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By Willard L. Hunter

The Bureau of Mines studied the effect of temperature upon the reduction of chromite by carbon and the relative reducibility of chromites as a function of their composition. Ferric oxide was also studied to provide comparative data. Pellets weighing approximately 1 gram and containing 70 percent ferric oxide, chromic oxide, or chromite and 30 percent graphite were subjected to closely controlled temperatures under a flow of argon for 15 minutes. The amount of CO and CO2 evolved was measured, and the reduced sample was analyzed by X-ray diffraction techniques. The reduction of Fe2O3 was studied over a temperature range of 600° to 1,400° C, while the reduction of Cr2O5 and chromite was conducted from 9000 to 1,621° C. The temperature above which appreciable reduction of Cr203 by graphite took place was 1,125° C. The temperature at which significant reduction started for three of the four chromite samples was approximately the same, indicating that there was concurrent reduction of iron and chromium oxides in the chromite mineral rather than selective reduction of iron oxides followed by reduction of chromic oxide. Rhodesian chromite appeared to dissociate at a lower temperature with concurrent reduction of iron. Based on the temperature at Which chromite was 50 percent reduced in 15 minutes, Transvaal chromite reduced most easily, followed by Mouat, then by Kampersian, and finally by Rhodesian DFC material. Statistical analysis of test results indicated that the ferric iron content of chromites affects their reduction behavior more than any other constituent.

Jan 1, 1966

By Willard L. Hunter

The smelting of tin slags was undertaken at the Bureau of Mines Albany Metallurgy Research Center (AMRC) to produce crude columbium-tantalum ferro-alloy as a unit operation in the production of pure columbium and tantalum oxides or chlorides. Columbium and tantalum-rich alloy was prepared during short unrelated campaigns over a total period of 12 years. Tin slags from Malaya and the Congo (Geomines) were smelted. These slags were reduced by carbon in a small, single-phase, steel-making furnace} a larger three-phase, steelmaking furnace, and a three-phase, submerged-arc furnace, In all cases depleted slags were fluid and easily tapped from the furnace. However, unless diluted by iron additions, the metal product was a viscous, high-melting, heterogeneous mixture that could be removed from the furnace only by hand rabbling.

Jan 1, 1966

By C. J. Walker

The Bureau of Mines undertook a theoretical and laboratory study to determine the feasibility of using ethylene as a tracer for natural gas in underground gas-storage reservoirs. The study indicated that ethylene was a useful gas tracer in underground gas storages. Tracer losses were not excessive. Laboratory tests were conducted at pressures as high as 500 psia in both wet and dry consolidated-sandstone cores, evaluating tracer loss with gas blends containing natural gas with different concentrations of ethylene tracer. Under certain conditions losses were less than 17 percent.

Jan 1, 1966

By H. A. Watson

Laboratory tests on three commercial methane detectors, two combustion-type detectors and one interferometer-type detector, were made by the Bureau of Mines to determine their response to certain single and multiple flammable gases mixed with normal and abnormal air atmospheres. Although both types of detectors responded accurately to methane-normal air mixtures, they did not show correct concentrations for other single flammable gases in air. Uniquely, the response of the interferometer-type detector to hydrogen was in a negative direction. The effects of individual gases in multiple flammable gas mixtures were approximately additive. In oxygen-deficient atmospheres the methane response of the interferometer-type detector erred on the high side, but only in very low oxygen concentrations were the combustion-type detectors affected-showing low, erratic methane readings.

Jan 1, 1966

By Raymond L. Lowrie

Coal deposits in the Boulder-Weld County coalfield in Colorado are analyzed in relation to economic factors governing the growth, stability, and competitive potential of the coal industry. Recoverable reserves, estimated to be 571 million tons, are discussed in detail, particularly those in the Erie and Frederick Quadrangles. Geology of the coal measures, quantity and quality of water resources, and chemical and physical properties of the coal are described. Coal production factors, including mining techniques and equipment, labor requirements, transportation facilities and rates, and markets, are considered for coal's position in competition with alternate fuels. Growth of the fuels market, through increasing thermal-electric power generation in the Denver Metropolitan Area, will stimulate coal production in Colorado. Reserves of the contiguous Boulder-Weld coalfield, if mined in a sustained, year-round, high-tonnage operation, could be used to supply much of that fuel demand.

Jan 1, 1966

By H. A. Watson

Laboratory tests on three commercial methane detectors, two combustion- type detectors and one interferometer-type detector, were made by the Bureau of Mines to determine their response to certain single and multiple flammable gases mixed with normal and abnormal air atmospheres. Although both types of detectors responded accurately to methane-normal air mixtures, they did not show correct concentrations for other single flammable gases in air. Uniquely, the response of the interferometer-type detector to hydrogen was in a negative direction. The effects of individual gases in multiple flammable gas mixtures were approximately additive. In oxygen-deficient atmospheres the methane response of the interferometer-type detector erred on the high side, but only in very low oxygen concentrations were the combustion-type detectors affected-- showing low, erratic methane readings.

Jan 1, 1966

By Bernard Porter

The rate of the heterogeneous reaction between high-purity uranium metal and uranium tetrafluoride in molten lithium fluoride was measured. The apparent heat of activation for the reaction is 16.91 kilocalories per mole of UF4. A surface-controlled mechanism is suggested in which UF4 is adsorbed on the uranium metal surface. Additional UF4 reacts with the adsorbed species and the metal site to form an activated complex that decomposes to the product UF3. The reaction is an important source of metal loss in the electrowinning of uranium metal.

Jan 1, 1966

By R. T. Sorensen

Research and testing in a small scale equivalent of a commercial flota-tion plant was completed on four low-grade, iron-bearing materials from the western Mesabi range. Closed circuit-flotation of calcium-activated silica with fatty acid collector developed data for comparison with the batch process and highlighted problems not evident from previous bench testing. The four ore samples contained from 27 to 39 percent Fe and were equally represented by nonmagnetic taconite and semitaconite type materials. Iron concentrates containing 6.0 percent, or less, SiO2 were made 5, all four samples. Of the two material types, the semitaconite was the ore amenable to treatment, yielding iron recoveries of about 90 percent as cc pared with 70 to 80 percent for the other. Pilot plant tests showed that concentrate grade made in batch tests could be duplicated in the closed circuit and demonstrated that the amount of recoverable middling iron varied considerably between ore samples. The continuous tests also showed that water temperature strongly influenced results in the treatment of one ore but apparently was of indifferent consequence in another. Progress in thickening and filtration of flotation concentrates was made through introduction of tapioca flour to serve the dual role of iron mineral depressant and flocculant.

Jan 1, 1966

By M. H. Rana

"A survey of our knowledge in the field of rock mechanics is presented from the viewpoint of applications in the mining industry. Aspects of rock mechanics of special interest to the industry are enlarged upon, with emphasis on the avoidance of over-generalization. The relationship between fundamental and practical rock mechanics is discussed, and the need for cooperation between the university and industry to further our knowledge of -useful rock mechanics is emphasized. An attempt has been made to establish the scope of rock mechanics, as applied to problems in the mining industry. This is brought about by projecting rock mechanics as a tool to be intelligently used rather than magic, capable of producing ""miracles."" Continued education is important for individuals engaged in the application 0f rock mechanics in the mining industry. The scope of this education is discussed from a viewpoint of better communication between industry and the education and/or re-search establishments engaged in this work.Finally, the dangers of over-emphasis on rock mechanics are mentioned, but a justification of the in-vestment in rock mechanics programs in mines is also presented."

Jan 1, 1966

By H. M. Smith

Data from the Bureau of Mines routine method for the analysis of crude petroleum are used to characterize crude oils. Some data are used directly while other data are used to calculate the aromatic) naphthene) and paraffin contents of the distillation fractions and the correlation index of the paraffin-naphthene portion of the fractions. The calculated properties show significant differences in composition between crude oils. The methods of calculation and interpretation of data are explained and illustrated.

Jan 1, 1966

By Jr. Norman

The Bureau of Mines investigated the thermoelectric properties of yttrium selenides and tellurides from room temperature to 900° C. X-ray crystallographic data were determined for the yttrium-selenium and yttrium-tellurium compounds that were orthorhombic with a cubic substructure. The yttrium selenides and tellurides exhibited semimetallic to insulator conduction properties with figures of merit of 10-9 to 10-4 °C-1. The mono-selenide and monotelluride behavior was partially degenerate; unsatisfied bonds were the source of the large number of charge carriers. The higher stoichiometry selenide compounds were intrinsic semiconductors) but with high electrical resistivities. A critical defect or impurity ionization energy for carrier activation appeared to exist in the majority of telluride compounds. Mobility and energy band determinations are required to interpret completely the observed effects in most of the compounds studied.

Jan 1, 1966

By Charles Goodeve

"BEFORE I begin, I should like to thank The Canadian Institute of Mining and Metallurgy for the honour they have bestowed in inviting me to give this address at the fourth annual C.I.M. Conference of Metallurgists banquet.Secondly, I should like' to convey the greetings of the Iron and Steel Institute of Great Britain in accordance with a request made by its Council at its last meeting. The I.S.I. hopes for the continued growth in strength of this annual Conference and in the collaboration between our respective societies.When I read the program of this Conference, it was brought home to me what a non-ferrons country Canada is. Also, I realized what enormous advances have been, and are being made, and what an ex-citing field non-ferrous metallurgy is for the scientist. This made me wonder, as I have done before, whether the future for steel was proof against these advances.At present, iron and steel stand astride the metallurgical world like a Colossus; I hope that the bronze industry will pardon my stealing their thunder and mixing my metaphors! Will this still be so in the future?The best way to answer this question is to take a look at the fundamentals to see why the iron atom dominates to such an extent that al! other metals are called ""non-ferrons."" Is its present position due to historical and therefore ephemeral reasons, or is there a fundamental difference between the atom of iron and those of other metals?"

Jan 1, 1966

By G. E. Johnson

Batch tests of coals and coal-derived materials were made by the Bureau of Mines to determine their effectiveness in removing organic contaminants (COD or chemical oxygen demand, comprising those organic compounds that can be chemically oxidized, and ABS or alkylbenzene sulfonate, common household detergents) from the final effluent of secondary-treated waste waters. The adsorptive capacities of flyashes, coals, including at least one sample of each rank found in this country, pretreated coals, and miscellaneous materials including commercial chars and coke, were determined and compared with that of granular activated carbon. The coals, though not as effective as activated carbon, possess an economic advantage--they are relatively inexpensive, and they can still be burned as fuel without any loss of fuel value after use in waste¬water treatment. A hvcb coal was found to be one of the best, having about one-fourth the capacity of activated carbon for COD, adsorbing about 4 percent of its weight before it became saturated. Several coals contained constituents that added to the COD content of the treated water. Thus knowledge of the performance of the coal is necessary to insure selection of a proper coal as adsorbent.

Jan 1, 1966

By Walter Kawa

Coals of various rank were reacted by the Bureau of Nines in plasma jets generated from argon and argon-hydrogen mixtures containing up to 33 volume-percent hydrogen. Average plasma temperatures ranged from about 3,400° to 12,000° C. Products were a solid residue and a gas containing hydrogen, methane, acetylene, diacetylene, and oxides of carbon. The highest yield of acetylene obtained with argon plasmas was 15 percent by weight of moisture- and ash-free coal. The data indicated that acetylene yields of 40 percent or higher can be obtained from the reaction of coal in argon-hydrogen plasmas, although results from these experiments could not be correlated with operating variables because of low recoveries plasma contained sufficient energy to heat the coal to temperatures as high 9,000 or 10,000° C, but complete devolatilization did not occur in any experiment.

Jan 1, 1966

By H. C. Fuller

Submerged combustion and inverse solubility methods were investigated as promising alternative means for crystallizing manganese sulfate from solutions produced by leaching manganese ores with either sulfuric acid or sulfur dioxide. Evaporation of water from typical manganese sulfate solutions by sub-merged combustion techniques enabled production of a slurry containing 32 to 39 pct MnSO4.H2O crystals suspended in a saturated solution of manganese sulfate. Such a slurry required further processing by thickening or filtration and drying to produce crystals of MnSO4.H2O. In a second approach, semicontinuous processing of manganese sulfate solu¬tions by thermal crystallization under pressure effected a recovery of 94.5 pct of the MnSO4.H2O as dry free-flowing crystals. Treatment of a solution containing about 100 grams manganese per liter at 189° C, produced a "barren" solution containing only 1.9 grams manganese per liter. Calculations made on comparable manganese sulfate solutions show that the heat requirement of the thermal crystallization method was about one-third to one-fourth that of the submerged combustion method.

Jan 1, 1966

By J. A. Cavallaro

The heats of formation of anhydrous barium carbonate (witherite), strontium carbonate (strontianite), and lead carbonate (cerussite) were determined by solution calorimetry. The solution mediums were hydrochloric acid for barium and strontium carbonates and perchloric acid for lead carbonate. The heats of formation at 298.15° K are as follows: BaCO3 -297.5 ± 0.8 kcal/mole; SrCO3 -294.6 ± 0.5 kcal/mole; and PbCO3 -168.0 ± 0.3 kcal/mole.

Jan 1, 1966

By Constantine C. Popoff

This report reviews and analyzes, by a simple analytical and logical reasoning, the conventional methods of reserve computations of mineral deposits described in various domestic and foreign publications. It brings together, formulates, and evaluates the principles underlying interpretation of exploration data; and ties such principles to the proposed classification of methods. The material is discussed in sufficient detail to allow general application.

Jan 1, 1966

By Francis X. Cannaday

The Bureau of Mines developed equipment to measure the sonic velocity of pulses transmitted through rock samples varying in size from laboratory specimens to mine pillars in place. Pulses are produced by electronically excited piezoelectric ceramic transducers. Special equipment components were developed by Bureau facilities; other components are commercially available. The technique permits a nondestructive, repetitive, stable, shaped pulse to be used in place of explosive caps or hammer blows. Longitudinal wave travel time measurements were taken on an oscilloscope screen; transverse wave measurements were taken under special field conditions. Results were consistently repeatable within the accuracy of the oscilloscopes utilized.

Jan 1, 1966

By Richard F. Link

A statistical technique, useful to analyze assay and other data characterized by location in three dimensions, is described in this Bureau of Mines report. If present, trends in the data are defined for the purposes of improving ore estimation, predicting ore beyond existing workings, and aiding geological interpretation. The technique is to fit linear and quadratic polynomial equations to the data through the statistical method of regression analysis. The fitted linear equations have the geometric form of hyperplanes; the fitted quadratic equations have the geometric form of ellipsoids or elliptic hyperboloids of one or two sheets. To visualize these three-dimensional forms, contour maps of a series of plane sections through the fitted surfaces are plotted. Both the fitting of the polynomial equations and the plotting of the con-tour maps are done by electronic computer to facilitate calculations and to obtain accurate results. Computer programs are described in appendixes. Methods employed are illustrated by an example analysis) based on data from a part of the Fresnillo mine) Zacatecas, Mexico.

Jan 1, 1966

By A. M. Sarem, J. M. Campbell

Molecular refraction is introduced as a new and improved third parameter for prediction of the PVT behavior of hydrocarbon systems. This parameter, characterizing the complex as well as the pure hydrocarbon systems (1) is a direct measure of London dispersion forces which affect the PVT behavior; (2) can be measured directly, accurately and easily for complex as well as pure hydrocarbon systems; (3) varies significantly between the reference substances thus allowing accurate interpolation of PVT properties; and (4) has a fundamentally sound basis. Molal average molecular refraction was used with the pseudocritical mixing rule proposed by Leland and Mueller to predict the molal volume of liquid and vapor for 84 published data points on nC4-nCI0, Cl-nC5, Cl-nC4-nC10 systems in the region of coexisting vapor-liquid and at the critical point. The same technique was applied to predict the densities of liquid hydrocarbon mixtures in the two-phase and single-phase regions near the critical point for seven different systems each having different properties of the heptanes-plus fraction, but all simulating the fluids of either gas-condensate or volatile oil reservoirs. A modification of the Leland-Mueller mixing rule for the determination of pseudocritical properties is also presented which yields more accurate liquid density predictions than the original form when used with the proposed third parameter. INTRODUCTION The PVT behavior of multicomponent systems has received widespread attention in the literature in recent years. A large portion of the reported work has stemmed from attempts to overcome the inherent difficulties encountered when using the standard compressibility-factor chart which shows 2 as a function of reduced temperature T, and and reduced pressure p,. This chart assumes that z, is constant for all systems. The error in this assumption is not pronounced for pipeline-type gases high in methane and low in heavy ends, particularly when contained at moderate pressures. For such gases the error in the calculated z is usually less than 2 to 3 per cent. However, the reliability of this approach becomes somewhat nebulous for gas condensate and volatile oil systems at high pressure. One logical approach has been to recognize the variation of 2,. This idea was first suggested by Meissner and Seferianl and used by Lyderson, Greenkorn and Hougen2 to prepare extensive tables of thermodynamic properties. Other third parameters have been proposed by Stockmeyer, Kihara, Riedel, Lightfoot, Bloomer and Pitzer. These were tested by Satter and Campbel13 for many gas mixtures and it was shown that they were inter-related. All of these third parameters have a common fault — they cannot be directly evaluated for the heptanes-plus fraction. Consequently, one necessary requisite of an improved method for predicting the density of multicomponent hydrocarbon systems, was development of a third parameter that could be evaluated for that fraction. PREVIOUS MULTICOMPONENT DENSITY PREDICTION METHODS Sage and Lacey4 suggested a method of using partial molal volumes for computing the density of hydrocarbon gas mixture for pressures to 3,000 psi. In this technique, they approximate the complex multicomponent gaseous mixtures by a quarternary system of methane, ethane, propane and butane. Sage, Hicks and Lacey5 suggest a method of using partial molal volumes for computing the density of hydrocarbon liquids. The results agree within 3 per cent of the experimental values. However, the composition range is limited to about 10 per cent by weight of methane. Consequently, this correlation does not cover the low-molecular-weight liquid similar to natural gasoline and high-pressure gas condensates.

Jan 1, 1966