Search Documents

By E. W. Davis

About a year ago several carloads of magnetite ore from New York state were sent to the Mines Experiment Station at the University of Minnesota for grinding and concentration tests. The flowsheet used minus ½-in. ore as feed to a 3 by 3-ft. overflow cylindrical ball mill operating at 37 r.p.m. in closed ciruit with a vibrating screen. The screen oversize was returned to the mill for further grinding and the screen undersize was concentrated magnetically. Several different screens, between 8 and 35 mesh, were used and it was desired to determine the capacity of the ball mill operating in closed circuit with each screen. From earlier tests using this flowsheet and equipment, it was known that when comparatively coarse screens were used it was necessary to increase the grinding dilution in the mill beyond that ordinarily used when grinding in closed circuit with classifiers. It was also known that after the circulating load had passed about 100 per cent of the original feed it tended to increase rapidly in amount, and grinding conditions appeared to become unstable. These conditions may be peculiar to this small ball mill but they were very marked in this series of tests. If conditions were not right, the mill would suddenly "go dead," and it was found desirable to operate so that the occasional rattle of balls against the lining of the mill could be detected. As the test proceeded, it was found that the cure for almost any difficulty that developed in the grinding circuit was to add more water to the mill feed. To begin with, the mill was operated at pulp densities of from 60 to 65 per cent solids but gradually it was found that with higher dilutions grinding conditions were more stable and the ball-mill power per ton of screen undersize decreased. Actually, the most satisfactory operating conditions were secured with a pulp density of about 40 per cent solids. The ore was hard but it was possible to grind ½-in. feed so that all would pass an 8-mesh screen with a power expenditure in the ball mill of less than 2½ kw-hr. per ton and with a circulating load of less than 50 per cent. With so high a dilution in the feed to the mill, it was feared that steel wear would be very high. However, the mill was not noisy, and in order to find exactly the grinding conditions, a special test was made at the end of the main series of tests. After the mill had been in operation for several hours and grinding conditions had become balanced, the power to all the equipment was shut off at a given signal. The ball mill made about one revolution after the power was turned off, and just as soon as the mill stopped, a spout was placed at the discharge trunnion and all of the pulp that flowed out of the mill was caught in tanks. The manhole in the mill was then opened and the whole mill charge dumped into other tanks. Both of these products were weighed, dried, and weighed again. The balls were screened out and weighed, and the dry solids were sized. In this way it was possible to determine the nature of the pulp and the ore within the mill under actual grinding conditions.

Jan 1, 1947

By Stephen Royce

[PAGE Ground Movement Adjacent to a Caving Block in the Climax Molybdenum Mine (TP 2000 by JOHN W. VANDERWILT, Min. Tech., May 1946. Discussion by STEPHEN ROYCE and the Studies of the Design of Shaped Explosive Charges and Their Effect in Breaking Concrete Blocks (TP 2157 by GEORGE B. CLARK, Min. Tech. May 1947. Discussion by PHILIP B. BUCKY, V. H. CLARK, E. D. GARDNER, M. H. HAWKINS, H. L. WALKER, and the author) 2 See TP 2377, Min. Tech., May 1948 for discussion of San Manuel ProsPect (TP 2255 by H. J. STEELE and G. R. RUBLY, Min. Tech., Sept. 1947. Discussion by L. KENNETH WILSON, ELDRED D. WILSON and the authors)] Ground Movement Adjacent to a Caving Block in the Climax Molybdenum Mine STEPHEN ROYCE•-It is interesting to note from B, Fig 2, how closely the subsidence limits approximate to the 60° angle of draw, which is so commonly found to rule in large scale rock subsidence. The tension cracks shown at B are commonly found in the initial stages of subsidence movement and spread like a halo about subsidence limits as movement extends. These tension cracks usually grow into escarpments later on. Apparently from the illustrations and description given, a system of vertical fractures is the predominating weakness in the wall rock at Climax, and therefore both tension cracks and escarpments are prevailingly vertical in attitude. The illustrations in Mr. Vanderwilt's article seem to conform to the general rule that yield by subsidence is heralded by tension cracks which foreshadow the appearance of the subsidence scarps which are both described in the paper and shown in Fig 2. The difference between the B side and the A side of Fig 2 is apparently caused mainly by the vertical fracturing which controls subsidence at Climax as compared to the relatively homogeneous rock formation at A upon which the original figure in Peele's Handbook was based. The draw at B is exactly 60°, while the draw at A is a little flatter. The influence of the vertical fractures explains the difference. The surprising feature is the relatively small deviation from the general 60° draw line, which is about the average of rock subsidence experience. The influence of local fracture systems, faults and bedding in controlling subsidence all the way from extremely low angles of draw to vertical is rather fully discussed in the Peele's Handbook article referred to. The more illustrations of subsidence there are published the better will be our knowledge. The general principles are pretty well established. The wide local differences reflect the effect of local conditions. This paper is a very valuable contribution to the subject, and for the benefit of the mining industry, it is to be hoped that there will be many more such clear and concise presentations. Particularly block caving is apt to be of greatly increasing importance in the future of a mining industry that must meet high labor costs. More examples of block caving from small scale to large scale operations like those at Climax will serve a vital need. JOHN W. VANDERWILT (author's reply)-I would like to thank Mr. Royce for his discussion; however, in his comments the meaning of subsidence, draw and tension cracks is not entirely clear. As used in my discussion of subsidence at Climax, subsidence refers to movements involving appreciable downward displacement. Tension cracks indicate only

Jan 1, 1947

By S. C. Sircar, D. R. Wiles

The rate has been studied of the hydrogen reduction of nickel ions in acetate -buffered solutions, using a nickel catalyst. At temperatures between 130°and 160°C, the rate is found to be proportional to the catalyst area, the nickel ion concentration, and the hydrogen pressure. The effect of hydrogen ions is to reduce the observed rate, likely by causing the reverse reaction (dissolution) to proceed. The experimental activation energy was found to be 25 kcal per mole. THE precipitation of metals and lower oxides from solution by hydrogen reduction has been quite actively investigated during the past few years.1 In the case of nickel, the kinetics of the precipitation have been studied in ammonia solution2 but extension of this study to acid solutions has not attracted much interest, largely because of the unfavorable thermodynamics at all but the lowest acidities. For example, Schaufelberger foundg that only 10 pct reduction of nickel could be effected in sulphate solutions. One kinetic study of the reduction of Ni++ has been reported by Knacke, Pawlek, and Sussmuth,4 in which the order of the reaction was found to be one in nickel ion and one-half in hydrogen pressure. No mention was made as to the part played by the nickel catalyst, or by the pH of the solution. Moreover, the activation energy reported (4 .12 kcal per mole) is so low as to lead to some question as to whether diffusion might be playing a major role in determining the kinetics. We have recently completed a study5 of the kinetics of the hydrogen precipitation of nickel from acetate-buffered acidic solutions whose results confirm and amplify those of Knacke et al. EXPERIMENTAL PROCEDURES The work was done in a high-pressure autoclavee by the usual technique of removing small samples of the solution for analysis. Nickel analysis was done colorimetrically by the dimethylglyoxime method.' The catalyst used was carbonyl nickel powder (Standard A powder of the Mond Nickel Co., Ltd.) which was found to be composed of spheres of less than 350 mesh. The surface area of the powder was determined in this laboratory by the B. E. T. method to be 1.85 sq m (m2) per g. The catalyst was added to the solution only after the proper temperature and pressure had been reached. Agitation of the baffled system was by a turbine-type impeller, rotated at speeds between 400 and 750 rpm. The reduction rate was found to be independent of the stirring rate, so it was assumed that diffusion in the liquid does not limit the rate. In typical experiments, the nickel concentration was unchanged during an induction period of variable length. The concentration then decreased sharply, and gradually levelled off to approach the final equilibrium value. In some cases, notably at high stirring rates, the nickel concentration was found to increase considerably during the induction period, and then to decrease. In all cases, the rate was determined from the slope of the tangent to the rate curve as the concentration first decreased below the initial value. This is seen in Fig. 1. The rate measurements were found to be reproducible to within about 5 and to be quite independent of the nature or duration of the induction period. The range of conditions used is given in Table I.

Jan 1, 1961

By E. D. Glass, R. C. Hessing

The volume of gas in storage reservoirs may be compuled from estimates of hydrocarbon pore volume and gas density. However, both are dificult 10 estimate accurrately. Further, no adequate method has been presented for estimating reservoir performance during operation for Volumetric gas-storage reservoirs. Normally, gas-storage reservoirs exhibit small pressure gradients in the area conr(zilliitg the storage wells, even under conditions of maximum injection or withdrawal. A zone of low permeability usally surrounds, and is in communication with, tile permeable zone which causes the storage reservoir to exhibit a definite pressure lag, as evidenced by lack of pressure stabilization after extended periods of shut-in. An analysis is presented for determining pore volume and gas in place, and for predicting future reservoir behavior of such reservoirs. The mathematical development is presented and a solution is shown for an operating storage reservoir. INTRODUCTION Depleted gas reservoirs arc often used for gas storage. The reservoir usually contains a permeable area in which numerous storage wells arc located. The permeable zone permits high deliverability and injectivity with relatively small pressure loss. However, pressure equilibrium may not be attained even after long periods of shut-in because of the fact that the permeable zone is in communication with an adjacent tight section. Most of these gas-storage reservoirs are sand lenses, such as ancient beaches or offshore bars. The areal geometry of these reservoirs is normally such that flow in the tight zone will be approximately linear, and the solutions presented here should apply. DISCUSSION For purposes of this paper, a gas-storage reservoir is considered to consist of a volume of permeable rock in communication with tight rock, all of which is surrounded by an impermeable barrier. Pressure gradients across the permeable zone are small due to low flow resistance and well density. Hence, the permeable zone is considered to be at a uniform pressure which is only a function of time as gas is injected or withdrawn. The tight zone is considered to be linear with uniform permeability and porosity, and the pressure in the tight zone is a function of both position and time. l'wo solutions for flow in this system are used to define the reservoir and determine its properties. The first solution is for an infinite linear tight zone in communication with the permeable zone. The expression for constant gas-withdrawal rate is Eqs. I and 2 ore superposed to account for varying rates of production or injection and are used to fit gas-storage field reservoir history. The solution for the infinite case, Eq. 1, is first applied to field data for early times following a shut-in period. Constants BDa and c are ohtained by a least-squares fit of pressure and rate data. After the pressure wave from gas injection or withdrawal reaches the external boundary of the tight zone, the infinite solution will no longer apply and pressure behavior should be more nearly represented by Eq. 2 for a gas reservoir in communication with a finite linear tight zone. The values of the constants found from curve-fitting Eq. 1 to the early time data may then be used in Eq. 2 that only the coefficient- L containing the unknown

By E. W. Davis

ABOUT a year ago several carloads of magnetite ore from New York state were sent to the Mines Experiment Station at the University of Minnesota for grinding and concentration tests. The flowsheet used minus ½ -in. ore as feed to a 3 by 3-ft. overflow cylindrical ball mill operating at 37 r.p.m. in closed ciruit with a vibrating screen. The screen oversize was returned to the mill for further grinding and the screen undersize was concentrated magnetically. Several different screens, between 8 and 35 mesh, were used and it was desired to determine the capacity of the ball mill operating in closed circuit with each screen. From earlier tests using this flowsheet and equipment, it was known that when comparatively coarse screens were used it was necessary to increase the grinding dilution in the mill beyond that ordinarily used when grinding in closed circuit with classifiers. It was also known that after the circulating load had passed about zoo per cent of the original feed it tended to increase rapidly in amount, and grinding conditions appeared to become unstable. These conditions may be peculiar to this small ball mill but they were very marked in this series of tests. If conditions were not right, the mill would suddenly "go dead," and it was found desirable to operate so that the occasional rattle of balls against the lining of the mill could be detected. As the test proceeded, it was found that the cure for almost any difficulty that developed in the grinding circuit was to add more water to the mill feed. To begin with, the mill was operated at pulp densities of from 60 to 65 per cent solids but gradually it was found that with higher dilutions grinding conditions were more stable and the ball-mill power per ton of screen undersize decreased. Actually, the most satisfactory operating conditions were secured with a pulp density of about 40 per cent solids. The ore was hard but it was possible to grind ½ in. feed so that all would pass an 8-mesh screen with a power expenditure in the ball mill of less than 2 1/2 kw-hr. per ton and with a circulating load of less than 50 per cent. With so high a dilution in the feed to the mill, it was feared that steel wear would be very high. However, the mill was not noisy, and in order to find exactly the grinding conditions, a special test was made at the end of the main series of tests. After the mill had been in operation for several hours and grinding conditions had become balanced, the power to all the equipment was shut off at a given signal. The ball mill made about one revolution after the power was turned off, and just as soon as the mill stopped, a spout was placed at the discharge trunnion and all of the pulp that flowed out of the mill was caught in tanks. The manhole in the mill was then opened and the whole mill charge dumped into other tanks. Both of these products were weighed, dried, and weighed again. The balls were screened out and weighed, and the dry solids were sized. In this way it was possible to determine the nature of the pulp and the ore within the mill under actual grinding conditions.

Jan 1, 1945

By Roscoe C. Clark

A study of the effect of various corrosive waters on five different types of cements indicated that those cements containing less than 5 per cent tricalcium aluminate were the most resistant to corrosion. INTRODUCTION Oil field experience indicates that some formation waters are excessively corrosive to some cements. A study has been made to determine the most corrosive waters and the relative resistance of various types of cement to these corrosive waters. PROCEDURE This study of the corrosion of cement was limited to an evaluation of the effect of various corrosive waters on five different types of cements. A determination was made of the types of cements which offer the greatest resistance to corrosion and of the chemical contents of waters found to be the most destructive to cements. The laboratory tests were conducted by immersing small cylinders of 20 samples of set cement in various corrosive waters. The initial mixing of most of the cement slurries was done using Tulsa tap water as the mixing water; however, a few of the slurries were mixed using a sulfate water as the mixing water. When the 20 samples had been immersed for a period of nine months, they were removed from their corrosive baths, inspected and photographed. The field tests were conducted by placing ten cement specimens, each contained in a screen wire thimble, in the gas anchors of insert pumps in wells in six different fields. The specimens were observed whenever it was necessary to pull the pumps and were returned to the 1aboratory when deterioration had reached a serious state. EXPERIMENTAL RESULTS In both the field and laboratory tests the resistance of the different cements to corrosion was determined by the condition of the samples and the number of samples of each that were in good condition at the end of the immersion period. Table I lists the various cements tested in the order of their resistance to corrosion with the most resistant at the top and the least resistance at the bottom. An analysis of Table I reveals that the upper half of the table predominates in slow set and sulphate resisting cement.: (low 3CAO.A12O3 content) while in the lower half the port-land and high early strength cements are in the majority. Of the last two the high early strength cements appear to offer less resistance to sulfate water corrosion. An investigation of the composition of the cements listed in Table I indicated that as a general rule the cements containing less than five per cent tricalcium aluminate will exhibit the greatest resistance to corrosion. The destructive action of various corrosive waters was compared by listing the waters in the order of those containing the largest number of samples that failed completely. These ratings are presented in Table II with the most corrosive waters listed first and the least corrosive last. Figs. 1 and 2 show the end views of cement samples which had been immersed in the baths of five per cent MgSO, water and the five per cent Na2SO4 water respectively in the laboratory. These .pictures are representative of the results obtained and present a pictorial evaluation of the corrosive resistance of various types of cements.

Jan 1, 1950

By C. E. Silverblatt, D. A. Dahlstrom

Previous bench-scale studies demonstrated that a substantial moisture reduction can be obtained by the application of steam to coal filter-cakes, particularly to those containing a limited amount of minus 200-mesh material. Consequently, U.S. Steel's Applied Research Laboratory conducted a study to determine the feasibility of steam filtration of 1/4 in. by 0 coal on a continuous pilot-scale installation in which an Eimco extractor is used. The test results showed that the moisture content of this coal could be reduced to 5.5% at a steam loading of about 175 lb of steam per ton of dry cake. In terms of steam consumption, this loading is calculated to be 1-1/2 lb of steam per lb of water removed. In some tests, only 1 lb of steam per lb of water removed was required. These levels of steam consumption are significantly less than the actual heat requirements of conventional thermal dryers. The satisfactory moisture reductions were obtained at filtration rates of 125 to 186 lb of dry solids per sq ft per hour. However, the proper design of commercial filters should improve the potential rates that can be attained. These results indicate that steam filtration has considerable economic potential for drying 1/4 in. by 0 coals and also has additional advantages over the conventional thermal drying of coal. The results of the previous bench-scale studies and those published by Burton' demonstrated that a substantial moisture-content reduction can be effected by the application of slightly superheated steam to coal filter-cakes, particularly to those containing a limited amount of minus 200-mesh material. Consequently, US Steel's Applied Research Laboratory conducted a study to determine the feasibility of steam filtration of 1/4 in. by 0 coal on a continuous basis. In the continuous process, the dewatering operation on the filter is conducted in stages. In the first, the bulk of the water in the feed slurry is removed by conventional mechanical dewatering on a portion of the filter before the steam is applied. In the second stage, steam is applied to the cake. The steam condenses and releases its latent heat, thereby reducing the viscosity of the remaining cake water; this reduced viscosity then facilitates further drainage and produces a cake of lower moisture content. Because of the availability of feed coal on a continuous basis and since steam was readily available from a low-pressure boiler, the Applied Research Laboratory selected for the test site a coal-preparation plant that cleans Pittsburgh Seam coal. A slurry of table and flotation coal in percentages as they occur normally was used as feed stock. Typical analyses of this slurry are shown in Table I. DESCRIPTION OF FILTER AND EXPERIMENTAL PROCEDURES An Eimco Extractor was selected for the evaluation of steam filtration in a continuous process. This unit was chosen because of its availability and its design features that permit relatively simple hood construction, instrumentation, and operation. A photograph of the Extractor is shown in Fig. 1. In the filter a cloth medium is used that travels horizontally and continuously with a grooved, rubber drainage belt. The total effective filter area was 12.5 sq ft. As the feed slurry flows by gravity from the feed box onto the medium,

Jan 1, 1964

By E. W. Davis

About a year ago several carloads of magnetite ore from New York state were sent to the Mines Experiment Station at the University of Minnesota for grinding and concentration tests. The flowsheet used minus ½-in. ore as feed to a 3 by 3-ft. overflow cylindrical ball mill operating at 37 r.p.m. in closed ciruit with a vibrating screen. The screen oversize was returned to the mill for further grinding and the screen undersize was concentrated magnetically. Several different screens, between 8 and 35 mesh, were used and it was desired to determine the capacity of the ball mill operating in closed circuit with each screen. From earlier tests using this flowsheet and equipment, it was known that when comparatively coarse screens were used it was necessary to increase the grinding dilution in the mill beyond that ordinarily used when grinding in closed circuit with classifiers. It was also known that after the circulating load had passed about 100 per cent of the original feed it tended to increase rapidly in amount, and grinding conditions appeared to become unstable. These conditions may be peculiar to this small ball mill but they were very marked in this series of tests. If conditions were not right, the mill would suddenly "go dead," and it was found desirable to operate so that the occasional rattle of balls against the lining of the mill could be detected. As the test proceeded, it was found that the cure for almost any difficulty that developed in the grinding circuit was to add more water to the mill feed. To begin with, the mill was operated at pulp densities of from 60 to 65 per cent solids but gradually it was found that with higher dilutions grinding conditions were more stable and the ball-mill power per ton of screen undersize decreased. Actually, the most satisfactory operating conditions were secured with a pulp density of about 40 per cent solids. The ore was hard but it was possible to grind ½-in. feed so that all would pass an 8-mesh screen with a power expenditure in the ball mill of less than 2½ kw-hr. per ton and with a circulating load of less than 50 per cent. With so high a dilution in the feed to the mill, it was feared that steel wear would be very high. However, the mill was not noisy, and in order to find exactly the grinding conditions, a special test was made at the end of the main series of tests. After the mill had been in operation for several hours and grinding conditions had become balanced, the power to all the equipment was shut off at a given signal. The ball mill made about one revolution after the power was turned off, and just as soon as the mill stopped, a spout was placed at the discharge trunnion and all of the pulp that flowed out of the mill was caught in tanks. The manhole in the mill was then opened and the whole mill charge dumped into other tanks. Both of these products were weighed, dried, and weighed again. The balls were screened out and weighed, and the dry solids were sized. In this way it was possible to determine the nature of the pulp and the ore within the mill under actual grinding conditions.

Jan 1, 1947

By A. M. Gaudin, C. S. Chang

Adsorption was measured for barium ion and laurate radical, using radioactively marked agents, over wide range of concentrations. Laurate adsorbed in absence of barium fails to float. With barium, flotation-effective laurate coating needs not exceed 5 pct of monolayer. Barium adsorption then is several fold larger. No barium laurate coating is obtained. IN general, fatty acids or their alkali salts do not cause clean quartz to float. However, the presence of multivalent ions, such as the alkaline-earth metal ions and heavy-metal ions, can activate quartz and thus make it respond to soap flotation. The mechanism of activation and soap flotation of quartz has been studied.'-' The problem was attacked by making flotation tests rather than by careful adsorption measurements on suspensions of ground quartz in solutions containing the activator and the collector. Attempts have been made to determine the adsorption of barium ion and calcium ion on quartz. The results have only qualitative value as the analytical methods were not adequately precise. Artificial radioactivity and progress in radioactivity detection have introduced a new analytical tool, which can have a sensitivity several orders of magnitude greater than that of other methods."-" In the experimental work described in this paper the radioactive tracers, barium 140 and carbon 14, were employed. Lauric acid was synthesized, having a radioactive carbon atom and was used with Ba" to study the adsorption of barium and laurate ions from aqueous solution on ground quartz. Flotation tests, using the vacuum flotation technique,' were run in conjunction with the adsorption experiments. The object of this investigation was to understand better the reaction mechanism of barium activation and soap flotation of quartz. Methods and Materials Quartz Sample Preparation: Lumps of hand-picked quartz, washed free of stains, were reduced in size to —20 mesh in laboratory crushers. The product was boiled in concentrated hydrochloric acid to remove the abraded iron. The cleaned product then was ground dry in a laboratory porcelain mill, using siliceous pebbles, to pass through a 200 mesh screen. The ground product was deslimed by sedimentation at 37 microns. This —200 mesh +400 mesh material was subjected again to boiling with concentrated hydrochloric acid, followed by washing with distilled water and further desliming. The cycle was repeated until no trace of iron could be detected in the wash liquor. During the final washing, the pH of the wash water was checked to insure the complete removal of the acid from the mineral. The quartz then was rinsed with conductivity water. The resulting product was dried in a drying oven and stored in mason jars. The impurities (spectrographic) were as follows: Al, 0.01 to 0.001 pct; Li, Mg, Mn, Na, each less than 0.001 pct; Fe and Cu not detected. The specific surface of the quartz sample was determined by the krypton gas adsorption method.' The average of two measurements was 881 sq cm per g. The calculated specific surface for 37/74-micron quartz particles, using a surface factor of 1.96; is 900 sq cm per g. This is in good agreement with the measured value of 881 sq cm per g. Beta-Counting Method: The radioactive isotope of barium used in the experimental work was barium 140. It has a sufficiently long half-life, 12.8 days, emits high-energy beta particles (up to 1.0

Jan 1, 1953

By R. J. Hopkins, L. B. Haney

On the basis of limited experimental work conducted at the Port Pirie smelter, it would appear that, by increasing the specific surface of sinter, and possibly that of coke as well, a marked increase in the rate and degree of sinter reduction in the furnace shaft can be achieved. Fusion-point tests have shown that this increased reduction means a much higher sinter fusion point and narrower plastic zone, while the more efficient utilization of coke in the furnace is inherent in the intensification of reduction by the provision of a more reactive sinter surface. Investigations aimed at increasing the ability to operate the blast furnace with a higher lead tenor of sinter reducing fuel cost proportionately, and at eliminating the loss in reduction potential in coke entering the furnace, as shown by the presence of appreciable proportions of CO in the top gases, are reported. Several lines for future investigations that could result in improved smelting methods are proposed. A SOMEWHAT informal presentation of ideas on lead blast-furnace smelting will be given in this paper. These ideas have been developed during observations of furnace behavior at Port Pirie and earlier at Mt. Isa, and have been guided by the results of laboratory experiments at Port Pirie. The authors do not intend to propound any particularly new theories, but present their ideas as a basis for discussion which may help toward a better understanding and improved control of blast-furnace operation. Performance variations of considerable magnitude occur from time to time at most lead blast-furnace plants. While Port Pirie is fortunate in having a very regular supply of high grade concentrates, it is no exception in this respect. Such irregularities are of considerable economic importance and they constitute a challenge to present-day metallurgists in their efforts to obtain an ever greater degree of control over furnace operation. In operating as Port Pirie does with a relatively high lead charge, it has been recognized for a long time that shaft conditions are ,of the greatest importance. A practical, or engineering, attack on the problem of accretions consisted of changes in furnace design, e.g., by widening the shaft to 10 ft above the bottom row of tuyeres, and by the provision of curved ends and vertical walls.' That this attack has had a great measure of success is shown by the fact that barring down of these wide furnaces is rarely necessary, shaft conditions have greatly improved, and sensitivity to charge variations has been markedly reduced. These modifications, followed by some metallurgical changes (chiefly the incorporation of pig iron into the furnace charge in 1948), have brought furnace operation to a point where some variables which were previously masked can now be studied. Accordingly, over different periods of time during the last five years, such variables as could be given numerical values have been recorded and subjected to statistical examination. The objectives of this work were: 1—to reveal the true importance of the different variables and 2—to show the proportion of total furnace variation which is unexplained and therefore referable to causes not measured at present? e.g., shaft accretions, sinter structure, coke structure, and others. Statistical Study of Variables In this work factors relating to furnace speed and lead reduction have been examined: 1—slag com-

Jan 1, 1955

By J. L. Thompson

There are two basic forms of the LPG-slug process: the gas driven and the water driven. The pressure required for miscibility between gas and LPG prohibits the use of the gas-driven LPG process in shallow reservoirs. The water-driven LPG slug process normally exhibits good sweep efficiency. However, displacement of the LPG by water is poor. An improvement in this process appears possible by injecting a slug of carbon dioxide between the LPG slug and the water drive. Laboratory experiments were conducted in homogeneous linear systems to determine the effect of pressure on the various displacement zones. In the carbon dioxide-LPG displacement zone, the effect of pressure on the displacement efficiency is negligible above the miscibility pressure. However, the displacement efficiency decreases linearly with decreasing pressure below the miscibility pressure. With water displacing carbon dioxide, it was found that the recovery of carbon dioxide after water breakthrough can be predicted from its solubility in water. A displacement test was conducted with LPG and carbon dioxide slugs large enough to avoid interference between the oil-LPG, LPG - carbon dioxide and carbon dioxide - water displacement zones. Under these conditions, essentially complete oil and LPG recovery was obtained. However, a substantial amount of carbon dioxide was left in the core at water breakthrough. INTRODUCTION It has been shown in homogeneous linear systems that essentially complete oil recovery can be obtained by displacement with a miscible fluid such as LPG. Economic considerations dictate that the valuable LPG also be recovered. Methods proposed for recovering the LPG include (1) displacement with natural gas at a pressure high enough to make the two fluids miscible1 (the disadvantage of this method is that the required pressure of about 1,500 psi is too high for shallow reservoirs) and (2) displacement of the LPG with water2 (principal disadvantage is that a large amount of LPG remains in the formation because of poor displacement efficiency). This paper treats an improvement in the water-driven LPG slug process3,4 where carbon dioxide is injected between the LPG and water. Carbon dioxide is completely or at least partially miscible with propane and soluble in water; thus, displacement efficiency is improved at both ends of the carbon dioxide slug. To minimize effects of other variables, all experiments were conducted in linear core systems. GENERAL PROCESS DESCRIPTION The displacements of propane by carbon dioxide and carbon dioxide by water are considered separately, assuming enough of each is injected to prevent mutual interference. Displacement descriptions are confined only to the part of the pore volume containing mobile fluids unless otherwise specified. The schematic representation is given in Fig. 1. Starting at the producing well, a zone containing only oil is followed by a zone containing a single-phase mixture of propane and oil. The concentration of propane increases in the direction of the injection well and ultimately grades to pure propane. Then follows a zone containing a mixture of propane and carbon dioxide in continuously varying proportions until 100 percent carbon dioxide is reached. In this zone, the concentration of carbon dioxide in the immobile water phase also varies from zero to full saturation. Whether the displacement of propane by carbon dioxide is of complete or partial miscibility depends on pressure and temperature (Fig. 2). If the horizontal line representing the prevailing pressure intercepts the boundary curves of the phase envelopes for the prevailing temperature (i.e., if the pressure is lower than the critical

By J. L. Zakin, G. K. Patterson, J. M. Rodriguez

Correlation has been obtained between drag-reducing characteristics for turbulent flow in a pipe and measurable properties of several polymer solutions. Several concentrations of high molecular weight polymethyl methacrylate in toluene, high molecular weight polyisobutylene in both toluene and cyclohexane, medium molecular weight polyisobutylene in cyclohexane and benzene and low molecular weight polystyrene in toluene were studied. Data obtained in these nonpolar solvents and literature data for more polar solvents were successfully correlated as the ratio of measured friction factor to purely viscous friction factor vs the modified Deborah number vrl/D0.2 where 71 is the first-mode relaxation time of the solution estimated by the Zimm theory. A shift factor which is a function of intrinsic viscosity 1/(4[?] - 1) allowed all the data obtained with nonpolar solvents to be correlated as a single function. For these systems, most of the data fit a single curve to within + 5 percent of the average friction factor ratio. The shift factor did not give a unique function of the data for the more polar systems. INTRODUCTION The phenomenon of drag reduction in polymer solutions was first studied by Toms1 in dilute solutions of polymethyl methacrylate in mono-chlorobenzene. The drag ratio for flow through circular tubes has been defined2 as the ratio of the pressure. drop of the solution to the pressure drop of the solvent at the same flow rate. The drag ratio is less than 1.0 for a drag-reducing fluid. Practical use of drag reduction is being made in fracturing operations in the petroleum industry.3 A more fundamental quantity is the friction factor ratio, defined as the ratio of the observed pressure drop to that predicted for a solution of the same viscosity characteristics and density at equal flow rates using the Dodge-Metzner friction factor equation4 Viscous solutions with drag ratios greater than 1.0 can have friction factor ratios less than 1.0. For practical applications, it is drag reduction which is of interest. However, for correlation the fundamental ratio is the friction factor ratio. In recent years, drag reduction has been studied extensively. Recent studies have shown that reasonable predictions of the incipience of drag reduction in polymer solutions can be made from the properties of the solutions and the flow Variables.5 However, it has not been possible to predict accurately the amount of drag reduction to be expected for a given polymer solution without any drag-reducing turbulent flow data on the same solution.6 For flow through circular tubes it is well established that there is a concentration effect and a diameter effect on drag reduction. Toms1 observed that drag reduction increases with an increase in the concentration of the solution up to an optimum concentration beyond which, due to the increased viscosity of the solutions, the drag ratio increased with an increase in concentration. Hershey 7 observed that for dilute Newtonian polymer solutions in nonpolar hydrocarbon solvents, a normal transition region may be obtained followed by a departure from the von Karman equation (on a friction factor-generalized Reynolds number chart). The point of departure is a function of diameter: the smaller tubes depart at the lower Reynolds numbers. Concentrated solutions may show no abrupt transition region, but merely an

By P. G. Meikle, C. T. Holland

The effect of the condition of friction upon the ultimate unit compressive strength as determined between the compressed faces of precisely machined coal specimens and specially prepared testing platens has been examined. Reductions of 30 to 40% in the ultimate unit compressive strength of these model coal pillars have been verified when lubricants areused between the faces as compared to non-lubricated faces. Increase in unit compressive strength due to confinement at each of three levels of friction appears to follow generally the widely accepted "1/2 power law", i.e. S - C (L/T)1/2 where S is the unit ultimate strength, C is a constant dependent on the coal being tested and the coefficient of friction acting at the compression surfaces and L and T are the least width and thickness of the specimen, respectively. Results suggest that the surface condition of both the specimen and platens should be mentioned in detail in conjunction with compression testing, for although the term (L/T)1/2 is adequate for all practical purposes, the coefficient C is directly dependent on the condition of interfacial friction, all else remaining constant. One phase of the investigation of the confining effect of friction on the ultimate unit compressive strength of small coal specimens has recently been completed at the School of Mines of West Virginia University. The efficient control of ground is of fundamental importance to successful mining operations and the design of support pillars has always presented the mining engineer with a difficult and intriguing engineering problem. Since about the turn of the century, many investigators have performed extensive laboratory tests on small coal specimens in efforts to solve some of the perplexing problems of strata control and pillar action in coal mines. A detailed review of this work would serve no purpose here, but a brief mention of the more significant contributions is in order. Muller16 was perhaps the first to illustrate the effect of confining pressure on the strength of coal specimens in compression. His work has recently been more carefully expanded by the experiments of Murrell17 in Great Britain. Rice and Enzian l9 observed that as the size of cubical test specimens increased, the unit compressive strength decreased. These observations were later supplemented by Lawall and Holland, 13 by Greenwald4,5 et a1 at the U. S. Bureau of Mines, by Gaddy3 as well as by Steart,22 Millard15 et a1 and Evans2 et al. Gaddy3 seems to have been first to quantify this relationship with his equation: S = K/vd , where S - ultimate unit compressive strength (psi), K = a constant dependent on the coal, and D =edge dimension (in inches). Holland7 concluded that the strength of coal as affected by lateral dimensions and thickness could be expressed as where K = a coefficient dependent upon the coal, L = least width of pillar (in.) and T = thickness of pillar (in.). Data supplied by this formula have been compared to the estimated stresses in pillars that had been standing for long periods in coal mines and in the cases so far studied the results indicate that the formula predictions are sufficiently accurate for engineering purposes (Holland11 ). This equation therefore is believed to be the simplest and most accurate tool available at the present time for approximating the strength of a coal pillar (over a specified range of L/T) in situ. However, Holland7,9 has indicated that friction between the coal pillars and the top and bottom rock

Jan 1, 1965

By Charles Prasky

ABOUT five years ago the Bureau of Mines began a study, at Minneapolis, of the various methods for beneficiating the low-grade manganese deposits of the Cuyuna range. Several samples of green carbonate slate from the Cuyuna range, containing about 7 pct Mn and about 28 pct Fe, were obtained for this study. The component minerals in the carbonate slate formation were so intimately associated that mineral dressing methods were not suitable for concentrating manganese to a ferrograde product. Although upgrading of manganese and iron minerals has been effected by flotation methods, it appears that manganese cannot be separated from iron except by chemical means. Because the flotation studies at Minneapolis were carried out simultaneously with the hydrometallurgical studies, only crude slate was available for process testing. An important economic consideration in selecting any one of the several chemical methods proposed for recovering ferrograde manganese is the availability of the chemical reagent. Fortunately, large tonnages of sulfur are available on the Cuyuna range in low-grade pyrite and pyrrhotite deposits that are readily concentrated by flotation to a suitable feed for a sulfide roasting furnace as indicated by a Bureau of Mines investigation in 195 0-1951.1 The roasted residue from the sulfide concentrates is a potential source of marketable iron oxide. Therefore, if these sulfide deposits were employed in recovering manganese, utilization of two heretofore unused mineral deposits would be accomplished. Laboratory investigations of several proposed leaching processes were made as a preliminary step in the investigation of hydrometallurgical methods for the treatment of Cuyuna carbonate slate using sulfur as a chemical reagent. From results obtained in the laboratory tests, these leaching processes did not appear entirely suitable for treating Cuyuna carbonate slate. The method developed at the North Central Experiment Station and selected for a more intensive pilot-plant investigation has been termed the differential high-temperature sulfatizing process. Essentially, this sulfatizing process consists of the following steps, described in the order in which the small-scale pilot-plant investigations were made. The first and perhaps most significant step in the process consists of a sulfate roast. Carbonate slate is roasted in an atmosphere of sulfur dioxide gas and air. The overall chemical reaction for converting manganese carbonate to a sulfate at a high temperature in a sulfur dioxide atmosphere follows MnCO8 + SO2 + 1/2 0, = MnSO4 + CO2 (H077°O = —64,180 cal per g mol) .' The need for concentrated sulfuric acid is avoided. Fine grinding is not essential. Removal of carbon dioxide from the slate during roasting produces a more porous structure and permits easier permeation by the sulfatizing gas mixture. The temperature limits for this conversion of manganese have been established as 600" and 850°C. Iron sulfate is unstable and is not formed at these temperatures; phosphorus is not converted to a water-soluble form; and polythionates are not formed. The second step in the process consists simply of a water leach of the sulfatized product. Manganese sulfate in the sulfatized product is dissolved in water. Iron, phosphorus, and calcium remain in the leach residue as water-insoluble products. The third and final step consists of the recovery of ferrograde manganese oxide from manganese sulfate leach solution. Water is evaporated from the leach solution, and impure monohydrate crystals of manganese sulfate are recovered. The moist crystals are formed into pellets or extrusions and thermally decomposed to produce a ferrograde manganese

Jan 1, 1958

By E. P. Miesch, P. B. Crawford

A study was made of the effect of permeable and impermeable lenses in a reservoir on the production capacity of a well. Both steady-state and unsteady-state data were obtained. An electrical resistivity model was used to obtain the steady-state data and thermal models. were constructed to obtain the unsteady-state data. The productivity of a well is affected very greatly only when the lenses are close to the well. The effect of circular lenses on the productivity ratio can be correlated with the distance from the center of the lens to the center of the well divided by the radius of the lens. When this dimensionless distance is equal to six or greater, the effect of the lenses on production capacity will be negligible. The pseudo steady-state productivity of a heterogeneous reservoir can be predicted using steady-state data. INTRODUCTION Many analytical solutions of reservoir behavior assume that reservoir rock is uniform and homogeneous. Although this assumption is used, all of the data from core analyses and well logging indicate that the reservoirs are heterogeneous. Very little work has been done on the performance of heterogeneous reservoirs. The work of Landrum,l et al. showed that transient phenomena in oil reservoirs could be studied with thermal models. Pickering and Cotman2 used thermal models to study flow in stratified reservoirs and investigated the effect of inhomo-geneities in oil reservoirs on transient flow performance. Loucks3 made a mathematical study of the pressure build-up in a system composed of two concentric regions of different permeability. Root, Silberberg and Pirson4 studied the effect of the growth of the flooded region on water influx predictions using a thermal model consisting of three concentric cylindrical regions of different thermal properties which simulated the aquifer, the flooded region and the unflooded portion of the original hydrocarbon region. Tomme, et a1.5 made a mathematical study of vertical fractures. The object of this investigation was to study the effect of highly permeable and impermeable lenses in the vicinity of the wellbore on the pressure depletion history of the well. Steady-state data were obtained for both conductive and nonconductive lenses that completely penetrated the formation. The lenses were symmetrically located at various distances from the wellbore. The unsteady-state data were obtained on seven thermal models. EXPERIMENTAL EQUIPMENT AND PROCEDURE STEADY-STATE DATA The steady-state data were obtained from an electrical resistivity model 30 in. in diameter and approximately 11/2 in. deep. The outside of the model was lined with a 30-in. diameter copper strip, which served as the outer boundary of the reservoir. The bottom was covered with a sheet of plexiglass so that it would be nonconductive. The model was filled with a slightly saline solution. The well size was varied from an 0.064-in. diameter copper wire to a 10-in. diameter copper cylinder. Readings were taken with an impedance bridge using AC current to prevent polarization at the contacts. Copper and wax lenses were used to represent infinitely conductive and nonconductive lenses, respectively. The resistance was first measured for each well diameter with no lenses in the reservoir. Then the conductive and nonconductive lenses were spaced symmetrically at various distances from the well and the resistance read from each lens location. The diameters of the conductive lenses were 3, 1.022 and 0.624 in., and those of the nonconductive lenses were 3, 2.25 and 1.563 in. The ratio of each resistance reading to the resistance reading with no lenses in the reservoir

Jan 1, 1965

By Meguru Nagamori

DURING the smelting of the sulfide ores of copper, nickel, and certain other metals, a matte phase is formed. For a better understanding of the physico-chemical properties of mattes, binary systems such as Cu-S, Ni-S, Fe-S, and so forth, should be studied, especially in the vicinity of liquid compounds such as Cu2S, Ni3S2, FeS, and so forth. These compounds are relatively stable in the solid state although they can exhibit appreciable deviations from stoichiometry. With small deviations from stoichiometry there are large changes in the activity of both sulfur and metal this is a characteristic of both solid and liquid sul-fides near the stoichiometric compositions. In the vicinityof molten Cu2S,1 for instance, the activity of sulfur increases about 100 times for a 0.012 increase in the mole fraction of sulfur and, correspondingly, the activity of copper decreases greatly. In this sens the minor deviations from stoichiometry should be carefully taken into account in studies of such metal-sulfur melts. Metal-sulfur melts may be considered to have properties intermediate between metallic solutions and molten salts, i.e., neither entirely metallic nor entirely ionic. The radius of the ion sZ- is 1.84 as compared with 1.04? for a single bond covalent s.2 It is therefore inferred that when the sulfur is more ionic its partial molar volume is larger, although metal-metal, metal-sulfur, and sulfur-sulfur interactions may bring about further complexities. Thus, it is to be expected that the molar volumes, which are derived from density-composition relations, will help in resolving the structure of the melts. In this study the maximum bubble pressure method with bubbling gases of H2, H2S, and Ar, .was employed to measure the density. EXPERIMENTAL Materials. Silver of 99.95 pct purity was melted in an alumina crucible and hydrogen gas was then bubbled through the liquid for the deoxidation. In preparation of Cu2S, electrolytic copper powder (>99.9 pct Cu) was mixed with precipitated sulfur and heated to 1200°C in an alumina crucible under a hydrogen atmosphere. Mixtures having the approximate compositions FeS and Ni3S2 were prepared by heating reagent grade electrolytic iron or reduced nickel powder with precipitated sulfur under a hydrogen atmosphere. The H2S gas was of 98.5 pct purity, the impurities being mostly CO2 and CS2 which hardly contaminate the melts. Apparatus. The crucible system is shown schematically in Fig. 1. To minimize the variation of melt composition during a density measurement, the apparatus was designed in such a way that either Ar, H2, H2S, or mixtures of these gases could be used as the bubbling gas. When the melt had a high partial pressure of sulfur, H2S gas was used. When the partial pressure of sulfur was so low that oxygen might dissolve in the melt, the use of H2 was preferred. In intermediate cases, argon or mixtures of H2-H2S were used. Density of Dibutylphtalate. Dibutylphtalate was used as the manometer fluid. Relative to distilled water, the density of the dibutylphtalate, pdib g per cc, was measured and found to be: pdib (25°C) = 1.046 i 0.002. With the use of the temperature coefficient reported by Kemppinen and Gokcen,3 the following value was

Jan 1, 1970

By E. F. Bailey, W. J. Harris

THE temperature of the ferrite to austenite re-action is established frequently by continuous heating experiments. However, equilibrium studies of this reaction have demonstrated that austenite may form at temperatures considerably below those at which the reaction is first observed during continuous heating. Because of this discrepancy, tempering is sometimes performed above the true critical temperature and in these cases austenite forms during tempering. The lowest temperature at which austenite forms and the kinetics of the reaction have been studied by Bain,' Bleakney and Gros-venor,2 and Dube and Cunningham. This austenite can affect the properties either as austenite per se, if it is retained at room temperature, or as a decomposition product if it transforms. The effect of austenite formation during tempering on low temperature impact properties of an 8 1/2 pct nickel steel was reported by Brophy and Miller4 in work published after the present investigation was initiated. They concluded that the improvement in low-temperature notch toughness which followed tempering at certain temperatures could be attributed to the austenite formed during tempering. Kramer et al.5 found anomalous hardness increases and embrittlement after tempering of a low-carbon manganese-nickel steel. They concluded that austenite formed during tempering, and that the decomposition products were responsible for the increase in hardness and the embrittlement. Quan-titative correlations of the microconstituents and mechanical properties were not made by these investigators. The present study was undertaken in order to establish the kinetics of formation of austenite at various temperatures, the characteristics of the decomposition of this austenite, and the relationship between mechanical properties and the phases present. Experimental Procedure A low-carbon manganese-nickel steel was selected because of the sluggishness of its austenite decom-position reactions. The composition of this steel in percent was: C, 0.10; Mn, 3.52; Ni, 2.34; Mo, 0.52; Cr, 0.17; Si, 0.19; V, 0.15; P, 0.019; and S, 0.020. Samples were prepared by forging sections from a large ingot to 3/4 in. bars. Formation and decomposition of austenite were investigated by dilatometric techniques which were checked by X-ray measurements. Dilatometer specimens were hollow cylinders 1 in. long, 1/2 in. diam, with a 1/8 in. central hole. All specimens were aus-tenitized for 1 hr at 1650°F and quenched in water prior to insertion in the dilatometer. Oxidation was prevented by using an inert atmosphere of purified nitrogen. Dilation was measured with a dial gauge which could be read by interpolation to 0.00005 in. Temperature was maintained within ± 3°F by a Brown Electronik Controller. Chromel-alumel thermocouple leads were welded to opposite ends of the specimen with the specimen serving as the hot junction. As a check on temperature uniformity comparison was made of the specimen temperature as measured with the chromel-alumel leads and the temperature of the center of the specimen as measured with a calibrated platinum—platinum-rhodium thermocouple embedded in asbestos in the central hole of the specimen. During heating a 5°F temperature difference was noted below 1000°F, but none above, while in cooling, a 5°F difference was observed from 1300" to 735°F, but none below. Heating rates of 35°F per min and cooling rates of 60°F per min were employed for all dilatometric studies. For transformation studies below room temperature, the dilatometer was allowed to cool to 150°F and then was quenched into liquid nitrogen.

Jan 1, 1951

By T. K. Perkins, L. E. Bartlett

Values of rock surface energy (i. e. energy required to form a unit area of new surface) are useful for interpretation of drilling and fracturing phenonema This paper describes the adaptation of a cleavage technique (splitting of large rocks under controlled conditions) for measuring surface energies. Values of surface energy obtained at room temperature and at low crack extension rates are reported for a variety of sandstones and limestones. Elastic moduli, tensile strengths and compressive strengths of the samples are also reported. The values of Young's moduli (measured in bending) are relatively low, probably because of the low stress levels imposed. Measured values of surface energy me generally higher than anticipated and probably reflect inelastic yielding near the extending tip of the crack. INTRODUCTION The technology of petroleum production includes many operations such as drilling and fracturing, which involve rock breakage. One of the fundamental properties of a rock needed to fully explain breaking and fracturing phenomena is the surface energy (i. e. the energy required to form a unit area of new surface). In this paper we describe an adaptation of the cleavage method (splitting of the rock under controlled conditions) to utilize large rock samples. Application of the theory of elastic cantilever beams and the Griffith concept of mechanical stability permits the calculation of surface energies from simple measurements. Values of surface energies obtained at room temperature on dry samples and at low crack extension rates are reported for a variety of sandstones and limestones. Measured values of Young's Moduli, compressive strengths and tensile strengths are also reported for the rocks. THE EXPERIMENTAL METHOD Equipment designed to cleave large rock samples is shown on Fig. 1. This equipment consists essentially of two steel blocks cemented to a rock sample and forced apart with a steel rod. A ball joint and a pivot prevent bending stresses in the rod. A differential thread arrangement permits the rod to advance only 0.012 in./revolution of the driving nut. The axial force in the rod is measured with type FA-50-12 Baldwin Lima Hamilton strain gauges and a BLH type 20 strain gauge reader. Separation of the blocks is measured with a Starrett 656617 dial gauge. The massive nature and design of the equipment minimize the amount of elastic energy stored in the steel parts as the stress in the rod is increased. This will permit the rock to split under controlled conditions as will become clear later. Fig. 2 shows a sketch of the rock sample during cleavage. Guide slots are cut longitudinally along the rock sample as suggested by Berry.1 An initiating slot is also cut across the top of the block to a depth of 1 to 2 in. During cleavage, elastic energy is stored in the flexed beams of rock of length C. If the length of steel rod L is held constant and the crack extends in length, then the elastic potential energy stored in the rock decreases. However, surface energy must be supplied as the crack extends in length. Griffith6 has proposed the following criteria for mechanical stability. The crack will extend as long as the potential energy available is greater than the surface energy required. However, the crack will stop extending when the change in potential energy with change in crack length is just equal to the change in surface energy with change in crack length. See Eq. 1.

By B. S. Butler

AN understanding of mineralizing solutions and how they carry and deposit metals is of prime importance to students of ore deposits. Lindgren states: "The whole problem surely is very complicated. One difficulty is that we know so little about the stability field of ore minerals."1 Lindgren further states: It is believed that they [the solutions] were in small part oxidized to sulphates, for instance, but in large part they were composed of hydrogen sulphide, alkaline sulphides and various halogen compounds. Doubtless, however, free carbon dioxide was present. Becker's view of the double sulphides as important constituents of the solutions probably holds good. In the fourth edition of Mineral Deposits2 Lindgren had changed his views somewhat: From the work of Day, Allen, Shepard, and others, it would seem probable that many of the volcanic gases are acid when given off but are in unstable equilibrium, and could not have preserved this acid character after having been long in contact with the surrounding rocks. It is believed that they were in small part oxidized to sulphates, for instance, but in larger part they were composed of hydrogen sulphides, alkaline sulphide, and various halogen compounds. Doubtless, however, free carbon dioxide was present. Becker's view of double alkaline sulphides as important constituents of the solution probably holds good. The writer wonders if progress would not result from an attack on the problem in steps, the steps to contribute to the attack on the whole. The initial step would deal with the simpler bodies of supposed magmatic (hydrothermal) origin, that is, those composed essentially of silicates, oxides, sulfates, and sulfides. The following discussion attempts to develop one step of a method that was proposed on a more comprehensive scale in 1929 by the writer and W. S. Burbank.3 The accompanying partial table (Table I) of the electromotive series is from a table distributed by Merck & Co. Inc., manufacturing chemists, prepared in turn from Fundamental Chemistry.& The electromotive arrangement brings together elements that in hypogene ore deposits occur: 1) in oxygen combination only; 2) in combination with sulfur as well as with oxygen; and 3) as sulfides, arsenides etc., and as native metals, see Table 11. The writer clearly recognizes that he is not qualified to discuss the formation of ore deposits as a chemical problem, but he feel that some of the relations that are met by the geologist can well be stated with the hope that the chemical explanation will be forthcoming. By consideration of a group including mainly the elements oxygen, hydrogen, sulfur and iron, complications are avoided, especially with elements of the lower electromotive group. The results can only contribute to the solution of the problem, not to the completion of it. The pH and Eh of the solutions and also temperature probably determine what minerals form. The mineral groups that contain elements high in the electromotive series are alumino-silicates, titanites, simple silicates, spinels, oxides, carbonates and sulfates, in all of which the elements are combined with oxygen. These groups are also recognized as the general order of temperature at which the minerals start to form, see Table 11. At low temperature are sulfides, arsenides, antimonides, sulfo-salts, and native metals, in all of which the elements are characteristically not combined with oxygen. The intermediate temperature group contains elements that form both oxygen compounds and sulfur compounds.

Jan 1, 1957

By A. M. Gaudin, C. S. Chang

Adsorption was measured for barium ion and laurate radical, using radioactively marked agents, over wide range of concentrations. Laurate adsorbed in absence of barium fails to float. With barium, flotation-effective laurate coating needs not exceed 5 pct of monolayer. Barium adsorption then is several fold larger. No barium laurate coating is obtained. IN general, fatty acids or their alkali salts do not cause clean quartz to float. However, the presence of multivalent ions, such as the alkaline-earth metal ions and heavy-metal ions, can activate quartz and thus make it respond to soap flotation. The mechanism of activation and soap flotation of quartz has been studied.'-' The problem was attacked by making flotation tests rather than by careful adsorption measurements on suspensions of ground quartz in solutions containing the activator and the collector. Attempts have been made to determine the adsorption of barium ion and calcium ion on quartz. The results have only qualitative value as the analytical methods were not adequately precise. Artificial radioactivity and progress in radioactivity detection have introduced a new analytical tool, which can have a sensitivity several orders of magnitude greater than that of other methods."-" In the experimental work described in this paper the radioactive tracers, barium 140 and carbon 14, were employed. Lauric acid was synthesized, having a radioactive carbon atom and was used with Ba" to study the adsorption of barium and laurate ions from aqueous solution on ground quartz. Flotation tests, using the vacuum flotation technique,' were run in conjunction with the adsorption experiments. The object of this investigation was to understand better the reaction mechanism of barium activation and soap flotation of quartz. Methods and Materials Quartz Sample Preparation: Lumps of hand-picked quartz, washed free of stains, were reduced in size to —20 mesh in laboratory crushers. The product was boiled in concentrated hydrochloric acid to remove the abraded iron. The cleaned product then was ground dry in a laboratory porcelain mill, using siliceous pebbles, to pass through a 200 mesh screen. The ground product was deslimed by sedimentation at 37 microns. This —200 mesh +400 mesh material was subjected again to boiling with concentrated hydrochloric acid, followed by washing with distilled water and further desliming. The cycle was repeated until no trace of iron could be detected in the wash liquor. During the final washing, the pH of the wash water was checked to insure the complete removal of the acid from the mineral. The quartz then was rinsed with conductivity water. The resulting product was dried in a drying oven and stored in mason jars. The impurities (spectrographic) were as follows: Al, 0.01 to 0.001 pct; Li, Mg, Mn, Na, each less than 0.001 pct; Fe and Cu not detected. The specific surface of the quartz sample was determined by the krypton gas adsorption method.' The average of two measurements was 881 sq cm per g. The calculated specific surface for 37/74-micron quartz particles, using a surface factor of 1.96; is 900 sq cm per g. This is in good agreement with the measured value of 881 sq cm per g. Beta-Counting Method: The radioactive isotope of barium used in the experimental work was barium 140. It has a sufficiently long half-life, 12.8 days, emits high-energy beta particles (up to 1.0

Jan 1, 1953