature range 1700–1750 K, and a stable phase of cristobalite with liquid appears in the temperature range 1750–2000. The maximum amounts of quartz, tridymite, and cristobalite are found at oxygen mole percent of 67.7%.

Mar 1, 2017

By W. C. Knopf, G. Samsel

For several years International Minerals & Chemical Corp. has used a radiation method to assay potassium content of products from potash and feldspar beneficiation. The procedure is rapid, accurate, and inexpensive and is easily handled, if necessary, by nontechnical personnel. Data are presented to show the accuracies that may be expected if the technique is used for control of pilot plants or large- scale plants. Natural potassium is composed of three isotopes -K39, K40 and K41. Five other isotopes, artificially produced, have been detected. In natural potassium only the K40 isotope, with a half life of 1.4 x 109 years, is radioactive. Its modes of decay are beta and gamma rays, positrons, and x-rays. Only the more abundant beta rays, however, are important in radiation measurements using geiger tubes.

Jan 10, 1958

By Xiaodi Huang, Matthew Andriese, Zheng Zhang, Jiann-Yang Hwang, Zhiwei Peng

"The thermal decomposition and regeneration behaviors of wüstite were investigated by in situ high temperature X-ray diffraction (HT-XRD) under non-isothermal condition at heating rate of 4 K min-1 in vacuum ranging from 294 K to 973 K. Wüstite on heating decomposes to magnetite and iron up to 823 K, above which it exhibits marked tendency to regenerate. Investigation of thermal stability of the reaction system shows that the decomposition proceeds under kinetic reaction control while the regeneration is under thermodynamic control. Kinetics study based on the Coats-Redfern integral approximation method indicates that the decomposition reaction follows a Komatsu-Uemura model-based diffusion-controlled kinetics with activation energy of 32.860 kJ mol-1. The thermodynamics analysis of regeneration reaction demonstrates that wüstite regenerates at lower temperature than stoichiometric ferrous oxide.IntroductionOwing to its importance in preparing various magnetic ceramic/metal nanocompostites or nanocrystals with high values of coercivity for the application as recording media, wüstite (non-stoichiometric ferrous oxide) has been attracting the attention of scientists over a long period [1-6]. The thermal behavior of wüstite was investigated by several researchers and phase transformations due to thermal decomposition and regeneration of wüstite during the heating in a specific temperature range was observed [7-9]. In spite of wüstite being found to dissociate to magnetite and iron at temperatures lower than 848 K and then regenerates at higher temperature, a clear understanding of the reaction mechanisms is clearly lacking [9]."

Jan 1, 2012

By G. Richards Gwinn

"Mica" is a group name for a number of orthosilicates of aluminum with magnesium, ferrous iron, and the alkalies. They are characterized by their high reflection and a basal cleavage so well developed that they can be split into exceedingly thin laminae, which are more or less tough, elastic, and transparent, according to variety. Barium, manganese, lithium, chromium, titanium, boron, and ferric iron occur in same varieties. Eight distinct species of true mica, which appear in the following table, are recognized by mineralogists, but only the first five are of commercial importance. [Species General Formula Muscovite H2KA13 (SiO4)3 Phlogopite [H,K, (MgF)]) Mg3A1 (Si04)3 Biotite (H,K)2(Mg,Fe)2(Al)Fe)2 (S104)3 Lepidolite K,Li Al(OH,F)2 Al (5103)3 Ros coalite H8K(Mg,Fe) (A1,V)4 (S103)12 Paragonite H2NaAl3(S104)3 Zinnwaldite (K)Li)3 FeAl3 Si5016(OH,F)2 Lepidomelene HK2F3IIIFe6III A13 (S104)9]

Jan 1, 1951

By M. J. Ferrante

Relative enthalpies of cuprous iodide (CuI) were measured at the Bureau of Mines to provide thermodynamic data for the advancement of min-eral technology. Enthalpy measurements between 298.15 and 1,396.3 K were made with a copper-block drop calorimeter. The temperatures of transition were measured by differential scanning calorimetry (DSC). Reversible transitions were determined at 643 K with a standard enthalpy of transition [(6Htr)] = 0.74 kca1/mol, at 679 K with a [6Htr = 0.65 kca1/mo1, and at 868 K] with a standard enthalpy of fusion [(6H~) = 1.895 kca1/mol.] Tabulated values are listed at selected temperature increments from 298.15 to 1,600 K for the standard relative enthalpy (HO -H298), heat capacity (CpO), entropy (SO), and Gibbs energy function [-(Go -H298)!T]. The enthalpy data are also given in the form of equations and combined with thermodynamic data from other investigations to derive values of standard entha1pies of formation [(~HfO)], Gibbs energies of formation [(6GfO)], and logarithms of the equilibrium constants of formation (log Kf).

Jan 1, 1987

By M. J. Ferrante

The Bureau of Mines determined the enthalpies of Ni3S2 relative to 298.15 K to provide new thermodynamic data for advancement of mineral science and technology. Enthalpies were measured with a copper-block calorimeter from 298.15 to 1,197 K. A solid-solid transition was found at 834±1 K, with an isothermal heat absorption of 13.32 kcal/mol. The temperature of this solid-solid transition was accurately measured by differential scanning calorimetry. Because Ni3S2 does not melt congruently, the heat of fusion of 4.70 kcal/mol was obtained by extrapolation of enthalpy measurements from the solid and liquid phases to approximately 1,064 K. Tabulated values are given for the relative standard enthalpy, heat capacity, entropy, and Gibbs energy function between 298.15 and 1,800 K. Enthalpies are also given in equation form and combined with data from the literature to derive values of standard enthalpies of formation and Gibbs energies of formation. Similar calculations were made for the reaction of crystalline and liquid nickel with gaseous diatomic sulfur for Ni3S-2(c, l).

Jan 1, 1982

The theme i wish to develop in this talk is how we might make use of the scientific and technological knowledge we now have ofextraction metallurgy to meet the present-day needs of the production industry.Before doing so, I would like to say a few words in tribute to Dr. G.K. Williams since he was a past master at precisely what I wish to talk about. I knew G.K., as everybody called him, during the time he spent at Avonmouth in the late 40's and in the 50's. Later, when he was ostensibly retired, I had the pleasure several times of lunching with him when I was visiting Melbourne.When G.K. was at Avonmouth, the Imperial Smelting Process was in that capricious adolescent stage in between the pilot plant and the full-scale commercial unit. G.K. was a great collector of process plant data which hung in cascades from the walls of his office and-from his hand-operated desk calculator. What G.K. understood very well were the basic metallurgical and engineering principles of what was going on in the sinter machine, the shaft furnace and all their ancillaries.

Jan 1, 1985

By L. B. Pankratz

Heat content measurements were conducted for GaPo.996 and InPo.986 over the temperature range from 298° to 1,100° K, and for In2S2.897 over the range from 298° to 1,200° K. Both the actual experimental data and values adjusted to conform with the stoichiometric compositions (GaP, InP, and In2S3) were reported. Entropy increments above 298.15° K were calculated for the stoichiometric compounds, and heat content and heat capacity equations were derived.

Jan 1, 1965