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By H. K. Livingston

A technique has been developed which makes it possible to determine the spreading pressure of liquids and solids, for simple systems. Data for surface tensions, interfacial tensions, spreading pressures, and contact angles for water, heptane, and silica are tabulated.' These results can be applied to the evaluation of capillary rise and displacement pressure in a petroleum reservoir. Appropriate equations are presented and the application of these equations is discussed. The presence of surface-active components affects both capillary rise and displacement pressure and also seems to influence the rate of fluid flow. The purpose of this paper is to supplement and bring up to date the last article on the subject of the surface chemistry of petroleum reservoirs, that of Garrison in the 1935 Oil and Gas Journa1.1 A discussion of the "adhesion tension" concept used by Garrison has been presented in another publication,2 together with the reasons for the recommendation that the term "adhesion tension" be abandoned. In view of the fact that some of the data used by Garrison have been superseded by more recent work, it seemed advisable to call attention to this fact and present the more important data currently believed to be correct. In the earlier paper, Garrison set up the equations that 'relate solid-oil and solid-water interfacial tensions to each other, and applied data from Bartell and Miller3 to these equations. However the adhesion tension measurements made by Bartell and Miller involved a confusion of symbols, so that they did not actually measure the spreading pressure, ?s — ?sf.2 The spreading pressure is a convenient method of indicating the amount by which the surface energy of a solid surface is lowered on immersion in a liquid or vapor. Since the initial value of the free surface energy is represented by the symbol ?s and the final value is ?sF, the spreading pressure is ?s — ?SF. A technique has now been developed4 that makes possible the determination of ?s — ?sF for simple systems. This method would be very difficult to carry out with a multicomponent system such as exists in the petroleum reservoir. However, already results have been obtained for ?s — ?sF for water and heptane in contact with silica and graphite. These values will be of the same order of magnitude as those in the petroleum reservoir. Accordingly, it is possible for the first time to discuss the surface-energy relations of the petroleum reservoir on a semi-quantitative basis. Preliminary Generalizations A petroleum reservoir may contain the following four phases: gas, hydrocarbon liquid, aqueous liquid, and solid. The three fluid phases are dispersed through the solid reservoir rock. If gravity were the only force acting, it is obvious that the

Jan 1, 1943

By H. K. Livingston

A technique has been developed which makes it possible to determine the spreading pressure of liquids and solids, for simple systems. Data for surface tensions, interfacial tensions, spreading pressures, and contact angles for water, heptane, and silica are tabulated.' These results can be applied to the evaluation of capillary rise and displacement pressure in a petroleum reservoir. Appropriate equations are presented and the application of these equations is discussed. The presence of surface-active components affects both capillary rise and displacement pressure and also seems to influence the rate of fluid flow. The purpose of this paper is to supplement and bring up to date the last article on the subject of the surface chemistry of petroleum reservoirs, that of Garrison in the 1935 Oil and Gas Journa1.1 A discussion of the "adhesion tension" concept used by Garrison has been presented in another publication,2 together with the reasons for the recommendation that the term "adhesion tension" be abandoned. In view of the fact that some of the data used by Garrison have been superseded by more recent work, it seemed advisable to call attention to this fact and present the more important data currently believed to be correct. In the earlier paper, Garrison set up the equations that 'relate solid-oil and solid-water interfacial tensions to each other, and applied data from Bartell and Miller3 to these equations. However the adhesion tension measurements made by Bartell and Miller involved a confusion of symbols, so that they did not actually measure the spreading pressure, ?s — ?sf.2 The spreading pressure is a convenient method of indicating the amount by which the surface energy of a solid surface is lowered on immersion in a liquid or vapor. Since the initial value of the free surface energy is represented by the symbol ?s and the final value is ?sF, the spreading pressure is ?s — ?SF. A technique has now been developed4 that makes possible the determination of ?s — ?sF for simple systems. This method would be very difficult to carry out with a multicomponent system such as exists in the petroleum reservoir. However, already results have been obtained for ?s — ?sF for water and heptane in contact with silica and graphite. These values will be of the same order of magnitude as those in the petroleum reservoir. Accordingly, it is possible for the first time to discuss the surface-energy relations of the petroleum reservoir on a semi-quantitative basis. Preliminary Generalizations A petroleum reservoir may contain the following four phases: gas, hydrocarbon liquid, aqueous liquid, and solid. The three fluid phases are dispersed through the solid reservoir rock. If gravity were the only force acting, it is obvious that the

Jan 1, 1943

By E. W. Cawthorne, R. I. Jaffee, C. M. Craighead

SOLUTION of a solid metal or alloy in a molten metal bath is used daily in melting operations, extractive metallurgical processes, and in brazing. It is generally recognized that temperature, time, agitation, and the composition of the solute metal and the solvent bath all affect solution rate. However, there is little information available in the literature on the kinetics of the process or the relative effect that these variables have on solution rate. In connection with an aluminum brazing study, data on the solution of aluminum in an A1-Si* bath to promote rapid solidification. The chemical analyses were made on drillings taken from the cast plates. The results of this work are listed in Table I. The thermal-analysis data were obtained on 200 gram samples cooled at approximately 1.5" per min. A calibrated chromel-alumel couple was used. The thermal arrests were recorded autographically on a General Electric photoelectric potentiometer recorder. The instrument was calibrated to 22.5 pct. The thermal emf was bucked with a Leeds and Northrup semiprecision potentiometer so that 1 mv represented the full scale of the GE recorder. Referring to Table I, it will be noted that the analytical results tend to be lower than the intended compositions by about 0.3 pct Si in the higher ranges. In view of the known difficulties in obtaining accurate silicon determinations by wet analysis when the silicon content is high and in view of the care that was employed in weighing and preparing the alloys, the intended compositions are believed to be more accurate than the analyses. Furthermore, when the thermal-arrest data are plotted against the intended compositions, a smooth curve is obtained, as shown in Fig. 1. This is not the case when the data are plotted against the analytical results. It will be noted from Table I that the 12.5 pct Si alloy (melt 4) showed a primary arrest at 577.6"C and the eutectic at 576.l°C. The metallographic examination of this chill-cast plate sample showed a small amount of primary silicon. These results, Fig. 1, place the eutectic at slightly less than 12.5 pct Si and are in rather good agreement with the unpublished Hanford data. In all of the subsequent work, the composition of the A1-Si dipping baths was determined by thermal analysis (spread between the primary arrest and the eutectic temperature) employing 12.5 pct Si and 577.2 °C as the composition and temperature of the eutectic. Material Preparation and Selection of the Techniques: At the beginning of this work, it was anticipated that, owing to oxide film present on the surface of the aluminum, difficulty would be encountered in obtaining rapid uniform wetting of aluminum specimens dipped in the A1-Si bath. The following etchants were investigated as possible methods of providing a thin uniform oxide film on the specimen surface: 1—phosphoric acid (H³O4), 2—fluoboric acid (HBFI), 3—sodium hydroxide (NaOH), and 4—hydrofluoric acid (HF). Tests with sheet .specimens (2x½x0.06 in.) of 2s aluminum prepared with these etchants indicated that the fast uniform wetting required for this work could not be obtained if any oxide film existed on the specimen surface. Tests were then conducted by dipping similar specimens etched in 5 pct NaOH and given a thin

Jan 1, 1956

By R. A. Morse, W. W. Owens, D. R. Parrish, T. M. Geffen

Laboratory studies of several factors affecting measurements of relative permeability were made using the three-section plastic-covered core technique. Results show that the core assembly, properly constructed, will perform as a single unit, and that the testing technique will, under suitable conditions of pressure gradient, gas expansion, and migration of partial water saturation, permit measurement of flow characteristics not affected by technique. Wettability equilibrium is readily established in cores exhibiting strong wetting preference to water or oil when initially saturated with water. Laboratory tests must be conducted so that saturation changes represent those that occur in the reservoir. Immediate implications of saturation history are (1:) that the possibility exists of increasing the displacement efficiency of solution gas drive reservoirs over the natural process, and (2) residual gas saturations following water flooding in gas or gas condensate reservoirs will be 15 to 50 per cent pore space rather than 1 to 11 per cent as generally believed. INTRODUCTION Solutions of petroleum reservoir problems pertaining to production performance require the use of true relative permeability characteristics. 'This relationship of fluid conductivity and saturation has been obtained by reservoir engineers in four ways, namely: 1. From past gross reservoir performance and the extrapolation of this data based on experience,1,2 2. By using published fluid flow relationships obtained in laboratory studies on general type porous materials,3, 4, 5 3. By attempting a mathematical derivation of flow behavior," using some experimentally obtained characteristics of reservoir rocks, and 4. By laboratory flow tests using representative rock samples of a reservoir. The first three methods listed above have shortcomings which make their use limited or questionable. Production characteristics of only certain processes are obtained from field data and these are not available at the beginning of a reservoir's producing life, at which time they are desirable. It is fortuitous if general fluid flow characteristics obtained experimentally have accurate application to specific field problems. Also, it is felt that at this time there is not sufficient knowledge of the flow behavior of oil, water, and gas in porous materials to enable applicable analytical description of this to be made based on other measured rock characteristics. Measurement of relative permeability in the laboratory offers the only direct method subject to adequate checking for determination of flow characteristics applicable to field problems. Primarily, this paper deals with laboratory experiments to establish the effects of several factors on the measurement of relative permeability and the practical significance of this knowledge. Laboratory flow tests are essentially model studies; the gross reservoir being represented by a small rock sample. It is necessary to simulate in experiments all the factors of importance which influence flow in the reservoir, as well a.; to eliminate effects peculiar to the model studied to assure measurement of valid flow behavior. Factors which affect the measurement and behavior of fluid flow in porous materials have been studied by other investigators.3,7,8,9,10,11 This analysis is not intended to evaluate fully all factors involved, but to establish first the validity of measurements by the technique used and then study flow behavior under various conditions. The studies reported are as follows: 1. Effects of pressure gradient, 2. Effects of gas expansion in tests conducted at near atmospheric pressure, 3. Effects of migration of a partial water saturation in oil-gas-water systems, 4. Effects If wettability characteristics of the system. and 5. Effects of the fluid saturation history. The first three are important only in laboratory measure-

Jan 1, 1951

By D. R. Parrish, T. M. Geffen, R. A. Morse, W. W. Owens

Laboratory studies of several factors affecting measurements of relative permeability were made using the three-section plastic-covered core technique. Results show that the core assembly, properly constructed, will perform as a single unit, and that the testing technique will, under suitable conditions of pressure gradient, gas expansion, and migration of partial water saturation, permit measurement of flow characteristics not affected by technique. Wettability equilibrium is readily established in cores exhibiting strong wetting preference to water or oil when initially saturated with water. Laboratory tests must be conducted so that saturation changes represent those that occur in the reservoir. Immediate implications of saturation history are (1:) that the possibility exists of increasing the displacement efficiency of solution gas drive reservoirs over the natural process, and (2) residual gas saturations following water flooding in gas or gas condensate reservoirs will be 15 to 50 per cent pore space rather than 1 to 11 per cent as generally believed. INTRODUCTION Solutions of petroleum reservoir problems pertaining to production performance require the use of true relative permeability characteristics. 'This relationship of fluid conductivity and saturation has been obtained by reservoir engineers in four ways, namely: 1. From past gross reservoir performance and the extrapolation of this data based on experience,1,2 2. By using published fluid flow relationships obtained in laboratory studies on general type porous materials,3, 4, 5 3. By attempting a mathematical derivation of flow behavior," using some experimentally obtained characteristics of reservoir rocks, and 4. By laboratory flow tests using representative rock samples of a reservoir. The first three methods listed above have shortcomings which make their use limited or questionable. Production characteristics of only certain processes are obtained from field data and these are not available at the beginning of a reservoir's producing life, at which time they are desirable. It is fortuitous if general fluid flow characteristics obtained experimentally have accurate application to specific field problems. Also, it is felt that at this time there is not sufficient knowledge of the flow behavior of oil, water, and gas in porous materials to enable applicable analytical description of this to be made based on other measured rock characteristics. Measurement of relative permeability in the laboratory offers the only direct method subject to adequate checking for determination of flow characteristics applicable to field problems. Primarily, this paper deals with laboratory experiments to establish the effects of several factors on the measurement of relative permeability and the practical significance of this knowledge. Laboratory flow tests are essentially model studies; the gross reservoir being represented by a small rock sample. It is necessary to simulate in experiments all the factors of importance which influence flow in the reservoir, as well a.; to eliminate effects peculiar to the model studied to assure measurement of valid flow behavior. Factors which affect the measurement and behavior of fluid flow in porous materials have been studied by other investigators.3,7,8,9,10,11 This analysis is not intended to evaluate fully all factors involved, but to establish first the validity of measurements by the technique used and then study flow behavior under various conditions. The studies reported are as follows: 1. Effects of pressure gradient, 2. Effects of gas expansion in tests conducted at near atmospheric pressure, 3. Effects of migration of a partial water saturation in oil-gas-water systems, 4. Effects If wettability characteristics of the system. and 5. Effects of the fluid saturation history. The first three are important only in laboratory measure-

Jan 1, 1951

By Robert G. Johnson, Richard J. Prosen

THE present work was done in connection with a program for investigating metal-to-ceramic braze techniques using the well-known reactivity of titanium with certain ceramic oxides. The investigation extended over the range of 0 to 30 pct Ti. The indium was obtained from the Indium Corp. of America and was specified to be 99.97 pct pure. The titanium was supplied by Metals Disintegrating Co. and was stated to be 99.5 pct pure. Each 2 to 4 g quantity of the alloy compositions studied was prepared using a mixture of 300 mesh powders pressed into pellet form. The pellets were heated in thin-walled molybdenum crucibles using a resistance-wound furnace in a vacuum less than 10-4 mm of Hg. Little reaction occurred between the molten alloy and the crucibles at the temperatures and short time intervals used. Only slight spectroscopic traces of molybdenum were found in the melt after a typical period of heating. The points shown on the phase diagram of Fig. 1 represent thermal arrest measurements. The phase boundaries shown are consistent with the thermal arrest and X-ray data obtained. The temperatures were determined using a Pt-Pt 10 pct Rh thermocouple with the junction spot-welded to a short molybdenum rod. The rod was almost completely immersed in the liquid metal, so that good thermal contact with the melt was achieved. The small mass of the crucible and its contents made it possible to obtain many heating and cooling curves in a few minutes time, an advantage which helped to minimize the effects of indium evaporation at the higher temperatures. A Brown strip chart recorder was used to display the thermal arrest curves. To check the technique, the melting point of 99.999 pure Al was measured and found to be within 1 of 660.2c, the accepted melting point. The upper limit of temperature with this technique was about 900°C beyond which the evaporation rate of indium became great enough to alter appreciably the alloy composition during the runs. A peritectic transition was found at 796°+ 5°C from 1.5 to 30 wt pct Ti. It was not found at 0.5 or 1.0 pct. A small super-cooling effect was observed. The melting-point transition to the B + L phase was found up to 20 pct Ti but not at 25 pct. Within the 1 deg accuracy of the measurement, the transition temperature was that of pure indium, 156°C. The liquidus line to the left of the 1.5 titanium point was located only approximately. The two crossed circle points at 1.0 and 0.5 pct Ti place a lower limit on the liquidus line and were determined by observing visually the cessation of vibrations in the melt caused by the damping effect as B-phase crystals were formed during cooling. The B-phase boundary was found at 23.8 pct Ti by X-ray analyses of small single crystals of the B phase isolated from 2 pct Ti melts. The compound was found to be Jetragonal with lattice dimensions of c = 3.052A and a = 10.094W. From the unit cell dimensions and the measured density of 6.42 i 0.05 g per cc, the compound was determined to be In4Ti3 which has 23.8 pct Ti. The calculated density of 6.44 g per cc is obtained assuming 2 mol

Jan 1, 1962

By J. Chipman, N. J. Grant, J. C. Fulton

This paper contains data on the distribution of silicon between liquid iron-silicon-carbon alloys saturated with respect to graphite and CaO-SiO2-Al2O3 slags under 1 atm of CO at 1600°C. The ranges of slag compositions studied were extended from the dicalcium silicate saturated liquidus composition up to silica concentrations at which Sic appeared as a stable phase. IN blast furnace operation it is not to be expected that slag and metal reach equilibrium with one another. Nevertheless, the silicon content of the metal varies with slag composition and with temperature in a manner which would be predicted from equilibrium considerations. Similarly, the distribution of sulphur between slag and metal does not attain an equilibrium state, yet the influence of slag composition is strongly analogous to its effect on the distribution equilibrium. The desulphurizing power of metallurgical slags has been shown to be highly dependent upon the FeO content of the slag. Moreover, the rate of removal of sulphur from slags is influenced by the oxygen potential of the slag-metal system. Thus it was shown by Grant, Kalling, and Chipman1 that the presence of MnO in slags which are low in FeO causes a marked slowing down of the transfer of sulphur from metal to slag. This led to the hypothesis that the slow removal of sulphur by blast furnace slags of more acid composition might be due in part to the effect of SiO2 on the oxygen potential of the system. This was verified in the work of Grant, Troili, and Chipman,' who found that the desulphurizing power of the more acid blast furnace slags could be markedly improved by an increase in the silicon content of the underlying metal. Their explanation of this improvement was that the higher silicon content of the metal decreased the rate of transfer of more silicon and, along with it, of oxygen from the slag to the metal. The slowness of the transfer of sulphur from metal to slag was the result of the slow reduction of SiO2 from slag to metal. Attempts to study the rate of sulphur removal had in the past resulted in very slow rates corresponding to the rates of silica reduction. It has become evident on the basis of these studies that further experimental studies on the rate of removal of sulphur must take these factors into consideration if there is to be a clear understanding of the rate of sulphur transfer under conditions simulating those existing in the blast furnace. It will be necessary, at least in a part of such study, to employ combinations of slag and metal in which the disturbing effect of silica reduction has been eliminated; in other words, to employ slag-metal combinations which are already in equilibrium with respect to the transfer of silicon. In preparation for such studies of desulphuriza-tion, a preliminary program of research on the distribution of silicon between slag and metal has been undertaken. This will ultimately include a comprehensive survey of the effects of temperature and slag composition on the equilibrium distribution of silicon between slag and metal. The present paper is a report on experimental methods employed and on

Jan 1, 1954

The rich Tiller seam in southwest Virginia averages 10 to 15 ft in thickness. But because it is separated into two benches, mining engineers for years considered it neither physically nor economically feasible to mine. Profitable recovery of this coal has been made possible only by: full-seam mining with automatic machines; and the largest and most highly automated coal preparation plant of its kind-a plant ten stories high which washes, screens, and dries at the rate of 1500 tph, and produces both metallurgical and steam coal products. The Moss No. 3 preparation plant of Clinchfield Coal Co. Div. of Pittston Co. is located at Clinch- field, Va., only a short distance from the 450-tph Moss No. 2 plant, and was designed, built and erected by Link-Belt Co.

Jan 7, 1959

By G. R. Brophy, A. J. Miller

The Grossmann principle1 for the calculation of hardenability of steel from composition is attractive because of its simplicity. It postulates that the hardenability of a steel for any particular grain size may be expressed in terms of an ideal critical diameter, which is the product of an ideal critical diameter for a "pure" iron-carbon base multiplied by a succession of factors for each element of composition contained, including the incidentals. It infers that the multiplying factor for a given quantity of an element is constant for all combinations of composition. Gross-mann has stated that in the great majority of cases the experimental values of hardenability are found to be well within 10 per cent of the calculated values. The validity of the scheme has been confirmed in principle by Crafts and Lamont2,3 and by Kramer et al.4 Their results differ from the original in the magnitude of the effect of some elements but, since they accepted the product concept and followed its direction, it is to be ex~ected that similar results would be obtained. Crafts and Lamont, in their second Paper, recognized that the factor relations for manganese and nickel were not continuously linear, but beyond certain critical amounts increase sharply. Austin, Van Note and Prater6 demonstrated nonlinear relations between hardenability and alloy contents. Their curves for chromium, silicon, manganese and nickel were all convex upward to show decreasing incremental effects. They concluded that Grossmann's factors under-evaluate the hardening effect of low percentage additions of these elements, and overevaluate the larger additions. More recently W. Stevens has found that the factor method fails when applied to complex steels containing two or three principal alloying elements other than carbon. Multiplying factors derived from his results bear a complex relation to composition and are not constant for a given amount of an element as the base composition varies. C. A. Liedholm7 found that, using either the Grossmann or the Crafts-Lamont multiplying factor values, not only were the relative hardenabilities of two heats of S.A.E. 6130 chromium-vanadium steel

Jan 1, 1947

By A. J. Miller, G. R. Brophy

The Grossmann principle1 for the calculation of hardenability of steel from composition is attractive because of its simplicity. It postulates that the hardenability of a steel for any particular grain size may be expressed in terms of an ideal critical diameter, which is the product of an ideal critical diameter for a "pure" iron-carbon base multiplied by a succession of factors for each element of composition contained, including the incidentals. It infers that the multiplying factor for a given quantity of an element is constant for all combinations of composition. Gross-mann has stated that in the great majority of cases the experimental values of hardenability are found to be well within 10 per cent of the calculated values. The validity of the scheme has been confirmed in principle by Crafts and Lamont2,3 and by Kramer et al.4 Their results differ from the original in the magnitude of the effect of some elements but, since they accepted the product concept and followed its direction, it is to be ex~ected that similar results would be obtained. Crafts and Lamont, in their second Paper, recognized that the factor relations for manganese and nickel were not continuously linear, but beyond certain critical amounts increase sharply. Austin, Van Note and Prater6 demonstrated nonlinear relations between hardenability and alloy contents. Their curves for chromium, silicon, manganese and nickel were all convex upward to show decreasing incremental effects. They concluded that Grossmann's factors under-evaluate the hardening effect of low percentage additions of these elements, and overevaluate the larger additions. More recently W. Stevens has found that the factor method fails when applied to complex steels containing two or three principal alloying elements other than carbon. Multiplying factors derived from his results bear a complex relation to composition and are not constant for a given amount of an element as the base composition varies. C. A. Liedholm7 found that, using either the Grossmann or the Crafts-Lamont multiplying factor values, not only were the relative hardenabilities of two heats of S.A.E. 6130 chromium-vanadium steel

Jan 1, 1947

By J. F. Ednie

SCRAP metals to the value of more than a billion and a half dollars were recovered in the United States in 1939 for further use in industry. Few people have any true conception of the magnitude of the secondary-metal industry as related to that engaged in the production of the primary, or virgin, metals; of its importance, particularly when a shortage of primary metals exists, as at present; or of the advance that has been made in standardizing and improving the quality of its products. Of the iron and steel produced in the United States in 1939 (the data used in this article are largely taken from Bureau of Mines reports for that year) just over 50 per cent came from scrap and slightly less than 50 per cent from ore. Of the principal nonferrous metals-aluminum, anti-mony, copper, lead, nickel, tin, and zinc-63 per cent came from domestic ores and 37 per cent from scrap. Fig. 1 presents graphically the relative tonnage and value of primary and secondary production of ferrous and nonferrous metals. In this chart only purchased secondary metals are considered, the figures being exclusive of "home" or "plant" scrap which amounts to rather large figures in the iron and steel industry. Incidentally, the chart shows that from the tonnage standpoint the iron and steel industry is some twenty times larger than the nonferrous industry, though with regard to the value of the product the ratio drops to about two to one.

Jan 1, 1941

By Ta M. Li

Expanded mine-mill capacity and greater operating flexibility are part of the dramatic changes taking place in the Tennessee mining operations of Asarco, Inc. Climaxed by the recent start-up of the $6.3 million Young mill in September 1975, Asarco has pushed Tennessee back into number one position as the leading zinc mining state. Furthermore, start-up of the Young mill is expected to insure a much-needed and continuing domestic zinc supply, at a time when US mines can only supply one-half of 1975 domestic consumption.

Jan 5, 1976

By W. M. Weigel

The rapid advance, during recent years, in the manufacture of articles that have been in common use for generations and the development of new materials entering into appliances and devices unheard of fifty years ago have created a demand for some of the more common non-metallic minerals. To supply this demand there has quietly developed a branch of the mining industry of which little is known by most mining engineers —the mineral-filler industry. In this paper, and generally in the trade, the term mineral filler is applied to a mineral used in its natural state after mechanical preparation only (such as grinding, milling and washing), without undergoing any chemical change and without exerting any chemical action on the substance with which it is incorporated. The consumption of mineral fillers is confined chiefly to large manufacturing centers in the Eastern and Northern Statcs. Where available, materials originating near the place of consumption are used, as most fillers bring a comparatively low price and, frequently, the freight may equal the cost of the finished filler at the mine. The Southern States have abundant deposits of non-metallic minerals suitable for fillers, which supply the manufacturing industries in adjacent states. Many of these deposits are equal to, or superior, in quality to those mined in the North, but they can not compete with them because of the freight rates. The mineral-filler industry has felt the present depression, but it has suffered less than most mining industries, for as a rule the mills are simple, the overhead expenses are low, and the labor is entirely local and can revert to farm work when the plant closes down. Many other deposits in the southern district will undoubtedly be developed when business revives and freight rates are adjusted. Most of the non-metallic mines are small and the tonnage handled is low in comparison with the tonnage involved in modern large-scale mining of coal, iron, copper, etc. On the other hand, at nearly all non-metallic

Jan 1, 1923

By W. M. Weigel

The rapid advance, during recent years, in the manufacture of articles that have been in common use for generations and the development of new materials entering into appliances and devices unheard of fifty years ago have created a demand for some of the more common non-metallic minerals. To supply this demand there has quietly developed a branch of the mining industry of which little is known by most mining engineers —the mineral-filler industry. In this paper, and generally in the trade, the term mineral filler is applied to a mineral used in its natural state after mechanical preparation only (such as grinding, milling and washing), without undergoing any chemical change and without exerting any chemical action on the substance with which it is incorporated. The consumption of mineral fillers is confined chiefly to large manufacturing centers in the Eastern and Northern Statcs. Where available, materials originating near the place of consumption are used, as most fillers bring a comparatively low price and, frequently, the freight may equal the cost of the finished filler at the mine. The Southern States have abundant deposits of non-metallic minerals suitable for fillers, which supply the manufacturing industries in adjacent states. Many of these deposits are equal to, or superior, in quality to those mined in the North, but they can not compete with them because of the freight rates. The mineral-filler industry has felt the present depression, but it has suffered less than most mining industries, for as a rule the mills are simple, the overhead expenses are low, and the labor is entirely local and can revert to farm work when the plant closes down. Many other deposits in the southern district will undoubtedly be developed when business revives and freight rates are adjusted. Most of the non-metallic mines are small and the tonnage handled is low in comparison with the tonnage involved in modern large-scale mining of coal, iron, copper, etc. On the other hand, at nearly all non-metallic

Jan 1, 1923

By James Douglas

In discussing the waste upon which hinges, or is supposed to hinge, so largely the preservation of our national resources, the conclusions reached would be more reliable if actual experience were consulted, and fewer deductions were drawn from general statements, which are often the product of the imagination. It cannot be questioned that the value of by-products has .not been sufficiently appreciated by us, and that our tardiness in recovering the useful ingredients of the escaping gas of our coke-ovens is one of the most glaring instances of shortcoming in that direction. And yet even for that sin there is some palliation in the immature condition of affiliated industries. I presume that it is admitted, without argument, that, except under very exceptional conditions, all the elements cannot be recovered from most of the ores or natural products which we treat. While it is a shame that the by-products from our coke-ovens should be dissipated, Edward W. Parker's report to the U. S. Geological Survey for 19061 supplies a fairly good excuse in justification of this appalling waste. He says (pp. 773 to 774.): " What has been already commented on in previous reports about the slowness of manufacturers to change from the better known but wasteful beehive practice to the by-product recovery method of coke manufacture is particularly emphasized in the statistics presented in this chapter. For it would appear from the table following that the construction of by-product ovens had about come to a standstill, especially when the records for the preceding five years are taken into consideration. At the close of 1901, when there were only 1,165 by-product ovens completed in the United States, there were 1,533 in course of construction, 498 of which were completed during the following year. At the close of 1902, 1,346 retort ovens were building, 293 of which were added to the completed plants in 1903. At the close of 1903, 1,335 new ovens were building and 954 of these

Jan 1, 1910

1. List of Manuscripts Seen in America 2. List of Manuscripts Seen in England 3. List of Maps Examined 4. List of Newspapers Examined 5. General Bibliography - Numbered Reference List

Jan 1, 1942

By Leon W. Dupuy

SUPPLEMENT THESE tables should accompany Figs 6, 7, 8, 9 and 10, respectively. To follow Fig 6: TABLE 2[a]-Drill Rod [ ] To follow Fig 7: TABLE 3-Rod Coupling [ ]

Jan 1, 1947

By J. C. Fisher, J. H. Hollomon, David Turnbull

Understanding of the diffusion problem has recently been furthered by the analysis of Birchenall and Meh1.l They pursued the problem of the variation of the diffusion coefficient with composition for non-ideal solid solutions. Their analysis follows the tradition of Wagner,l Jost, Dehlinger, and Darken & who assumed the net flux of diffusing material to be proportional to the gradient of a quantity related to free energy. The basic assumption in Birchenall and Mehl's formulation of the problem is that the net flux of diffusing material is proportional to a thermodynamic activity gradient. To estimate the applicability of the derived relations, they corrected the diffusion coefficients of carbon in austenite by utilizing Smith's6 activity data for carbon, and the diffusion coefficients for zinc in copper with activity data computed from the vapor pressure measurements of Har-greaves.' The corrected coefficients for carbon were virtually independent of carbon concentration. For the diffusion of zinc in copper a moderate variation of diffusion coefficient with concentration remained after the correction. The problem of diffusion can be formulated in another way than that used by Birchenall and Mehl. The method is that of chemical rate theory and has been used by Eyring and his coworkers8,9 as well as by Eyring and Zwolinskilo in a discussion to Birchenall and Mehl's paper. As yet the method has not been applied to substitu-tional solid solutions. On the basis of their assumptions, Eyring and Zwolinski derived a relation between the diffusion coefficient and activity that is identical with that of Dehlinger and Darken but which does not correct for the variation of the diffusion coefficient with concentration as well as does the relation derived by Birchenall and Mehl. It was thought that the theory of diffusion would be more complete if the inconsistency between the two analyses could be rationalized and if diffusion in substitu-tional alloys were analyzed on the basis of the concepts of the chemical rate theory. Chemical Rate Theory According to the theory of absolute reaction ratess the reaction +..... +X, Eq I is viewed as taking place in two steps. First the reactants A1, A², . . . A; combine to form an activated complex M with which they are in equilibrium: A1 + A1+ . . . + A=M. Eq 2 Second the activated complex decomposes to give the products XI, XZ, . . . Xi: M?X, + X²+ . . . +Xi Eq g It has been showns that the number of activated complexes decomposing per unit volume per unit time is given by the expressiont kT -h CM † The transmission coefficient has been taken as unity.

Jan 1, 1949

By David Turnbull, J. H. Hollomon, J. C. Fisher

Understanding of the diffusion problem has recently been furthered by the analysis of Birchenall and Meh1.l They pursued the problem of the variation of the diffusion coefficient with composition for non-ideal solid solutions. Their analysis follows the tradition of Wagner,l Jost, Dehlinger, and Darken & who assumed the net flux of diffusing material to be proportional to the gradient of a quantity related to free energy. The basic assumption in Birchenall and Mehl's formulation of the problem is that the net flux of diffusing material is proportional to a thermodynamic activity gradient. To estimate the applicability of the derived relations, they corrected the diffusion coefficients of carbon in austenite by utilizing Smith's6 activity data for carbon, and the diffusion coefficients for zinc in copper with activity data computed from the vapor pressure measurements of Har-greaves.' The corrected coefficients for carbon were virtually independent of carbon concentration. For the diffusion of zinc in copper a moderate variation of diffusion coefficient with concentration remained after the correction. The problem of diffusion can be formulated in another way than that used by Birchenall and Mehl. The method is that of chemical rate theory and has been used by Eyring and his coworkers8,9 as well as by Eyring and Zwolinskilo in a discussion to Birchenall and Mehl's paper. As yet the method has not been applied to substitu-tional solid solutions. On the basis of their assumptions, Eyring and Zwolinski derived a relation between the diffusion coefficient and activity that is identical with that of Dehlinger and Darken but which does not correct for the variation of the diffusion coefficient with concentration as well as does the relation derived by Birchenall and Mehl. It was thought that the theory of diffusion would be more complete if the inconsistency between the two analyses could be rationalized and if diffusion in substitu-tional alloys were analyzed on the basis of the concepts of the chemical rate theory. Chemical Rate Theory According to the theory of absolute reaction ratess the reaction +..... +X, Eq I is viewed as taking place in two steps. First the reactants A1, A², . . . A; combine to form an activated complex M with which they are in equilibrium: A1 + A1+ . . . + A=M. Eq 2 Second the activated complex decomposes to give the products XI, XZ, . . . Xi: M?X, + X²+ . . . +Xi Eq g It has been showns that the number of activated complexes decomposing per unit volume per unit time is given by the expressiont kT -h CM † The transmission coefficient has been taken as unity.

Jan 1, 1949

By John Chipman, Daniel Dutilloy

The equilibrium of gaseolis H2O-H2 mixtures with liquid iron-phosphorus alloys in the range 0 to 3 pct P is used to establish the increuse of the activity coefficient of oxygen, in the presence of phosphorus. Two different sampling techniques are used. THE importance of oxygen as a refining agent in steelmaking operations makes it desirable to improve our understanding of its behavior. Phosphorus which is always present in the ores has adverse effects on steel properties and its removal is necessary. The present study was undertaken to evaluate the interaction of oxygen and phosphorus in molten iron. Bookey, Richardson, and welch1 have studied the phosphorus-oxygen equilibria in liquid iron in the presence of lime. They used a mixture of hydrogen and water vapor to control the oxygen potential and worked with crucibles made of tetracalcium phosphate and lime. At low phosphorus concentration, i.e., at high oxygen, they observed a marked deviation in their results. They tentatively ascribed this to a large negative effect of oxygen on the activity of phosphorus. This was then included by chipman2 in his review of interactions in liquid iron. Pearson and Turkdogan 3 have later reported an interaction parameter They equilibrated a mixture of hydrogen and water vapor with an iron-phosphorus alloy contained in an alumina crucible and sampled the melt by suction in a silica tube. The solubility of oxygen in iron-phosphorus alloys has been studied by Levenets and Samarin.4 They reported an interaction parameter

Jan 1, 1961