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By J. G. Donaldson

Binary alloys of molybdenum and tungsten were prepared by the Bureau of Mines in laboratory-scale experiments by hydrogen reduction of their vaporized hexafluorides. Near-optimum deposition parameters were determined, and the nature of the deposited alloys was investigated. Dense, homogeneous alloys were codeposited between 650° and 750° C with a reduction efficiency of more than 75 percent. The alloy composition was uniform when the hydrogen ratio in the gas feed mixture did not exceed 3 times the stoichiometric requirement. Regulating the proportions of the metal hexafluorides in the gas feed provided a large degree of control over the composition of the deposit. Hardness of the deposits varied directly with the proportion of excess hydro,,,, in the gas feed and with the weight-percent of tungsten in the alloy. Hardness was not affected by deposition temperature over the range 650° to 750° C for specimens of similar composition. Extreme brittleness and unsuitable physical shapes of the alloys prevented tensile strength measurements.

Jan 1, 1966

By Louis A. Panek

Determining the change of stress in rock based on measurements of the deformation of a drill hole is a procedure that is increasing in popularity. A closely related procedure involves the applicat10n of this principle to determine the existing stresses in a rock medium, by cutting free (core drilling) an annulus containing the drill hole. In this Bureau of Mines report, expressions are derived from which one can calculate the stress ellipsoid--the three-dimensional change of stress, or the existing three-dimensional stress field, as the case may be. Study of these equations shows that the stress components in three dimensions can be determined by measurements in only two drill holes, and yields general principles that are useful in planning an efficient program of drilling and measurement. Procedures are given for calculating the least squares estimates of the stress components and their standard errors, and for evaluating or comparing calculated values by means of standard statistical inferences.

Jan 1, 1966

Jan 1, 1966

By Shiou-Chuan Sun

The froth flotation of coal, differing greatly from that of most minerals1-5, is not improved but rather impaired by temperatures higher than room temperature6-10 This phenomenon has long taunted us for an explanation. Gayle and Associates 8,9 reported the lack of relationship between their contact angle measurements and their flotation of American coals under various temperatures. Bailey and Whelan6 stated that the viscosity of flotation reagents, offering some clue for their flotation of British coals at low temperatures, could not be put forward as an explanation either in whole or in part for the effect of temperatures on coal-flotation. In this paper, a froth hypothesis is proposed to explain the flotation behavior of coals under various pulp temperatures. Test work involved the flotation of coals and the frothing of reagents.

Jan 1, 1966

By Elton L. Litchfield

The techniques for direct initiation of detonation, developed by the Bureau of Mines, have been applied to gaseous mixtures of oxygen with methane, 'thane, propane, butane, or hexane. An exploding wire was used as the initiation source to determine minimum stored electrical energies required to effect detonation of mixtures between one-half and two times the stoichiometric fuel ratios. Detonations were obtained in the most easily initiated mixtures of ethane, propane, butane, and hexane for initiation energies between 24 and 33 joules at 1 atm and 28-43 joules at 0.5 atm initial pressure. Methane mixtures, at 1 atm, were not observed to detonate when initiated with up to 484 joules.

Jan 1, 1966

By E. A. Loria

The Bureau of Mines analyzed the effects of oxygen, nitrogen, and carbon on the tensile properties of electrorefined vanadium in terms of the Petch equation. The effects of the different impurities and grain sizes on the yield and flow stress between 2730 and 770 K were studied. For specimens of like composition, the values of the Petch parameters 01 and ky obtained by two different methods, extrapolation and grain size, were nearly the same. For high-purity electrorefined vanadium, the 01 value at 2730 K was 10,300 psi (5,150 psi shear). The 01 values for this metal at 1950 and 2730 K were lower by factors of 3 to 4 than for three less pure samples of commercial vanadium metal of equivalent grain size. Nitrogen was more effective than oxygen in increasing 01' the increase being about twice as much for the same impurity level. Carbon produced a slight increase in 01 up to 0.024 percent and then a gradual decrease in 01 to 0.11 percent, the maximum carbon content studied. The corresponding ky values followed the same trend in regard to oxygen and nitrogen additions, whereas the addition of carbon produced no variations at either temperature. Dislocations in vanadium are anchored by carbon, oxygen, and nitrogen with increasing firmness in that order. The high purity of electrorefined vanadium was confirmed by low yield stress and high ductility throughout the low temperature range. The metal also exhibited profuse twinning with high ductility at 1230 and 770 K. The effective surface energy for fracture, y, was found to lie between 3.3 and 3.6 x 1()4 erg cm-2?

Jan 1, 1966

By James A. West

THE South Asian countries of India, Ceylon, Pakistan, Afghanistan, Nepal, Bhutan, and Sikkim have a large variety of mineral resources; however, in spite of mineral industry growth during 1964, development of resources remained far short of possible development, and, in terms of value of trade in minerals, the area remained a sizeable net importer. India's mineral industry is by far the most significant; its minerals production in 1964 accounted for more than 90 per cent of the total value of all minerals produced in the area. The total value of all minerals produced in South Asia in 1964 was only about 1 percent of the area's estimated gross national product of $55,125 million. Despite the rather small current contribution of minerals to the economy, development of mineral resources figures prominently in plans for the industrial development of the nations of this area.

Jan 1, 1966

By D. C. Crowell

This publication presents the results of a laboratory investigation of displacement of gas by injection or imbibition of water into sandstone models under essentially isobaric conditions. A brief discussion of scaling requirements is included. The influence on residual gas saturation of independently varying the parameters of dimensional ratios of the porous media, rates and methods of flooding, surface tension, initial water saturation, and permeability is shown. Of these variables, increased initial water saturation and decreased surface tension reduced residual gas saturation significantly, whereas variations in flooding rate and dimensional ratios had no apparent effect. No correlation was evident between absolute permeability and residual gas saturation.

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 J. E. McMenamin, R. B. Hall

"With the emphasis in the past decade on larger and more efficient equipment for open-pit operations, the Normandie mine of the Asbestos Corporation has followed the trend, switching from the smaller type of percussion drills to down-the-hole rigs. One 5 Y2 -in. percussion drill is still in use, but is limited to a ""smooth blasting"" role or to the control of the slope on final benches.In keeping with the times, an attempt was made to eliminate, as much as possible, the use of high explosives and to maximize the percentage of ammonium nitrate -fuel oil mixture. As the concentration of ground water increased with increased mining depths, small pumps were initially employed for the dewatering of boreholes. This proved unsuccessful, and a hole-blowing rig was built and a conversion to plastic liners made. The acquisition of a bulk-mix AN-FO truck has permitted the changeover from an AN premix to an ammonium nitrate prill -fuel oil combination at the borehole."

Jan 1, 1966

By W. J. Stickney

"Over-all recovery of cadmium has been increased at the plants of the Hudson Bay Mining and Smelting Co., Limited, since the construction of a slag fuming plant and baghouse where smelter flue dust is recovered. This pa-per outlines the distribution of the cadmium in plant products from the concentrator to the refining department.The leaching of cadmium-bearing precipitates from the zinc plant is also discussed. This consists of a two-stage leach; first with sulphuric acid and then with copper sulphate. Details of the leaches are outlined along with the safety measures practised in handling the hydrogen and arsine evolved.The paper describes the final preparation of electrolyte for the refining cells by purification for copper and thallium. Deposition of cadmium, using a polyacrylamide as an addition agent, is discussed.An outline is given of the melting procedures, under either sodium hydroxide or zinc chloride, and of the sub-sequent treatment of the dross to recover entrained cadmium and thallium."

Jan 1, 1966

By Harold M. Smith

This report presents a complete qualitative picture of knowledge of the composition of petroleum as of April 1965. The material is presented in detail on two imaginative maps--one, the Hydrocarbon Hemisphere, depicts the hydrocarbons that have been identified in petroleum; the other, the Heterogeneous Hemisphere, shows the sulfur, nitrogen, and oxygen compounds that have been found. All compounds are placed on the maps according to boiling point. The accompanying text illustrates by structural formulas the several types of hydrocarbon and nonhydrocarbon compounds identified, presents some quantitative data, and points out the possible geochemical significance of a number of the compounds. The possibilities of the Petroleum World of the future are discussed as a function of needed research,

Jan 1, 1966

By Patterson J. H

An infra-red absorption study has been made of crocidolite, country rock. and associated host rocks from Wittenoom Gorge. The spectrum of the country rock is appreciably different from those of crocidolite and the magnetite-rich host rocks which are closely similar. A process to separate crocidolite-bearing ore from country rock based on infra-red emission is therefore possible in theory.

Jan 1, 1966

By Harold M. Smith

This report presents a complete qualitative picture of knowledge of the composition of petroleum as of April 1965. The material is presented in detail on two imaginative maps--one, the Hydrocarbon Hemisphere, depicts the hydrocarbons that have been identified in petroleum; the other, the Heterogeneous Hemisphere, shows the sulfur, nitrogen, and oxygen compounds that have been found. All compounds are placed on the maps according to boiling point. The accompanying text illustrates by structural formulas the several types of hydrocarbon and nonhydrocarbon compounds identified, presents some quantitative data, and points out the possible geochemical significance of a number of the compounds. The possibilities of the Petroleum World of the future are discussed as a function of needed research,

Jan 1, 1966

By James Paone

Drillability of rocks by mechanical means is closely related to the physical properties of the respective rocks, Various approaches by previous investigators on rock drillability are presented, as well as recent techniques studied by the Bureau of Mines. The studies show drillability concepts based on (1) theoretical drilling equations derived from laboratory drilling experiments extended to field drilling results and on (2) a statistical method where multiple regression analysis is used to develop a prediction equation for drillability.

Jan 1, 1966

By Mary S. Esfandiary

This is a revision of a directory of coal research organizations throughout the world that was first published in 1961 as Bureau of Mines Information Circular 8008. Because of the wide acceptance of the first edition, a revision which would supply up-to-date information on coal research and which would facilitate communication among organizations of similar interest seemed important. This compilation includes the names and activities of organizations of various types-government, university, private, and industry. The areas of investigation that each organization is engaged in are indicated in broad terms: Analysis and constitution, mining and geology, preparation, briquetting, combustion, high-and low-temperature carbonization, gasification, conversion to solid and liquid fuels, and health and safety. Publications issued by and describing the work of each organization are cited; almost all of the organizations also publish results of their investigations in the technical press. Selected technical and trade publications that publish information on the science and technology of coal and are not published directly by any of the organizations listed are cited in the pages following the list of organizations in each country. Information that would improve coverage and accuracy of the next revision of the publication will be welcomed by the Bureau of Mines.

Jan 1, 1966

By R. G. Agarwal, Ramey Jr. H. J., Al-Hussainy R.

Although it has long been realized that gas recovery from a water-drive gas reservoir may be poor because of high residual saturations under water drive, it appears that only limited infomlation on the subject has been available until recently. This study was performed to show the qiiantitative potential importance of water influx. Results indicate that gas recovery may be very low in some cases: perhaps as low as 45 per cent of the initial gas in place. Gas recovery under water drive appear to depend in an important was on: (I) the prodirction rate and manner of production; (2) the residual gas saturation; (3) aquifer propertie.); and (4) the volumetric displacement effciency of water invading the gas reservoir. The manner of estimating water-drive gas reservoir recovery can vary considerably. Examples are: the steady-state tnethorl. the Hurst modified steady-state method, and various unsteady-state methods such ac. those of van Ever-dingen-Hurst, Hurst, and Carter-Tracy. The Carter-Tracy water influx expression was used in this study. In certain cases, it appears that gas recovery can be increased significantly by controlling the production rate and manner of production. For this reason, the potential importance of water influx in particular gas reservoirs should he investigated early to permit adequtrtr planning lo optirtize the pay reserves. INTRODUCTION In recent years, the economic importance of natural gas production has become increasingly apparent. This has been evidenced by more intensive exploration efforts aimed at gas production, and exploitation of both deep, as well as low-permeability gas reservoirs. Technical developments such as deep-penetration fracturing have made development of such formations economically feasible. Unfortunately, water influx has forced abandonment of a number of gas reservoirs at extraordinarily high pressures. Although reservoir engineering methods for estimating water influx have long been available, it appears that application of these methods to the water-drive gas reservoir has been sporadic.'a Available methods for estimating water influx which can be applied to the water-drive gas reservoir problem include the steady-state method,1 the Hurst modified steady-state method and various unsteady-state methods such as those of van Everdingen-Hurst. Hurst, and Carter-Tracy. Interesting applications of these solu- tions to gas reservoir and the aquifer gas-storage problems have appeared recently.3,12,14 The experimental study of residual gas saturations under water drive by Geffen et al. in 1952 indicated that residual gas saturations could be extremely high. A value of 35 per cent of pore volume is often used in field practice when specific information is not available. The study of Geffen et al. showed that residual gas saturation might be much higher in some cases. Naar and Henderson concluded that the residual non-wetting phase saturation under imbibition should be about half of the initial non-wetting phase saturation. The Naar and Henderson result that residual gas saturation under water influx should be about half the original gas saturation is recommended as an estimate if laboratory measurements are not available. Thus, it is clear that a considerable portion of the initial gas in place might be trapped in a water-drive gas reservoir as residual gas at high pressure. A full water-drive would result in loss of residual gas trapped at initial reser.voir pressure. Consideration of transient aquifer behavior leads to the conclusion that high-rate production of water-drive gas reservoirs could result in improved gas recovery by reduction of the abandonment pressure. However, there appears to be little quantitative information on this possibility. One of the few advantages of water-drive gas production appears to be improved deliverability through water-drive support of the reservoir pressure. There may also be an advantage in higher condensate recovery caused by pressure maintenance for gas-condensate water-drive reservoirs. In view of the preceding, this study was made to assess the potential importance of water-drive in gas reservoir engineering. The Carter-Tracy approximate water-influx expression was used because this equation offers some advantages in hand-calculation which do not appear to have been generally recognized.' However, calculations were performed in the main with a high-speed digital computer to permit evaluation of the effect of water-drive under a large variety of conditions. CALCULATION METHOD Water-drive gas reservoir performance can be estimated in a manner completely analogous to oil reservoir calculations: a materials balance is written for the reservoir, and a water influx equation is written for the aquifer. Siniltaneous solution provides the cun~ulative water influx and the reservoir pressure. When reservoir performance data (gas produced and reservoir pressures) are available, it is usually possible to match performance data to determine the initial gas in place and the water influx parameters —

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 James R. Dunn

The nature of water and clay in carbonate rocks is currently being investigated at Rensselaer Polytechnic Institute by various thermal and sorption techniques. Two basic concepts 'led to the present research. (1) To explain the expansion and contraction on wetting and drying of some unsound argillaceous carbonate rocks, it was postulated that the pore space around each clay particle is such that when water is sorbed by the clay, force is exerted against the pore walls. (2) The clays in expansive rocks are rejected from the growing dolomite crystals during their growth, and form a more or less connected network, thereby becoming "wettable," or available to water. New quantitative cold differential-thermal-analysis (electrocalorimetric) equipment was designed and constructed to check the "limited space" and "wettable clay" concepts and to determine the thermal nature of the transition of water to ice in rocks. This DTA equipment can detect the release of heat in freezing of less than 0.001 per cent water in a rock. Twenty-three rock cores (nine sound and fourteen unsound) and 4 procelain cylinders for standards were studied. In the nine sound rocks and in all the procelain cylinders, the rapid freezing of from 50 to 100 per cent of the water was readily detectable after 7 to 10° C of supercooling. No further freezing could be detected to -20° C. However, in eleven of the fourteen unsound rocks, no freezing was detected to as low as -40° C; in the other three, less than 50 per cent of the water froze. As a check of the DTA measurements, adsorption isotherms were determined for all materials. Calculations of theoretical freezing points for sorbed water again demonstrated that the least sound rocks had the most nonfreezable water. "Frost" sensitivity in these carbonate rocks is, therefore, probably not the result of the force of expansion of water to ice. The disruptive force is believed to result from expansion of sorbed, ordered water on clay surfaces. The relationship between the unfilled rock pores after 24-hour water saturation and the water sorbed at 85 per cent humidity at 30° C (i.e., the theoretical nonfreezable water delineates the sound and unsound carbonate rocks.

Jan 1, 1966

By Severn P. Brown

Cement plants in the central Hudson River valley utilize limestones of the Helder-bergian Series of the Lower Devonian. Chiefly calcilutites, calcarenites, and cherty calcisiltites, these rocks represent progressively deeper environments, from lagoonal to neritic, with scattered reef deposits. Stratigraphic continuity is marked, and a layer-by- layer analysis shows strikingly constant chemical compositions. The structural picture varies from flat-lying and relatively unfaulted beds on the northwest, through gently folded and faulted beds on the north, to complex overturned beds with closely spaced imbricate faults on the south. Operating techniques are simpler in the north, where grade control is effected chiefly by the initial layout of the faces. In the south, grade control requires flexibility and frequent adjustment of faces or scheduling. A system of quarrying along strike has been developed, grade being computed from a cumulative foot-per cent graph of the critical oxides in each mappable layer. Balancing shovel production among the many faces is simplified by comparing production requirement ratios with ratios of the various types of rock in each face. Drilling and blasting limits are geologically controlled if warranted, or large blasts embracing several rock types are shot and the resulting pile of broken rock is staked along shovel limits.

Jan 1, 1966