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By D. P. Morton

Since 1923, which closed the speculative era in the bituminous coal fields of the United States, there have been wide annual fluctuations in the national production of bituminous coal. These changes in annual output have been variously attributed to: (1) increased competition from petroleum products, natural gas and hydroelectric power; (2) lower unit consumption of coal; and (3) fluctuations in the general business level. The purpose of this paper is to measure, from a practical standpoint, the net effect upon the annual trend of bituminous coal production, and to give those who are interested a basis for estimating in advance the probable output of bituminous coal. It can readily be shown that changes in the level of general business affect the national production of bituminous coal more than does any other factor. Therefore it is necessary to use some standard measure of the relative business level for purposes of comparison. The Federal Reserve Board Index of Industrial Production offers the basis for such a measure.l This Index, a weighted composite of 81 different series, rests upon the averages of the years 1935 to 1939 as 100, and is presented graphically in Fig. I. Even a cursory examination of the chart will indicate a definite uptrend for industrial production over a period of years. This uptrend is due to at least two factors: (I) an actual increase in national population, and (2) a probable increase in the per capita consumption of goods. This means that there is no such thing as a fixed Normal, rather Normal is a variable, tending to increase from year to year. In order to measure the amount of annual increase in normal, the Index of Industrial Production must be studied in relation to its major components, Durable Goods and Nondurable Goods, Durable Goods are those made from the lasting materials such as iron, steel, other metals, lumber, stone, cement, clay, glass. Nondurable Goods are those for early consumption, such as foods, textiles, tobacco, chemicals, paper, gasoline, and goods made of leather and rubber. The purchase of Durable Goods may be postponed, but Nondurable Goods must be purchased currently unless the standard of living is lowered. The Federal Reserve Indexes of durable and nondurable goods are shown graphically, 1920 to 1939, on Fig. a (pp. 764-765 of ref. I). It is apparent that fluctuations in the production of nondurable goods are not nearly so wide as in the production of durable goods, and that the curve of Industrial Production (Fig. I) would fall between the two curves on Fig. 2. It would, however, seem logical that both curves should follow the same long-term trend, or that over a period of two to three decades the relative proportion of durable and nondurable goods, in periods of normal production, should be the same. It is neces-

Jan 1, 1942

By D. P. Morton

Since 1923, which closed the speculative era in the bituminous coal fields of the United States, there have been wide annual fluctuations in the national production of bituminous coal. These changes in annual output have been variously attributed to: (1) increased competition from petroleum products, natural gas and hydroelectric power; (2) lower unit consumption of coal; and (3) fluctuations in the general business level. The purpose of this paper is to measure, from a practical standpoint, the net effect upon the annual trend of bituminous coal production, and to give those who are interested a basis for estimating in advance the probable output of bituminous coal. It can readily be shown that changes in the level of general business affect the national production of bituminous coal more than does any other factor. Therefore it is necessary to use some standard measure of the relative business level for purposes of comparison. The Federal Reserve Board Index of Industrial Production offers the basis for such a measure.l This Index, a weighted composite of 81 different series, rests upon the averages of the years 1935 to 1939 as 100, and is presented graphically in Fig. I. Even a cursory examination of the chart will indicate a definite uptrend for industrial production over a period of years. This uptrend is due to at least two factors: (I) an actual increase in national population, and (2) a probable increase in the per capita consumption of goods. This means that there is no such thing as a fixed Normal, rather Normal is a variable, tending to increase from year to year. In order to measure the amount of annual increase in normal, the Index of Industrial Production must be studied in relation to its major components, Durable Goods and Nondurable Goods, Durable Goods are those made from the lasting materials such as iron, steel, other metals, lumber, stone, cement, clay, glass. Nondurable Goods are those for early consumption, such as foods, textiles, tobacco, chemicals, paper, gasoline, and goods made of leather and rubber. The purchase of Durable Goods may be postponed, but Nondurable Goods must be purchased currently unless the standard of living is lowered. The Federal Reserve Indexes of durable and nondurable goods are shown graphically, 1920 to 1939, on Fig. a (pp. 764-765 of ref. I). It is apparent that fluctuations in the production of nondurable goods are not nearly so wide as in the production of durable goods, and that the curve of Industrial Production (Fig. I) would fall between the two curves on Fig. 2. It would, however, seem logical that both curves should follow the same long-term trend, or that over a period of two to three decades the relative proportion of durable and nondurable goods, in periods of normal production, should be the same. It is neces-

Jan 1, 1942

By J. F. Wolff, Anson A. Betts

The following correspondence relating to a paper bearing the above title, presented by J. F. Wolff, at the New York meeting in February, 1917, and published in the Transactions, Volume LVI, page 142, has passed between the author of the paper, and Mr. Anson G. Betts, and is interesting, although it was received much too late for incorporation in its proper place in Volume LVI. Anson G. Betts, Asheville, N. C.—1. I should like to ask Mr. Wolff if he finds from analysis of the iron formation and of the iron ore, and from the relative amounts of each in each unit area of the formation, unleached and after leaching, that the iron remains entirely insoluble and the total quantity still remains present; or whether he finds that some of the iron is removed, or possibly even added by deposition from the water passing through the formation. 2. The water that passed into the iron formation had to go somewhere; was it absorbed by underlying formations through hydration, or, after passing through the ore formation, did it come to the surface in springs at a lower elevation, or how did it escape from the ground? 3. I should like to ask Mr. Wolff whether he finds that the iron formation in the sedimentary series does not come next to the quartzites and generally between the quartzites and slates. J. I?. Wolff, Duluth, Minn.—1. In common with others, you appear to have some hesitancy in accepting the fact of the removal, by solution, of the enormous quantity of silica which has been leached out of portions of the Biwabik iron formation, thus forming orebodies of merchantable iron ore. I believe that even Dr. Waldemar Lindgren once hesitated to accept this fact. However, the evidence is so simple and absolutely conclusive that the fact is established beyond all question. At the contact of orebodies with their rock walls, the bands of iron ore in the orebody can be seen in contact with the corresponding bands of original iron oxide in the rock wall, and the chert layers in the rock wall can be seen to give place to fine granular material (fine silica and iron oxide) and pore space. This is especially noticeable where slumping at the rock walls has not been so great as to displace the layers in the orebody from their contact with their corresponding layers in the rock wall. Although complete analyses of the entire original rocks in the iron series have not been made in any place, to my knowledge, from the best data at hand as to the average analysis of the Biwabik series and the

Jan 1, 1920

Engineers who are in charge of industrial operations, and their number is legion, sense as much as anyone the present feeling of unrest in the' country and more than anyone else realize the present inefficiency of labor. Undoubtedly the two phenomena are closely correlated and no doubt are due to a multitude of causes which it will be impossible to enumerate. From my experience in mining I estimate that the present efficiency of labor is only about two-thirds of what it was under pre-war conditions. In the mining industry, at least, we have not a large surplus of men looking for work and usually under these conditions men are rather more independent and will not work as efficiently and faithfully as if they felt there were plenty of men ready to take their places. Wages in metal mining have advanced more than the increased cost of normal and sane living. The result is that the men often work fewer days in a month and do not seem to have very much interest in their work while actually engaged in it. Then again, they have been listening to the more or less vague propaganda of the I. W. W. and the radical wing of the socialists, who are harping on the fact that the distribution of newly created wealth is unfair and that the laborer really is not working for himself or his fellow laborers but is carrying on his exertions for the benefit of a small and lim-ited class of exploiters. A continued harping on this view is bound to influence the judgment of even a conservative workman who is not a student of economics and who hears little or nothing upon the other side. I am a great believer in the common sense of the American people and in the long run I do not think that they will be carried away by unsafe doctrines. The trouble with so many of these propagandists of industrial in-equality is that they do not differentiate between production and dis-tribution. Even if we admit that distribution is unfair, unless goods are produced there will be nothing to distribute. A great many unthinking people seem to feel that wages are paid out of a pot which is inexhaustible and do not realize that eventually what comes out of the pot can never exceed what is put into it. The workman is not paid in money but is paid in goods, money as we all know being used simply as a measure of value and a medium of exchange, and that all that can be used to pay the laborer is what he produces.

Jan 11, 1919

By C. Richard Honeycutt, Frederick C. Langenberg, Guenter Pestel

Otto Schaaber (Institut für Harterei-Technik, Bremen-Schönebeck, Germany)— Langenberg, Pestel, and Honeycutt gave an interesting example of the grain refining effect nonstationary magnetic fields may execute on a solidifying metal. Probably some additional comments, based on more than a decade of experience with this method of influencing crystallization, may be useful. They refer to an attempt to explain the mechanism of grain refinement by such fields, and to recent European developments which have not been mentioned in the paper. I. During studies of the temperature distribution in a metal body near the phase boundary solid/liquid, an anomaly was observed under certain special conditions: a) direction of heat transfer as horizontal as possible, b) steady state (equilibrium, i.e,, solidification resp. melting rate exactly zero). In the liquid phase, immediately adjacent to the phase boundary, the temperature was found to be constant over an appreciable distance in spite of a high value of heat transfer (40.000 to 70.000 keal/ m2h).3 Convection, which might explain this phenomenon, could not be observed. Therefore another explanation had to be sought. The assumption that a metallic melt, especially at temperatures near the point of solidification, contains some sort of atomic arrangement with a higher degree of order than the surrounding liquid, now is generally accepted. Considering the differences in energy between such an arrangement and its environs, a transport of heat even in absence of any temperature gradient is conceivable by continued formation and redissolution of regions with a higher degree of order, i.e., with lower energy level.3 At this stage, it was not necessary to postulate any special condition as to the form or size of these regions or the distance between arrangements to be newly formed and those to be redissolved. However, a simple consideration shows that an energy transfer from one region to another will only be possible without loss of energy, if the distance between will be equal to the lattice parameters, and if, secondly, crystallographic axis or planes will be parallel.4 By the way, this assumption might give a reasonable explanation of the well known orientation effect of the heat flow during solidification. Any measures to prevent columnar crystallization should act upon this ordering mechanism: a) the regions with a lower energy (higher order) should not be allowed to arrange themselves parallel to the direction of heat flow, and their growth should be disturbed; b) all conditions leading to an appreciable heat flow of uniform direction should be avoided or removed. Condition a) may be satisfied by a physical force preferably under 90 deg to the main axis of the columnar crystals (i.e., parallel to the solidification front) acting on the ordered regions; condition b) by equalizing any differences in

Jan 1, 1962

By J. Weijdema, D. N. Dietz

In the conventional underground combustion process (dry combustion) much heat is left behind in the swept formation and goes to rva.rte. Econonmy can be improved by heat recuperation through water injection. This is most advantageous if done at the earliest opportunity before much heat is dissiputed to cap and base rock. Water injected simultaneously with the air will flash to superheated steam, which passes through the combustion front together with the nitrogen from the air. A condensation front traveling up to three times as fast as the combustion front drives out the oil. In this type of wet combustion, the water evaporates before it reaches the combustion zone. The evaporation front travels more slowly than the combustion zone. If so much water is injected that the evaporation front overrun the combustion front, combustion in that spot will be quenched and some unburned fuel will be left behind. Air reacts with the oil farther down-stream where steam temperatures occur; at steam temperature, the air reacts rapidly with the oil. Velocity of the combustion front is increased thereby and is governed essentially by the water-injection rate. In the extreme case of high water-injection rate, a short heat wave of constant length is driven through the formation by water injection. Once this wave has been established, no more heat need be generated than that required to make up the heat losses from the short heat wave; a relatively low rate of air injection will suffice. The feasibility of partially quenched combustion has been confirmed in tube experiments. A heat wave at steam temperature is observed. Chemical analyses of flue gas indicate preferential burning of hydrogen while a carbonaceous residue is left in the formation. Introduction A disadvantage of so-called dry in situ combustion is that air-compression costs are rather high. An air consumption of about 400 std cu m/cu m (400 scf/cu ft) of formation swept is an accepted figure. This high consumption is mostly wasted since much heat is left behind in the depleted oil sand. Methods were investigated for recuperating as much as possible of the heat left behind. This paper deals only with basic principles and is confined mainly to one-dimen- sional flow without lateral heat losses; experiments were conducted in relatively narrow, well insulated tubes. If some water is injected with the air, it will turn to superheated steam in an evaporation front, which should travel behind the combustion front. The steam having passed the combustion front causes a steam drive by a condensation front that can travel faster than the combustion front. The latter needs to travel only part of the distance covered by the oil-displacing condensation front, and thus consumes less air. The water-air ratio would seem limited to that at which cold water overruns the combustion. This limitation was deliberately exceeded considerably in theory and experiments. It was found that combustion is then indeed quenched, but only locally. Farther downstream, the oxygen finds residual oil at steam temperature, which is suficiently high to ensure rapid oxidation. Thus, the combustion front uses only part of the available fuel because it is chased through the formation faster than its normal velocity. No heat is left behind. This new process is called "partially quenched combustion". At the upper limit of the water-air ratio, a small heat slug is moved through the formation by the flow of water and steam. Only a small flow of air is needed since it has only to generate sufficient heat to make up for the lateral heat losses of the short heat slug. Theory Although many factors complicate underground combustion, the processes will be presented in their simplest form. For this reason, one-dimensional flow without lateral heat losses is assumed. Heat conduction in the direction of flow also is disregarded. Under these conditions, dry combustion causes very high temperatures. The heat-carrying capacity of the gas stream is small. Heat generated by oxidation of a residual oil saturation is retained in the sand. The available fuel determines the air requirement and the temperature obtained. Accepting the often-mentioned air consumption of 400 std cu m/cu m (400 scf/cu ft) formation, we calculate a temperature of the swept sand of 1,200C (2,192F) (Fig, I). If water is injected at a modest rate with the air, it will flash to superheated steam upon contact with the heated sand. One cu m (35.31 cu ft) of hot formation will evaporate about 0.5 cu m (17.66 cu ft) of water, and thereafter will accommodate (at an estimated 0.80 saturation and an assumed 0.40 porosity) another 0.3 cu m (10.59 cu ft) of water in cold condition. As long as less than 0.5 + 0.3 = 0.8 cu m (28.25 cu ft) of water is injected for every 400 std cu m (14,125 scf) of air (water-

Jan 1, 1969

By J. Szekely, V. Stanek

Steady state heat transfer and fluid flow rates are predicted for the counter-current contacting of gas and solid streams. For a .fixed pressure drop across the bed the convective heat transfer rate is affected by the gas flow rate, which in turn is affected by the temperature distribution in the system. Variations in bed voidage and in particle size were found to change the predicted temperature profiles quite markedly, in particular when the thermal capacities of the gas and solid streams were equal. IN Part I we examined the effect of step and pulse changes in the inlet gas temperature on transients in the flow of gases through fixed packed beds. Here we shall discuss heat flow and fluid flow interactions in the counter-current heat exchange between packed solids and a gas stream. Counter-current heat exchange in packed beds has been extensively studied. In his now classical paper, Furnas' assumed constant property values and developed a simple analytical. expression for the temperature profiles in the gas and in the solid stream. A highly sophisticated analysis of counterflow systems, allowing for transients and interparticle conduction was developed by Amundsen. In preparing a very readable review of this topic Elliott' also presented a number of elegant solutions, including the case involving heat generation. A great deal of work has been done on the application of these concepts to the modelling of the blast furnace. However, in all this previous work the mass flow of the gas was regarded as a quantity independent of the gas-solid heat exchange process. In the following we shall consider counter-current heat exchange between a gas stream and a packed bed of solids, under conditions where the pressure drop across the bed is specified, rather than the mass flow of the gas. FORMULATION Consider a packed bed, extending from y' = 0 to y' = L, in which moving solids and a moving gas are contacted in a counterflow arrangement. Let cold solids, with an initial temperature Tsi and mass flow GA, enter at y' = L, and hot gas with an initial temperature of Tgi and mass flow Gg enter at y' = 0. In contrast to the problems considered in Part I this system has a nontrivial steady state and we shall restrict our attention to the study of the pressure drop flow relationships and the resultant temperature distributions for steady state conditions. Under these conditions the formulation of the problem requires the statement of the following: 1) heat balance on the gas 2) heat balance on the solids 3) the mechanical energy balance equation and in addition the knowledge of the equation of state, and a functional relationship between viscosity and temperature and an expression for the heat transfer coefficient in terms of the other parameters. On neglecting temperature gradients within the solids and for a constant mass flow of the gas, the solution to this problem is well known.'" The expressions for the temperature profiles of the gas and solid streams may be put in the following form: where Tg and T, denote the dimensionless gas and solid temperatures respectively, y is a dimensionless distance, and R is the ratio of the thermal masses. These quantities are defined as follows: For the particular case of equal thermal mass capacities by the gas and the solid, that is R = 1, the Eqs. [1]and[2] simplify to Eqs. (71 and[8], respectively: i.e., the resultant profiles are linear. As for most practical cases , solutions given by Eqs. [7] and [8] will contain only the inlet temperatures as parameters. For a fixed, predetermined value of C;b the above

Jan 1, 1970

By Robert W. Elayer

In August 1973, Fluor Utah, Inc. was awarded a contract by the Office of Coal Research (now part of the Energy Research and Development Administration), Department of the Interior, for the examination of the unique problems of large-scale surface coal mining to supply coal conversion complexes. The project consists of two phases: (I) data base development and organization and the formulation of a mathematical computer modeling system for surface mining; and (II) computer manipulation of the data base in accordance with the model to formulate several typical preliminary mine and preparation plant designs. Phase I is scheduled for completion by the end of July 1975 and Phase II is scheduled to be complete by the end of January 1977. This paper briefly discusses the effort for only one aspect of this project-the foundation for geologic modeling developed in Phase I. The Phase I task of geologic modeling can be broken down into two subtasks: (1) identify areas containing sufficient resources of surface-minable coal to support at least one large-scale mining complex, and (2) characterize the coal deposits in these areas for computer storage and retrieval. Identification of Resource Regions The basic production design criteria for large-scale surface mining, as stated in the contract, is the production of 75,000 tpd, or more, of bituminous coal. Based on a constant total Btu delivered to the preparation plant, daily production requirements for the different coals are as follows: Bituminous Coal 75,000 tons Subbituminous Coal 99,500 tons Lignite 143,500 tons Although surface mining on this scale is presently non-existent, it is deemed that future operations, in order to meet the increased energy demands, will have to look forward to much larger scale mining complexes. These tonnage requirements are meant to be used only for the delineation of general areas suitable for large-scale surface mining, termed "Strippable Coal Resource Regions." They were determined largely from the latest complete detailed coal resource estimates of the U.S. Bureau of Mines. Nine strippable coal resource regions, containing over 100 billion tons of strippable coal resources, were identified [(see Fig. 1)]. The delineation of these regions was based entirely upon estimates of surface-minable coal resources and the production design criteria for large-scale surface mining. If surface-mined coal was combined with underground production, or if smaller production rates were specified, then other areas which were omitted here would be included in the regions. Changing the outline of the regions, however, would not add any new mining situations to be studied in Phase II. Characterization of Coal Deposits The second subtask involved the general characterization of the coal deposits contained in the strippable coal resource regions. The geological information gathered

Jan 1, 1976

I do not think too much emphasis can be placed upon creation of favorable climate for development of foreign mineral resources to feed the hungry maw of our industrialized nation. We have become dependent, not only upon the ten raw products indicated in Mr. Bancroft's article, but upon 71 mineral substances listed by DMPA as in short supply. Forty-four of these are metals, 9 are chemical minerals and 18 are nonmetallic minerals. Of this list only 8 are produced in any large quantity in the United States, and all are vital in peace-time industry. Even more, they are absolutely essential for defense. This represents our present needs. But if our consumption and requirements are projected over the next 25 years as is done by the President's Materials Policy Commission-The Paley Report-our future outlook becomes appalling. The divergence of consumption over production, even allowing for substitution and conservation, will widen in the future. This means our dependence upon foreign raw materials, mainly minerals, will grow. What are the chief foreign sources of minerals for our future needs? They are chiefly Latin America and the dominions and colonies of the Western European nations. The British Commonwealth countries contain in abundance those minerals which the U. S. lacks. Of 32 of the most critical minerals the Commonwealth is deficient in 7 and lacks only 1; whereas the U. S. is deficient in 18. Strikingly, our deficient minerals are abundant in the Commonwealth and several of their deficiencies are in excess in the U. S. Resources of the two nations complement each other. If Europe should be overrun by an unfriendly power that could control the destinies and resources of the European dominions and colonies, our industrial life would be placed in severe jeopardy. Therefore, I heartily endorse Mr. Bancroft's statements regarding the Point IV program, provided the program is wisely administered and implemented. It is from the underdeveloped countries, as pointed out by Mr. Bancroft, that most of our future mineral supplies will have to come. Many of the underdeveloped source countries are African colonies and dominions of Western European nations. Our present aid to Europe, therefore, is not, as many infer, a purely one-sided affair; it safeguards our future industrial development and security. Development aid directly to the underdeveloped countries through a well administered Point IV program, can do much, I believe, to safeguard our prosperity. I regard it as a wise investment for future U. S. mineral needs. Dr. Alan M. Bateman Department of Geological Sciences Yale University Mr. Howland Bancroft's article, The Broadening Road to Foreign Investment, appeared on page 666 of the July MINING ENGINEERING.

Jan 1, 1952

By H. E. Stauss

THE time-to-fracture test has been applied to pure platinum and to two alloys of platinum under the special conditions of small cross-sectional area of the specimens and of a test temperature above the annealing temperature. While the results are similar in character to those secured with large specimens of steel at temperatures below the annealing temperatures, two differences are noted: (I) an upward inflection in the curves for log stress vs. log time for the alloys, and (2) a sharp break in the curve for log stress vs. log time for pure platinum when single crystals filled the wire. The experiments showed that: (I) platinum and 10 per cent rhodium-platinum maintained their strengths at 1100°C. better than did 10 per cent iridium- platinum, and (2) the rhodium-platinum after a time exceeded the iridium-platinum in strength at 1100°C. Platinum alloys in their service at high temperatures encounter conditions some- what similar to those that exist in the usual form of the time-to-fracture "l test with steel. This paper is intended primarily to present results obtained by a "time-to- fracture" test under conditions approximating actual service for platinum (at the temperature 1100°C. under oxidizing conditions) with three materials, pure platinum (99.99 per cent), a platinum alloy with lo per cent iridium, and a platinum alloy with 10 per cent rhodium. The experimental procedure differed from that previously used in this type of measurement in that the samples were of small diameter (0.010 in.), were fully annealed, and were tested at a temperature definitely above their annealing points (600°C., 1000°C. and 1050°C., respectively, for 60 per cent cold reduction and 15 min. heating time2,3). The experimental arrangement was similar to that previously described,4 using as heating unit a small, horizontal, platinum- wound furnace, ½ by 12 in., maintained at constant temperature by an automatic controller. The samples were 0.010-in. wires, which had been annealed at 1200°C. by drawing them slowly through the furnace. The time-to-fracture was measured electrically. Elongation was not determined because of the difficulties inherent in the experimental arrangement. Life-that is, the time-to-fracture-was considered the important property in these first tests. No attempt was made to measure the reduction in area, but the types of fracture were noted qualitatively; in the text they are referred to as (I) the normal, plastic, or necked fracture, (2) the knife-edge fracture, and (3) the brittle or intercrystalline fracture with small reduction of area. Results for different constant applied stresses are plotted in Fig. I. In all cases at least two trials were made for each stress, although they cannot always be indicated separately on the curves. The breaking stresses drop very rapidly to a small frac-

Jan 1, 1943

By R. D. Young, E. A. Harre

Nitrogen exists in two broad categories commonly designated as elemental nitrogen and fixed nitrogen. Elemental nitrogen is found in nature as a diatomic molecule and constitutes about 78%, by volume, of the earth's atmosphere. Fixed nitrogen is a common term used for nitrogen that is chemically bound to other elements. Although elemental nitrogen is very abundant, nonleguminous plants cannot utilize nitrogen unless it is in the chemically combined form. The content of this chapter is confined to fixed nitrogen since the uses and properties of elemental nitrogen and the fixed nitrogen compounds are different. Certain bacteria associated with legumes are able to fix atmospheric nitrogen, but not to the extent required by succeeding nonleguminous crops. The need to use fertilizers containing fixed nitrogen compounds to grow food crops has been recognized for hundreds of years, and from antiquity farmers have used organic wastes such as animal manures, vegetable wastes, sewage sludge, fish scraps, etc., containing these compounds for fertilizers. These organic materials have a low nitrogen content, however, and cannot support large-scale food production. Known commercial-size deposits of natural nitrates containing much higher nitrogen content exist only in Chile, and the possibility of the discovery of other significant deposits is remote. The Chilean deposits were the major source of nitrogenous fertilizers until the Haber-Bosch process for the production of synthetic ammonia was developed. In the Haber-Bosch process, nitrogen reacts with hydrogen at high temperatures and pressures and in the presence of a catalyst to form ammonia. Modern plants use air, water, and natural gas or other hydrogen sources to produce the ammonia that is now the key building block of the fixed nitrogen industry. Several major problems that developed in the 1970s continue with the nitrogen industry into the 1980s. These are (1) the continuing sharp escalation in the cost of feedstocks for ammonia production as well as all energy sources, and (2) the very steep increase in the investment cost of production facilities. More than 75% of the fixed nitrogen produced domestically is consumed as fertilizers. The types of materials used as fertilizers have changed significantly during the past years. There has been a trend from the use of low-analysis fertilizers to types which contain high percentages of plant nutrients. The average plant nutrient content (N + P2O5 + K2O) of fertilizers used in the United States has increased from 18% in 1930 to 32% in 1960 and today approaches an average of 44%. In the case of nitrogen fertilizers, the low analysis natural nitrates (16% N) gave way to ammonium sulfate (20% N) after about 1920. After World War II, ammonium nitrate (33.5% N) previously used in munitions, became established as the leading nitrogen fertilizer. Urea use as a fertilizer (46% N) began in the 1960s, and in the past 10 years has become the world's leading solid nitrogen fertilizer. Nitrogen Materials Anhydrous Ammonia-Anhydrous ammonia is a colorless gas at ambient temperatures and pressures and has a sharp pungent odor. Anhydrous ammonia is stored and transported as a liquid in high-pressure cylinders and tanks at ambient temperature, and in low-pressure tanks, barges, and ships at -28°F. Anhydrous ammonia is applied directly at 4 to 7-in. depths in the soil as a high-pressure liquid by special applicators, after which it expands to a gas that dissolves in the soil moisture or is absorbed on soil colloids. In other systems ammonia is metered into irrigation water and is thereby introduced into the soil.

Jan 1, 1983

By J. Halpern, D. R. McKay

SOME of the most important hydrometallurgical developments in recent years relate to processes involving the oxidation of sulfide minerals in aque- ous suspension at elevated temperatures by air or oxygen under pressure. Among these is the acid pressure-leach process which has been developed, particularly for the treatment of pyritic uranium ores.1-5 In this process, an aqueous suspension of the ore is digested in an autoclave, in which an overpressure of air or oxygen is maintained, at temperatures above 100°C. Oxidation of the pyrite (FeS,)

Jan 1, 1959

By B. K. Larkin, H. R. Bailey

A model Of heat flow in an underground combustion process is studied. This model includes convection effects and thus is more general than previous studies which considered conduction as the only mechanistn for heat transfer. Both linear (tube run) and radial (field application) geometries are considered. The effects of ignition heaters, vertical losses and finite source width are considered for the linear case. The results are in the form of equations and are presented in graphical form for a number of cases. Convection effects increase frontal temperatures about 25 per cent over those computed for conductive transfer for typical field operating conditions. This increase in temperature is a result of heat being transported toward the front by the injection gas. Even greater temperature increases are realized as the per cent oxygen in the injection gas decreases. It is well known that compression costs are of considerable importance in estimating the economic feasibility of underground combustion. By assuming an ignition temperature for the combustion fuel, predictions of limiting conditions on fuel density and injection rate necessary to sustain the combustion zone are made. For typical field conditions, at least 0.75 lb/cu ft of fuel are needed with air as the injection gas. If the injection gas is 10 per cent oxygen and 90 per cent nitrogen, this figure is 0.69 lb/cu ft. INTRODUCTION The possibility of increasing oil recovery by underground combustion has been considered for many years. Recent field tests indicate that the underground combustion process is technically feasible. The economic feasibility depends to a large extent on the amount of air which must be injected to sustain combustion. Prediction of the success of employing underground combustion in a particular reservoir must be based on existing field tests, laboratory tube runs"' and solutions of mathematical or analog models. Vogel and Krueger5 devised an electrical analog of the heat transfer problem in an underground combus-ion process. They considered the problem of heat conduction from a cylindrical source with increasing radius assuming no vertical losses. Bailey and Larkin and Ramey solved the corresponding problem including vertical losses by considering a mathematical model of the conduction process. Ref. 9, 10 and 11 also present information related to the subject study. The present paper generalizes these results to include both conduction and convection mechanisms for heat flow. A model of the conduction-convection process is described. The partial differential equations governing this model are written and solved for a number of cases of interest. The formulas are evaluated and the results are presented graphically. A CONDUCTION-CONVECTION MODEL Description of the Model A number of models are employed in this paper, each of which approximate a particular physical situation depending on the geometry, i.e., linear or radial flow, the type of vertical heat losses, the nature of the source, etc. The geometry for both the linear and radial case is shown in Fig. 1. A particular linear model is described in this section, and variations from this model are described in later sections of the paper. Consider a homogeneous, semi-infinite porous prism with lateral sides insulated as shown in Fig. 1. The left end, x = 0, is heated for a time t, with a plane heater supplying a constant heat flux and during this time; gas (nitrogen) is passed through the pores of the prism at a constant mass flux. At time t, the heater is turned off and air is injected in place of the nitrogen. This causes combustion to take place, and a uniform source of width 1 is formed which moves at a constant velocity v, to the right. The frontal velocity v, is related to the gas velocity v,, through stoichiometric considerations

By O. Jay Myers

THE war effort has furnished the necessary impetus for better magnesium foundry practice. Four or five years ago, there were but a few formulas in general use for cores and mixtures for magnesium castings. Certain sands, binders, and inhibitors were specified and the proportions of these materials in each mixture were maintained between very narrow limits. As more and more war industries entered the field, much research was carried out and methods and practices were improved. Magnesium founding is still in a state of flux; therefore it is not uncommon to find one foundry spraying inhibitors on its cores, and another foundry using sand mixtures with incorporated protective agents. The basic core or dry-sand mold mixture for magnesium in use today is compounded with sand, core oil or resin binder, cereal, and moisture. Core oil or resin binder are added for baked strength while the cereal binder and moisture are for green strength. The normal mixtures (based on the weight of the sand) contain from 0.5 to 1.5 per cent of both cereal binder and core oil, and the moisture content varies between 1.5 and 5 per cent. The ratio of core oil to cereal binder varies from 60:40 to 40:60, while the correct amount of moisture depends upon the method of coremaking. PROTECTIVE AGENTS In all magnesium practice, protective agents are used in conjunction with the core and molding sands to prevent oxidation of the metal. The use of these inhibitors is not novel, but publications covering this field are not entirely adequate. Beck1 says Magnesium alloys decompose water to form magnesium oxide, hydrogen being liberated in the process (Mg + H20 -+ H21 + MgO). This reaction results in the blackening of the skin and the appearance of areas of porosity on the casting surface, the cavities of which are filled with a grey oxide powder (these are termed `burns'). Although sand cores for magnesium castings are thoroughly dried during the baking cycle, burning will take place on the castings unless the metal is protected properly. This type of burning is more difficult to define than the "water-magnesium" reaction cited by Beck. A possible explanation may lie in the following equation: 2Mg + 02 -s 2MgO Here, the source of the oxygen is not water, but the air in the mold cavity, together with the chemically combined oxygen in the core-binding media. Generally, two methods are used to prevent this reaction from taking place.

Jan 1, 1945

By John H. Hollomon

IN recent papers, O'Neill,1 Vivian,2 and Zener and Hollomon3 have reviewed some of the information concerning the relations between stress and strain during plastic deformation. Since further information has been obtained since these reviews were published, this paper attempts to further coordinate and amplify the knowledge concerning the plastic deformation of metals in simple tension. Ordinarily the results of tensile tests of metals are presented as graphs in which the load divided by the original area is plotted as a function of the percentage of elongation measured over some specified gauge length. The interpretation of graphs of this sort is limited, since the stress required to deform the metal at any stage of the deformation is actually the load divided by the instantaneous rather than the original area. Furthermore, each increment of the deformation is performed on metal that has been previously deformed, and, as pointed out by Ludwik,4 the strain could be more effectively defined: [e = In A t][I] where a is the strain and Ao and A are, respectively, the original and instantaneous areas. The results of the tensile tests can be more effectively presented and interpreted if the stress* (load divided by actual area) is plotted as a function of the strain as defined above. A schematic curve of this type is presented as Fig. I. In a previous paper,6 the concept of Ludwik7 concerning the flow and fracture of metals was successfully employed to explain some of the puzzling results of notched-bar impact tests of steel. It appears that the use of this concept is very fruitful and should be kept in mind in any study of the deformation characteristics of metals. Ludwik considered that a flow stress-strain curve of a metal was essentially a locus of points that described the stress required for plastic flow of an infinite number of specimens, each with a different strain history determined by the preceding part of the flow curve. Each of these specimens can also be considered to have a fracture strength. Unfortunately (or fortunately depending upon the point of view), all the specimens, except the one deformed to the fracture strain, flow and do not fracture. Even though the metals do not fracture, the concept of a fracture-strength curve seems

Jan 1, 1945

By Bernard G. Carbajal

The dielectric properties and thermal stability of glow-discharge polytnerized films of styrene, chloro-benzene, and other organics and photoresist filrns are presented. Variations in the glow-discharge polymerization procedure are related to thermal stability. Thermal treatwzents to improve the dielectric properties of both positive (A2 340) and negative (KMER) photoresists are given. THIS study of the dielectric properties of thin organic polymer films is part of a program to investigate the electronic applications of organic materials. Thin organic polymer films have been produced in an ac glow discharge,13 with a low-energy electron-beam process,4 and in an rf dicharge. A process has been developed during the course of this program for forming thin organic polymer films in a dc glow discharge. These glow-discharge polymerized (GDP) films exhibit some useful dielectric and insulative properties. Variations in the properties of the GDP films can be induced by changes in the source material (monomer) andor in the conditions of the glow discharge. Thin organic polymer films can also be produced from typical positive and negative photoresists. Some variations in the properties of the photoresist films can be induced by suitable post-application treatments such as thermal crosslinking. The properties of interest in this study are dielectric constant, dielectric strength, resistivity, and thermal stability. POLYMER FILM PREPARATION I) GDP Films. The GDP films were prepared in a dc glow discharge in an atmosphere of organic monomer vapor. The details of the glow-discharge procedure have been presented previously.6 Briefly, under the influence of a dc glow discharge organic vapors can be polymerized in the vapor phase and the resultant polymer (GDP film) deposits on and in the vicinity of the cathode. Substrates placed behind a screen cathode can be uniformly coated over all exposed areas. Pattern definition can be achieved using normal mask stencil techniques. Table I presents the pertinent parameters in the preparation of GDP styrene. Conditions of Forrrzation of GDP Styrene. The rate of deposition for GDP films was monitored using a current-time integrator. The thickness of the deposited film for a given set of experimental conditions was a function of the current-time integral. The fifth row in Table I is a compilation of the deposition rate of GDP styrene films. Other organic monomers behave in a similar fashion. With the exception of the highly halogenated saturated hydrocarbons, all organics subjected to the conditions of the glow discharge form GDP films. 11) Photoresist Films. Photoresists are normally recognized to exist in two forms, a low molecular weight, soluble polymer form (A) and a high molecular weight, crosslinked insoluble form (B). Typical negative photoresists are applied in the low molecular weight form A and converted to the high molecular weight form B by the action of light. (Positive photoresists are applied in form B and converted to form A by the action of light.) Eastman Kodak Metal Etch Resist (KMER) has been chosen as a typical negative photoresist. Polymer film samples were prepared in the same configuration used for GDP films. The KMER was applied in the usual fashion using a 120°C drying step (infrared-lamp heating) and a 180°C post-bake. Care must be taken to completely remove the solvent in the drying step and to properly develop and postbake to exposed photoresist. If the photoresist film is not properly dried and postbaked, severe blistering and peeling will occur during subsequent elevated-temperature exposure. Thickness can be controlled by varying the viscosity of the form A photoresist and the spin rate at application. AZ 340 was chosen as a typical positive photore-

Jan 1, 1967

THE refining period of an open-hearth heat blends imperceptibly into the finishing period, during which final adjustments are made in slag composition, in bath action and temperature, and in composition of the steel, in order to prepare it for casting into ingots. Operations must be governed by the consideration that alterations in the character of the heat during the finishing period must be held to a minimum. In a broad sense, the finishing and deoxidation period of a heat may be said to be- gin when the action of the last ore addition has ceased, and to end when the teeming of the ingots is completed. INGOT STRUCTLIRES A survey of the relative advantages and disadvantages of different types of ingot structure is required because deoxidation treatments during the finishing period control the amount of gas evolved during solidification and consequently determine the type of ingot structure. Four classes of ingots are recognized, de- pending upon the degree of deoxidation to which the steel has been subjected. These types are killed, semikilled, capped, and rimmed; typical examples of their structures are represented by ingots 1, 2, 5, and 7, respectively, of Fig 9-1. The actual ingots from which these cross sections were sketched were all poured to the same height (indicated by the dotted lines) in the same type and size of bottle-top molds. The eight drawings of the figure represent selected types of ingot structure in a continuous series from "dead killed" to "wild," resulting from variations in the total quantity of gas evolved, from none at all to copious amounts, during solidification of the steel in the mold. Killed and semikilled steels are adjacent at the "quiescent" end of the ingot structure series where only small amounts of gas are evolved. The term "quiescent" describes the action of the molten metal during and subsequent to the teeming of killed and semikilled steels. Capped and rimmed steels are adjacent at the

Jan 1, 1964

By Harold Earle Cook

The purpose of this paper is to state briefly the inspection requirements of the Bureau of Ordnance, the specifications governing the inspection, and the physical and chemical properties of the steel used in the construction of ordnance for our Navy. It would be of interest to evoke discussion on points in these specifications which do not tend to insure the production of the very best material for the purpose intended. In other words, what requirements of our specifications are useless and also in what manner are our specifications deficient? It might be well at the start to answer the first criticism of this paper which will probably be made, and that is that the title does not agree with the subject matter. Considering metallographic work as covering only the macroscopic and microscopic examination of metals, this paper will have gone beyond the subject; but it is believed that a broader definition of metallography is that it is the study of the relation of the internal structure of metals and alloys to their composition and to their physical and other properties. The internal structure of steel is dependent on its physical and its chemical properties. These physical properties are dependent on the chemical composition and the mechanical and thermal treatment of the steel. So it seems that this subtitle would not be entirely necessary and that the title " Metallography of Steel for Ordnance Purposes" would cover a study, not only of what we can learn of macroscopic and microscopic examination, but broadly of the whole subject of the specifications, the fulfillment of the requirements of which produce the structural conditions revealed by macroscopic and microscopic examination. I will refer but briefly at the beginning to the microscope and its uses in our inspection. It is only very recently that the Bureau of Ordnancc has furnished certain of its inspection offices with a portable Tassin outfit for the microscopic examination of steel. Since that

Jan 1, 1916

By M. Muskat, R. D. Wyckoff, H. G. Botset

The flow of liquids through porous media is known to follow Darcy's law which states that the velocity of flow is proportional to the pressure gradient. This law is but a statement of the facts obtained from experimental studies and is, therefore, uncontroversial. It should be men-tioned, however, that it applies only when the flow is viscous in nature and that at excessive velocities which tend to produce turbulence, the velocity is proportional to some power of the pressure gradient, the exponent ranging from 1 to 0.5 as the degree of turbulence increases. However., experiments with media having permeabilities corresponding to those of actual producing horizons show conclusively that the actual flow of liquids in a producing horizon must be viscous except perhaps in the immediate vicinity of a well producing at a high rate. Therefore, one is justified in assuming Darcy's law to hold for cases of practical interest, as will be implicitly assumed in this discussion Given this basic law of flow it is possible, theoretically to obtain solutions to any problem of viscous flow of dead liquids1 by the usual methods of potential theory. However, problems of practical interest often present such complex geometrical configurations of sources and sinks (driving sources and output wells) as to make the analytical solutions extremely difficult or even impossible. It is useful, therefore, to note that Darcy's law is precisely equivalent to the law of electrical conduction, so that the pressure distribution in steady state porous flow of liquids is exactly the same as the potential distribution in an electrical conducting medium.2 This analogy permits the use of electrical models wherein the potential distributions may be measured with far greater facility and accuracy than is possible in actual fluid-sand models. Such electrical models were used in determining the pressure distribution about complex arrays of wells, an example of which will be shown later in the discussion of the 5-spot flood. One phase of the porous flow problems which is of considerable practical interest involves the tracing of an advancing fluid front. Thus,

Jan 1, 1933

By Kenneth A. Moon

An exact statistical treatment of a one-dimensional model is used as a basis for evoluating the reliability of certain simplified expressions for the activity of the solute in interstitial solutions, including one obtained from the exact expression by setting the repulsive interaction equal to infinity. The latter approximation is found to be satisfactory at low and moderate concentration if the repulsive interaction is large, even though not infinite. A similar expression (identical if the co-odination number is two) is derived from the quasichemical expression of Lacher, and is recommended as the best available expression for the excess configurational entropy of interstitial solutions with excluded sites. Some reasonable models are discussed, and the nature of the saturated solutions is determined by inspection. Some of the models reduce to the one -dimensional case. An analysis is given of the excess partial entropy of hydrogen in V-H; Nb-H; and To-H solutions. MOST treatments of the statistical thermodynamics of interstitial solid solutions have followed the classic paper1 of Lacher in making the simplifying assumption that the configurational entropy of the solution is ideal. However, it is becoming increasingly apparent that there are many interstitial solutions with very large so lute-solute repulsions, and for these the assumption of ideal entropy is not valid or useful. It is important to realize that with substitutional solutions large repulsions between the component atoms must lead to phase separation, whereas in interstitial solutions the free energy of the solution is not drastically increased by large solute-solute repulsions until intrinsic saturation is reached at the concentration where further solute would be forced to enter a site in which it would experience the repulsive effect of one or more solute atoms already present. In the limiting case of an infinitely large repulsive interaction, the excess free energy would be attributable entirely to excess entropy, the enthalpy of mixing being zero. AS will be shown below, even if the repulsions are less than infinite, a treatment based on an assumption of infinite repulsions may be very satisfactory up to moderately high concentrations of the interstitial component. Often in solutions where large repulsive interactions exist, there are also small interactions — often attractive—between solute atoms in configurations other than that corresponding to the large repulsion. In such cases the excess free energy will consist of an excess entropy term attributable to the large repulsive interactions, and an enthalpy term corresponding to the other small interactions. Nomenclature to differentiate succinctly between important cases would be a convenience. In this paper the nomenclature shown in Table I will be used. In Table I, and in the preceeding discussion, excess quantities are defined in terms of standard states which are pure solid solvent and pure (possibly hypothetical) solid saturated phase of the structure in question. In practice, it is more convenient to choose the interstitial element as a component, and its conventional standard state. This will add a composition-independent term to the excess entropy and the enthalpy. The earliest paper known to the present author which treats the thermodynamics of athermal interstitial solutions was given by schei12 in 1951, but the statistical derivations in that paper are open to criticism. Speiser and Spretnak were the first to give a correct statistical treatment,3 limited, however, to concentrations sufficiently low that the number of empty sites excluded from occupancy by more than one filled site is negligible. The purpose of the present paper is to extend the statistical treatment to more concentrated solutions, and to examine the magnitude of the errors introduced by assuming that the repulsive interactions are infinite when in fact they must be finite. THE QUASICHEMICAL APPROXIMATION Fortunately, a standard method already exists for taking into account the effect of large interactions upon the entropy of mixing. This is the quasi-chemical method, in which the probability of existence of a given pair of solute atoms in a certain proximate configuration is assumed to be proportional to exp(-w/kT), where w is the energy increase of the solution when the two atoms are moved from isolated locations in the solution to the configuration in question. A quasichemical treatment of interstitial solutions was given in 1937 in a widely neglected paper by Lacher.4 The result comes out

Jan 1, 1963