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GEORGE S. RICE (written discussion *).-An interesting and important question arose during the coal famine of last winter as to whether the development of new mines should be discouraged on account of the need of labor for the necessary construction and development work at a time of scarcity of labor, more especially as there was an apparent overcapacity of existing mines. The question was referred to the author for his comments, which led to the study of the statistics. The essential results of this study are indicated on the accompanying chart, which illustrates, among other things, the increase in production or consumption, and the estimated maximum production capacity of the bituminous and sub-bituminous mines of the United States. The curves shown are based on data published in the "Mineral Resources" of the United States Geological Survey, and cover the period from 1900 to 1916 inclusive. The following curves have been drawn from the data secured: 1. Average number of days that the mines worked. 2. Yearly total production of bituminous and sub-bituminous mines. 2a. Yearly production of machine-mined coal. 3. Average annual production, equivalent to consumption, for a period of 17 years. 4. Number of coal mine employees each year. 5. Estimated capacity of mines, on basis of 300 working clays in the year. 6. Estimated drop in capacity if no new mines are opened. Considering these curves and the data from which they were constructed: It will be noted that the average number of days the miners worked varied from 193 in 1908 to 234 in 1900, the average being 217. The causes for so many idle days out of the possible total number of working days in the year are well known, namely: (a) Lack of business; (b) lack of cars. Taking the country as a whole, (a) is the important factor, which might otherwise be expressed as being an excess of productive capacity. The yearly production of the mines, which is practically synonymous with consumption, has shown a steady increase, with a few set-backs. An average line has been struck which indicates that the average annual increase of production has been 18 million short tons (16,330,000 metric tons).

Jan 5, 1918

By R. W. Kobler, D. A. Dahlstrom

Since the development of the pelletizing process in the fifties for relatively high purity pellets from low grade taconites, there have been several distinctive changes in filter construction for the dewatering step preceding balling. In the original large pilot plant run by Reserve Mining Co. in Babbitt, MN, the disk type filter employing agitation (Agidisc filter) was selected as the most economical. Size was limited to 2.1 m (6 ft, 9 in.) in diameter. The second generation occurred in the sixties with a jump to 2.70 m (8 ft, 10 in.) in diameter to reduce capital costs per annual ton of pellet. In the early seventies, the third generation was the steam drying disk filter which became necessary to achieve balling moistures with specific surface areas of 2200 cm2/g to as high as 3800 cm2/g caused by finer grinding to obtain higher purities. Finally, the fourth generation has recently been developed to reduce maintenance costs and further improve hydraulics to ensure minimum moisture contents.

Jan 1, 1980

By Anal J. Mehta, Theodore D. Tiemann

Growing demand for steel and increasing dependence upon foreign ore makes the need for developing the technology for treatment of low-grade iron ores greater than ever before• Representative of these added interests were the studies carried on at the University of Wisconsin• These studies included among others: anionic and cationic flotation, magnetic separation, roasting followed by magnetic separation, electrostatic separation, a hydrogen reduction process,6,7 and caustic digestion• The idea of removing silica by caustic extraction is not new•-1; The principle of concentrating siliceous iron ores by this method is based on the fact that silica is soluble in sodium hydroxide solution while iron oxides are essentially insoluble• For this process to be economically feasible, it is believed that some method of recovering silica from solution as a marketable by-product, with recycling of spent liquor is necessary. Precipitation of silica with carbon dioxide will allow subsequent causticizing of the spent liquor with lime• Caustic thus produced can be recycled for digestion• A flowsheet of the envisioned process is given in [Fig• 1] The purpose of this paper is to describe results obtained from the investigation of carbon dioxide precipitation of silica from sodium silicate solutions, which could be later applied to the caustic extraction process to treat low grade siliceous iron ores, particularly taconites.15 Theoretical Considerations The soluble silicates of sodium include sodium orthosilicate (2Na2O•SiO2), sodium metasilicate (Na20•SiO2), sodium disilicate (Na1O•2SiO2), and more highly siliceous products approaching Na2O•4SiO2• These materials have been described in detail by Vail•16 Stones has reported that the extraction of silica is not significantly affected by the amount of silica in solution until the Si02/Na20 ratio exceeds that of orthosilicate (Ratio = 1/2)• However, as the Si02/Na2O ratio exceeds that of metasilicate (Ratio = 1), silica extraction is significantly impaired• The present experimental work was confined to orthosilicate and metasilicate solutions, as to be successful the envisioned commercial process for the extraction of silica from siliceous iron ores would operate in this region. The mechanism of extraction of silica from aqueous sodium silicate solutions is complex in nature. For the carbon dioxide process-18 of core and mold making in which silica is also precipitated from sodium silicate solutions by gassing with carbon dioxide, the reaction of aqueous silicates with gaseous carbon dioxide has been represented by the equations: [ ] However, these equations are very much oversimplified• It has been shown that the reaction between aqueous sodium silicates and carbon dioxide gas is ionic in nature 18 Considering this fact and the mechanism for digestion of silica in aqueous sodium hydroxide, the overall conversion of aqueous sodium silicates to solid silica may be represented in ionic form by the following equations: [ ] Silicon in the silicate ion is shown here with a coordination number of 6• This may be in doubt, but it is known that ion (SiF°)-2 exists; it seems logical that the Si (OH) e 2 ion should be equally capable of existence•

Jan 1, 1977

For the year ending February, 1917 PRESIDENT L. D. RICKETTS,1 NEW YORK, N. Y. PAST PRESIDENTS BENJAMIN B. THAYER,1 NEW YORK, N. Y. WILLIAM L. SAUNDERS,2 NEW YORK, N. Y FIRST VICE-PRESIDENT SIDNEY J. JENNINGS,1 NEW YORK, N. Y. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y SECRETARY BRADLEY STOUGHTON, NEW YORK, N. Y.

Jan 12, 1916

G. D. Kneip, Jr., and J. 0. Betterton, Jr. (Union Carbide & Carbon Corp., Oak Ridge, Tenn.)—The authors have contributed to the theory of zone melting by considering the effects of the solidification of the final zone on the distribution curves for the finite length bar. However, they do not consider in sufficient detail the restrictions imposed by the particular metals involved. Eq. 4 has the analytical solution which is equivalent to Pfann's' equation for normal solidification of the final zone. For distribution coefficients less than one, it is apparent from this form of the equation that, as the solidification approaches completion, the concentration attains extremely large values which are inconsistent with the density of physical materials. The necessary restrictions then are that the solute concentration cannot exceed the density of the alloy, or more frequently, the solubility limit in the solid phase. Secondly, the distribution coefficient cannot be constant from 0 to 100 pet solute unless the liquidus and solidus coincide over this whole region. It would thus be more correct to impose limits on the solubility such as would be indicated by a typical eutectic diagram. Furthermore, in this case the assumption that the distribution coefficient remains constant is more likely to be realized. Eq. 4 should then be replaced by the following C,,(x) =k/L-x [ ?11 3 C11 (x)Ddx - ?11 4 Cn(x)dx= k[Cn (L-l)/k] [ L-x/l]x-1 L-l = x = L-l [kCenterlie/Cn (L-l)]1/k-1 The typical shape for the distribution curve in the final zone is indicated schematically in Fig. 12 for the simple eutectic case. The solidification proceeds according to Pfann's' expression until the concentration reaches the maximum solubility in the solid phasc. At this point, the concentration changes abruptly to the eutectic composition and remains at this value for the duration of the solidification. The width of the flat region, and the back reflection of this effect into the concentration curve on subsequent passes, depends upon the ratio of the eutectic concentration to the original concentration, upon the distribution coefficient, and upon the number of passes. Similar effects on the concentration curves in the first zone length would be expected in many systems for which the distribution coefficient is greater than one, and where the maximum solubility is not too much larger than the original concentration. The discussers agree with the authors that the assumption that the liquid is uniform in concentration should be considered with caution. Kneip and Better-ton' have shown, however, that in floating zone refining of zirconium, using induction heating, the distribution of iron agrees with theory which assumes a uniform liquid composition. Hence, in this case, the experimentally realized distribution coefficient agrees with the present phase diagram within the experimental uncertainty. L. Burris, Jr., C. H. Stockman, and I. G. Dillon (authors' reply)—The authors are happy to have received the comments of G. D. Kneip, Jr., and J. 0. Betterton, Jr., which provide additional insight into the zone refining process. It is true that the equations developed are inapplicable if the solute solubility in the solid phase is exceeded. However, this restriction on the use of the equations was clearly stated in the paper. A closer approach to

Jan 1, 1957

For the year ending February, 1917 PRESIDENT L. D. RICKETTS,1 NEW YORK, N. Y PAST PRESIDENTS BENJAMIN B. THAYER 1 NEW YORK, N. Y. WILLIAM L. SAUNDERS,2 . NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS,1 NEW YORK, N. Y. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 10, 1916

By Nelson Severinghaus

Consolidated Quarries Corp. must conduct operations for an average sales price of $1.25 per ton, about the same price at which stone was sold 25 years ago when the dollar was worth twice what it is now. To maintain success in a competitive business, the company must solve the usual production problems, which will be discussed here in the order they occur in the flowsheet. Most crushed stone quarries must first remove soil and decomposed rock. Although seasons of lower sales sometimes release regular quarry excavating and haulage equipment for this purpose, overburden is often too extensive for this method to be used. In such cases, special equipment must be assigned or the job may be contracted. As many earthmoving contractors have heavy duty specialized equipment well suited to overburden removal, they should be seriously considered before the job is undertaken. Pockets of clay beneath peaks of hard stone sometimes defy mechanized removal. Pick and shovel laborers at this point might be supplanted by more ingenious use of pumps and water or some other mechanical means. Where overburden is extremely heavy or difficult to remove, underground mining must be considered.

Mar 1, 1956

The Committee on Nominations begs to submit the following names as its nominees for the respective offices indicated: For President, SIDNEY J. JENNINGS, New York. For Vice-Presidents, WALTER H. ALDRIDGE, New York; MARK L. REQUA, San Francisco. For Directors, J. E. JOHNSON, JR., New York; ALLEN H. ROGERS, Boston; HOWARD N. EAVENSON, West Virginia; ROBERT M. RAYMOND New York; WILLET G. MILLER, Canada.

Jan 12, 1916

For the year ending February, 1917 PRESIDENT L. D. RICKETTS,1 NEW YORK, N. Y. PAST PRESIDENTS BENJAMIN B. THAYER,1 NEW YORK, N. Y. WILLIAM L. SAUNDERS,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS,1 NEW YORK, N. Y. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON, NEW, YORK, N. Y.

Jan 7, 1916

By B. M. Larsen, K. Heindlhofer

THIS paper describes a relatively simple electrical apparatus that, through the close analogy between the flow of heat and of electricity, enables one to solve quickly and with satisfactory accuracy many complex problems in heat flow. This device, developed in 1935, has proved especially useful in the solution of certain practical problems relating to the design and efficiency of regenerators for an open-hearth furnace or coke oven, yielding within a few hours information that would take weeks or even months to acquire by mathematical1.2 or experimental3 methods of comparable accuracy. Its description now is prompted by growing interest in such analogues, as shown by several recent papers.4.5 The analogy between flow of heat and of electricity appears to have been recognized first by Maxwell who, in his famous Treatise on Electricity and Magnetism (1881) says: The analogy between the theory of the conduction of electricity and that of the conduction of heat is at first sight almost complete. If we can take two systems geometrically similar, and such that the conductivity. for heat at any part of the first is proportional to the conductivity for electricity at-the corresponding part of the second, and if we also make the temperature of any part of the first proportional to the electric potential at the corresponding point of the second, then the flow of heat across any area of the first will be proportional to the flow of electricity across the corresponding area of the second. .. Thus, in the illustration we have given, in which flow of electricity corresponds to flow of heat, the electric potential to temperature, electricity tends to flow from places of high to places of low potential, exactly as heat tends to flow from places of high to places of low. temperature He noted, however, that this analogy is restricted: ... there is, however, one remarkable difference between the phenomena of electricity and those of heat. Suspend a conducting body within a closed conducting vessel by a silk thread, and charge the vessel with electricity. The potential of the vessel and of all within it will be instantly raised, but however long and however powerfully the vessel be electrified, and whether the body within be allowed to come in contact with the vessel, or not, no signs of electrification will appear within the vessel, nor will the body within show any electrical effect when taken out. But if the vessel is raised to a high temperature, the body within will rise to the same temperature, but only after a considerable time, and if it is then taken out it will be found hot, and will remain so till it has continued to emit heat for some time. The difference between the phenomena consists in the fact that bodies are capable of absorbing and emitting heat, whereas they have no corresponding property with respect to electricity. According to this statement the application of the analogy would be limited to problems of steady flow that do not involve heat-capacity effects. In spite of this

Jan 1, 1945

By William Rawles

THIS report is the first of a series planned by The Mineral Inquiry, organized by the American Institute of Mining and Metallurgical Engineers to make factual studies of the world's mineral resources in their political and international relations. The efforts of The Inquiry are directed toward filling certain notable gaps in available information, without duplication of many other investigations touching this field which are being conducted by other organizations, public and private. Much of its work is indirect-suggesting topics for study by other individuals and organizations and aiding in their planning and correlation. The present report is designed to show the nationality of the commercial control of mineral resources, in addition to the geographic distribution of production by nation-in other words, the overlapping of political and commercial control. Detailed accuracy cannot be claimed for the figures presented. For some companies division of ownership by nationality has been very difficult to ascertain, as many companies are reluctant to dis-close the extent of their holdings in other corporations, and the impossi-bility of tracing all stock ownership is obvious. Also there are frequent changes in the distribution of stock control. The percentages given rep resent only the participation that has been identified definitely, even though it is known in some cases with fair certainty that larger interests exist, as, for instance, American participation in foreign chromite companies. In bringing together these figures we have had the cordial co-operation of the United States Bureau of Mines, the United States Geologi-cal, Survey, the Mineral Division of the Bureau of Foreign and Domestic Commerce, the Brookings Institution, and of many specialists connected with the mineral industries covered. The report does not cover the entire list of minerals: Coal, although it is one of the most important minerals, was omitted because not more than one or two per cent of the world's production comes from mines that are owned by companies foreign to the countries where the coal is produced. Others, such as gold, are omitted because sufficient data have not yet been accumulated. It is hoped that some of these may be covered in subsequent reports. It is not our purpose here to discuss the significance of the figures sub-mitted, but only to point out the general nature of the problems on which they have a bearing.

Jan 1, 1933

By Ralph B. Stevens

INTRODUCTION Underground fires continue to be one of the most serious hazards to life and property in the mining industry. Although underground mines are analogous to high-rise buildings where persons are isolated from immediate escape or rescue, application of technology to locate and control fire hazards while still in their controllable state is slow to be implemented in underground mines. Even in large surface structures such as hotels, often only fire protection systems which meet minimal laws are implemented due to the high cost of adding extensive extinguishing systems, isolation barriers, alternate ventilation, escape routes and alarm systems. Incomplete and ineffective protection occasionally is evidenced where costs would not seem to be a factor, such as the $211 million MGM Grand Hotel fire November 21, 19801. Paramount in increasing fire safety and decreasing the threat of serious fire is early warning followed by proper decision analysis to perform the correct action. However, very complex fire situations can be produced in structures such as high-rise buildings and underground mines simply because of the distances between the numerous fire-potential locations and fire safe areas. Other complexities arise when normal activities occur that emit products of combustion signaling a fire condition to a sensitive fire/smoke sensor. For example, the operation of diesel equipment or the performance of regular blasting can produce combustion products that reach the sensitive alarm points of many sensors2. Smoke detectors for surface installations provide fire warning when occupants are at a distant location or when sleeping, thus greatly reducing injuries and property damage. However, when installed in the harsh environments of underground mines, fire and smoke detection equipment soon becomes inoperative, unreliable, or requires excessive maintenance. The U.S. Bureau of Mines has performed many studies and tests to improve fire and smoke protection for underground mine workers3. This paper describes several USBM safety programs which included in-mine testing with mine fire and smoke sensors, telemetry and instrumentation to develop recommendations for improving mine fire safety. It is hoped that the technology developed during these programs can be added to other programs to provide the mining industry with the necessary fire safety facts. By recognizing fire potentials and being provided with cost-effective, proven components that will perform reliably under the poor environmental conditions of mining, mine operators can provide protection for their working life and property equal to that which they provide for themselves and their families at home. The basis of this report is two USBM programs for fire protection in metal and nonmetal mines4,5 and one coal program6. The data was collected beginning in May 1974 and continuing through the present with underground tests of a South African fire system installed at Magma Mine in Superior, Arizona, and a computer-assisted, experimental system at Peabody Coal Mine in Pawnee, Illinois. The conduct of each program was as follows: • Define the problem and its magnitude in the industry • Develop concepts to solve or diminish the problem • Review available hardware or systems approaches to fit the concepts • Install and demonstrate the performance of a prototype system through fire tests in an operating mine. MINE FIRE FACTS Whether in coal or metal and nonmetal mines, the potential severity of fire hazard is directly related to location. As shown in Figure 1, fire in intake air at zones A, B, C or D can cause contamined air to route throughout the mine quickly if not detected, isolated or rerouted. Causes and location of former metal and nonmetal fires are represented in Table 1; the cause and location of fatalities and injuries is shown in Table 2. Coal-related fires and their impact on deaths and injuries are graphed in Figure 2; their locations are described in Table 37. Significantly the table shows that the hazard to personnel was three times greater for fires occurring in shaft or slope areas, and the percentage of deaths and injuries was four times that of other areas. Number of Persons Affected A 129-mine sample indicated that from 8 to 479 employees per shift work in underground metal and nonmetal mines, and that deeper mines have larger populations, as shown in Figure 3. Coal mining relates similar employment, and a 16-state sample of 670 mines employing at least 25 persons shows the distribution in Figure 4. Drift mines accounted for 58 percent of the sample but employ only 45 percent of the underground workers.

Jan 1, 1982

By E. W. Pehrson, J. W. Furness

NONMETALLIC MINERALS, exclusive of fuels, may be divided into three groups: Building materials, fertilizer minerals, and miscellaneous minerals. Building materials, such as sand, gravel, slone, lime, and the ingredients of cement and clay products, occur widely in nature and are thus available near consuming centers at relatively low prices. Cost of transportation over great distances deters any' substantial movement in world trade. On the other hand, fertilizer minerals, such as phosphate rock, potash, nitrates, sulfur, and pyrite, and the miscellaneous nonmetallic minerals, such as long-fiber asbestos, mica, graphite, fluorspar, and china clay, do not have such widespread occurrence and consequently contribute the major part of the world's commerce in such minerals. The U. S. Bureau of Mines has prepared charts showing the inter-

Jan 1, 1936

By W. J. Leas, L. A. Rapoport

As a preliminary, consicleration is given to the conventional definition of relative permeability and to the conditions governing the simultaneous flow of oil and gas through porous media. For the conditions of flow prevailing throughout most of a gas drive reservoir, the oil and gas can reasonably be supposed to be in capillary equilibrium with each other. Under these conditions, and these conditions only, the relative permeability to liquid can be expressed as a function of saturation. The relative permeability to liquid in that case is dependent upon the distribution of fluids which itself is shown to be related to the capillary pressure, and, in turn, to the saturation. As a consequence, relative permeability to liquid can be expressed in terms of the volume and surface area of a network of liquid channels bounded by the rock and the gas phase. While the volume of this network can be evaluated accurately, the surface area cannot. However, for any such volume, maximum and minimum values of the corresponding surface area can be calculated from capillary pressure data. It is then possible to establish for any saturation the limits within which the value of the relative permeability to liquid must lie. As a consequence of the theoretical development, the validity of an experimental method for measuring relative permeability to liquid which utilizes a stationary gas phase is demonstrated. In this method capillary barriers are cemented to the ends of the core sample to permit the maintenance of capillary equilibrium between the two phases. At the same time, this procedure eliminates undesirable secondary phenomena such as end effects, fissure effects, etc., the presence of which adversely affect the results of other laboratory methods. The results obtained by theoretical calculations, and experimentally, are discussed. In view of the overall precision that can presently be obtained in reservoir calculations, the agreement between the calculated and measured relative permeability to liquid data can be considered satisfactory. In conclusion, for reasons of economy and simplicity, the procedure of calculating limiting relative permeability to liquid curves from capillary pressure data is indicated for general engineering purposes. It is shown that the above procedure can easily be extended to the cases where connate water is present. Its use for reservoir studies is particularly recommended in conjunction with the method for measuring relative permeability to gas' which simultaneously yields the capillary pressure data necessary for the calculations. THEORETICAL Definition of Relative Permeabilities — Basic Equations for Heterogeneous Flow The equations by which the relative permeability concept is defined and upon which the formulation of all of the gas-oil flow problems rests at the present time are expressed as: V, = — Grad PL = — Grad PL ....(la) PL µL, k k KG VG = —K - Grad PG k- Grad Pc .... (lb) Mo where ,. and G refer to liquid and gas; V is the volumetric rate of flow per unit gross area. µ the viscosity, Grad P the potential gradient. and k the specific permeability of the porous medium.* (For horizontal flow, Grad P becomes the pressure gradient; otherwise, gravity must be included.) According to these expressions, each of the constituent phases is considered similar to a homogeneous system where the volumetric rate of flow is proportional to the pressure gradient, and for each of which the constants of proportionality, k, and kG, are termed effective permeabilities. by analogy to the specific permeability as defined by Darcy's law in its original form. In order to obtain a convenient basis of comparison, the effective permeabilities are referred to the specific permeability, k, of the considered porous medium, with the help of the relations: k1. = KI. k kQ = Kn k..........(2) K,. and Kr. are defined as the relative permeabilities to the liquid and to the gas phase respectively, and frequently expressed in per cent of specific permeability. It may be seen that Equations (1); which appear to be a direct generalization of Darcy's law, correspond to the assignment at any given time of a set of "local" permeabilities to each point of the porous medium, and represent in a differential form the two fluid flow system as a simple superposition of the individual single flow systems. The above interpretation implies that the effective or relative permeabilities are independent of pressure or rate of flow,

Jan 1, 1951

By L. A. Rapoport, W. J. Leas

As a preliminary, consicleration is given to the conventional definition of relative permeability and to the conditions governing the simultaneous flow of oil and gas through porous media. For the conditions of flow prevailing throughout most of a gas drive reservoir, the oil and gas can reasonably be supposed to be in capillary equilibrium with each other. Under these conditions, and these conditions only, the relative permeability to liquid can be expressed as a function of saturation. The relative permeability to liquid in that case is dependent upon the distribution of fluids which itself is shown to be related to the capillary pressure, and, in turn, to the saturation. As a consequence, relative permeability to liquid can be expressed in terms of the volume and surface area of a network of liquid channels bounded by the rock and the gas phase. While the volume of this network can be evaluated accurately, the surface area cannot. However, for any such volume, maximum and minimum values of the corresponding surface area can be calculated from capillary pressure data. It is then possible to establish for any saturation the limits within which the value of the relative permeability to liquid must lie. As a consequence of the theoretical development, the validity of an experimental method for measuring relative permeability to liquid which utilizes a stationary gas phase is demonstrated. In this method capillary barriers are cemented to the ends of the core sample to permit the maintenance of capillary equilibrium between the two phases. At the same time, this procedure eliminates undesirable secondary phenomena such as end effects, fissure effects, etc., the presence of which adversely affect the results of other laboratory methods. The results obtained by theoretical calculations, and experimentally, are discussed. In view of the overall precision that can presently be obtained in reservoir calculations, the agreement between the calculated and measured relative permeability to liquid data can be considered satisfactory. In conclusion, for reasons of economy and simplicity, the procedure of calculating limiting relative permeability to liquid curves from capillary pressure data is indicated for general engineering purposes. It is shown that the above procedure can easily be extended to the cases where connate water is present. Its use for reservoir studies is particularly recommended in conjunction with the method for measuring relative permeability to gas' which simultaneously yields the capillary pressure data necessary for the calculations. THEORETICAL Definition of Relative Permeabilities — Basic Equations for Heterogeneous Flow The equations by which the relative permeability concept is defined and upon which the formulation of all of the gas-oil flow problems rests at the present time are expressed as: V, = — Grad PL = — Grad PL ....(la) PL µL, k k KG VG = —K - Grad PG k- Grad Pc .... (lb) Mo where ,. and G refer to liquid and gas; V is the volumetric rate of flow per unit gross area. µ the viscosity, Grad P the potential gradient. and k the specific permeability of the porous medium.* (For horizontal flow, Grad P becomes the pressure gradient; otherwise, gravity must be included.) According to these expressions, each of the constituent phases is considered similar to a homogeneous system where the volumetric rate of flow is proportional to the pressure gradient, and for each of which the constants of proportionality, k, and kG, are termed effective permeabilities. by analogy to the specific permeability as defined by Darcy's law in its original form. In order to obtain a convenient basis of comparison, the effective permeabilities are referred to the specific permeability, k, of the considered porous medium, with the help of the relations: k1. = KI. k kQ = Kn k..........(2) K,. and Kr. are defined as the relative permeabilities to the liquid and to the gas phase respectively, and frequently expressed in per cent of specific permeability. It may be seen that Equations (1); which appear to be a direct generalization of Darcy's law, correspond to the assignment at any given time of a set of "local" permeabilities to each point of the porous medium, and represent in a differential form the two fluid flow system as a simple superposition of the individual single flow systems. The above interpretation implies that the effective or relative permeabilities are independent of pressure or rate of flow,

Jan 1, 1951

For. the year ending February, 1917 PRESIDENT L. D. RICKETTS,1 NEW YORK, N. Y. PAST PRESIDENTS BENJAMIN B. THAYER,1 NEW YORK, N. Y. WILLIAM L! SAUNDERS,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS,1 NEW YORK, N., Y. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON, NEW-YORK, N. Y.

Jan 2, 1917

By H. H. Kellogg

Equations representing the standard free energy of formation as a function of temperature, for thirty metallic chlorides, are presented and plotted on a free-energy vs. temperature diagram. The use of these data for calculations on reduction of metallic chlorides, refining of metals with chlorine, and chlorination of metallic oxides and sulphides is illustrated. CHLORINE metallurgy' has attracted metallur- gists for more than a century because the unusual properties of the metallic chlorides—low melting point, high volatility, and ease of formation from the oxides—make possible many useful extractive processes. Interest in chlorine processes is undergoing a renaissance due to present availability of chlorine at relatively low prices, and to recent advances in technology. During the present century there have accumulated a considerable number of reliable values of the thermodynamic constants for the metals and their chlorides. These data permit the calculation of free-energy equations for many metallurgically important reactions. Consideration of free-energy values makes possible certain predictions of the direction and extent of a given reaction, as well as the effect of temperature, pressure, and composition upon the result. Reaction rate, although not predictable from free-energy data, is usually sufficiently great at elevated temperatures that diffusion of the reactants and products to and from the zone of reaction determines the actual rate. Thus, if the free-energy indication is favorable, the chances are good that a high temperature metallurgical reaction will proceed at a reasonable rate, if adequate provision for rapid diffusion has been made. This paper presents standard free-energy equations for a number of metallic chlorides, based on data which are scattered throughout the literature. The equations are presented in a form that simplifies their use, and typical examples are given of the application of free-energy data to metallurgical processes. Free Energy of Reaction The free-energy change (AG) of a reaction is the true measure of the "driving force" of the reaction under a given set of conditions, and this is related to the standard free-energy change (AGO) of the reaction as follows: For the reaction: bB + cC = dD + eE ?G = ?G°+RTln ADd. AEA / ABb. ACc where A, = activity of constituent (i) T = absolute temperature, OK R = gas constant The criterion of a spontaneous reaction from left to right, at constant temperature and pressure, is a negative value for the free-energy change (?G). The standard free energy of the reaction is equal to the free energy of the reaction when all the reactants and products are at unit activity, since under these conditions the second term on the right-hand side of eq 1 is equal to zero. The concept of activity is treated fully in many textbooks on chemical thermodynamics1 and in a recent article by Chipman.2 Briefly, the activity (A,) of a constituent (i) is a measure of the reactivity of this constituent relative to its reactivity in some arbitrary standard state. For liquids and solids the standard state most often used is the pure liquid or solid constituent. Thus the activity of a pure liquid or solid in a metallurgical reaction is equal to unity. Gases under moderate pressure and at elevated temperatures behave very nearly as 'idea1 gases,' and the standard state is chosen as the gas at 1 atm pressure. The activity of an ideal gas is therefore equal to its partial pressure, and this relation is sufficiently exact for real gases in most metallurgical reactions. For a liquid or solid solution there is in general no simple way to express the activity of a constituent as a function of its concentration, and activity must be determined by experiment. A few solutions follow a so-called 'ideal' behavior, and if the pure constituent is chosen as the standard state, the activity of a constituent in an ideal solution becomes equal to its mol fraction. When a reaction reaches a state of thermodynamic equilibrium at constant temperature and pressure, AG becomes equal to zero and eq 1 reduces to: [ADd . AEe ?G°=RTln Abb ¦ Ac c equilibrium [2] The brackets surrounding the activity term are used to emphasize that each of the activities is an activity under equilibrium conditions—not just any arbitrarily assigned value. The bracketed term is the equilibrium constant (K) of the reaction. Eq 2 makes possible the calculation of equilibrium activities for a given reaction, if AGO is known at the desired temperature. The standard free-energy equations presented in this paper were calculated from the fundamental thermodynamic values of enthalpy of formation at 298°K (AH°,), standard entropy at 298°K (So298), heat capacity as a function of temperature (Cp), and enthalpies of transition, fusion, vaporization, and sublimation for the various constituents. Where possible the data reported in the recent "Selected Values of Chemical Thermodynamic Properties," published by the Bureau of Standards," were used. A large number of data came from the publications

Jan 1, 1951

For the year ending February, 1917 PRESIDENT L. D. RICKETTS,1 NEW YORK, N. Y PAST PRESIDENTS BENJAMIN B. THAYER 1 NEW YORK, N. Y. WILLIAM L. SAUNDERS,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS,1 NEW YORK, N. Y. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 10, 1916

By Richard Birk

Rf sputtered quartz has been successfully used in multilayer interconnects for MOS devices. The target potential was 2000 v peak to peak with a frequency of 13.56 Mc per sec. The sputtering rate was approximately 60A per min with an operating pressure of argon gas at 10 to 15 p. The dielectric strength is 8.0 x 10' v per cm and the pinhole density is less than 2 x 10-2 per sq mm. Infrared absorption peaks for the Si-O vibrational bands we at 9.4, 12.4, and at 22.5 p. The etch rate of the sputtered SiO2 is 1200A per min. MOS devices have been fabricated using multilayer interconnects with no degradation of electrical characteristics. MULTILAYER interconnects require an insdating film between the metal layers which can be deposited below any potential eutectic temperature. Sputtered Si4, which can be deposited with substrate temperatures below 200°C, satisfactorily meets the multilayer insulation requirements and has been used to prepare MOS circuits with multilayer interconnects. The physical and electrical properties of rf sput-

Jan 1, 1969

For the year ending February, 1917 PRESIDENT L. D. RICKETTS,1 NEW YORK, N. Y. PAST PRESIDENTS BENJAMIN B. THAYER,1 NEW YORK, N. Y. WILLIAM L. SAUNDERS,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS1 NEW YORK, N. Y. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY . BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 5, 1916