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By J. Leja, A. Pomianowski

This paper deals with equimolar solutions of xanthate and alkyl trimethyl ammonium bromide adsorption on copper, nickel and sphalerite powders. After an exposition of the experimental methods used and the results obtained, a thorough discussion leads to the conclusion that some molecular association between xanthates and CnTAB's does take place in the bulk of the solution as well as at the air/liquid interface. A spectrophotometric study of xanthate solutions alone and their mixtures with equimolar amounts of alkyl trimethyl ammonium bromide (CnTAB) has established the additivity of ultraviolet spectra (190 to 400 mµ) for potassium ethyl xanthate (KEtX) and C12TAB. No obvious effect of C12TAB addition on the decomposition rate of KEtX was observed, the half life of which was established as 29±3 days at 22°C and pH ~ 6. In mixed solutions of longer xanthate homologues (e.g. hexyl and nonyl) and equimolar CnTAB, colloidal precipitates are gradually formed which contain primarily the corresponding xanthate molecules. The kinetics of collector abstraction by copper, nickel and sphalerite powders were studied in 10-5 to 10"3 M solutions of KEtX alone and in equimolar mixtures of KEtX and CI2TAB. Presence of C12TAB caused a two to three fold increase in the amounts of xanthate (equivalent to many monolayers) abstracted by copper and nickel powders (and in their rates of abstraction) but had no effect on the abstraction of xanthate by unactivated sphalerite (equivalent to less than a monolayer). The adsorption of C12TAB itself from the mixed solutions was very low, at most one monolayer only, and was not influenced by the nature of the solid powder used. A change in the rates of abstraction, observed with copper powder, was interpreted as a completion of a multilayer coating (completely enveloping the grains of powder) following which the rate of reaction between solution and substrate becomes controlled by diffusion through this coating. Work of Buckenham and Schulmanl on molecular associations between different collectors has shown unusual synergistic effects in flotation of individual minerals using mixtures of xanthates and alkyl trimethyl ammonium bromides. The objectives of the present work were: 1) to determine whether these molecular associations between the two types of collectors (indicated by strong surface tension lowering in Buckenham and Schulman's work) take place at the air/liquid interface only or in the bulk of solution as well 2) to establish whether different solids adsorb any species from the mixture of these amphipatic molecules preferentially or as molecular complexes 3) to establish whether there are any differences in the kinetics of adsorption. Metallic copper and sphalerite powder were chosen as adsorbents since they represent two extremes since copper readily adsorbs multilayers of xanthate (and is easily floated with ethyl xanthate) while unactivated sphalerite does not appreciably adsorb xanthate but is known to be readily floated by the amine type collectors. Metallic nickel was included because the infrared spectroscopic work2 on xanthate

Jan 1, 1964

The amount of coal used in the Colonies before the Revolutionary War was very small, and few records of it can be found, these all being in the Public Records Office in London. The exports and imports for the years 1768 to 1772, inclusive, are shown in Table 3, which apparently do not include the early shipments from the Virginia field. For the three years 1769 to 1771, the imports from Great Britain-their only source-totalled 17,943 tons, or an average of 5,981 tons per year. If the shipments from Richmond for the same period were available, this average would probably not exceed 6,800 tons per year. In Table 4 the shipments of coal from the James River ports for the period 1758 to 1769 are shown. A few of them are re-exports of coal brought from England, but the great majority are undoubtedly of coal produced in Virginia, and the movement was partly to West Indian ports but mainly to Atlantic ports from Baltimore to Portsmouth, N. H. (Piscataway). In Table 5 the data in Tables 3 and 4 are combined, the exports being deducted, and this summarizes all the available data on the amount of coal consumed in the Colonies before the separation from England. As has already been stated there has been a tremendous amount of work done in the Richmond field over a long period of time, many mines were opened and in some cases operated for years, and practically no accurate data remain or have been published to show what was done. There are undoubtedly manuscripts still remaining that will contribute to much of the knowledge of this field, and it is well worth the while of the proper state authorities to collect all the information that can be found anywhere, to enable the future development of these coal deposits to benefit by the record of what was done in the past. Table 22 shows all the methods of shipment from this field, and all of the data available about tonnages moved over each of them. The shipments by the Chesterfield and Clover Hill Railroads are largely duplicated in some of the other columns, but allowance has been made for this in the estimated totals. In addition to the difficulties experienced with similar data for the other states, these Virginia records have one peculiarly their own; it was the custom to allow 5 pecks to the bushel of coal at the pit and only 4 pecks at the docks or at vessel side. In most of the figures it is not stated to which point they apply, and a considerable error may exist due to this cause, although certainly it does not apply to all of them. The notes show the sources of the figures used, and while it is probable that the totals are lower than the actual amounts produced, the data given are the most complete that can now be assembled.

Jan 1, 1942

By M. C. Leverett, W. B. Lewis

The dynamic behavior of a multiple fluid system is completely describable in terms of driving forces and resistances to flow. The latter are proportional to the viscosity of the fluid under consideration and inversely proportional to a property of the system termed the " effective permeability " to that fluid, a property therefore defined by this relation. Since three phases are usually present in oil reservoirs, it is essential to know the effective permeabilities to the several fluid phases, and the relationship between the composition of the fluid in the pore space and that of the flowing stream, in order to handle satisfactorily certain problems of oil production. In this regard, there are many unknown factors and parameters, and many that can be evaluated only indirectly. However, it is expected that work along lines similar to this present undertaking will help materially in solving these problems. .. . . Previous workers in this field have investigated the two-phase systems, water-gas,' water-oil2 in unconsolidated sands, and water-gasg in consolidated sands. The extension of the study of the flow of heterogeneous fluid systems from two to three phases involved only slight changes in technique. The apparatus used in the present work, except for slight changes to be described, was that used by Leverett in his water-oil experiments.~ Correlation and interpretation of data were made by methods analogous to those used in two- phase work. The relative permeability to a phase—the effective permeability divided by the permeability of the system to a homogeneous fluid—was employed throughout in correlating the rate of flow of that phase with the composition of the pore space. Quantitative measurements of two independent physical properties of the system were required to determine the composition of the pore space. As in the two-phase work, the fraction of water was determined electrically, The gas fraction was determined by measuring changes in volume accompanying measured pressure changes. Suitable account was taken of the solubility of the gas in the liquid phases, and of the vapor pressure of the water phase. Since this work was exploratory in nature, no attempt was made to obtain highly accurate numerical results. Reasonable precision and reproducibility were sought. Experimental Procedure variables Considered.—Of the properties of the fluids, the oil viscosity is most likely in practice to vary widely. Variations in oil viscosity were therefore included in this work, but variations in other properties of the fluids are as yet unexplored. It appears unlikely that the normally encountered variations will produce significant changes. ~h~ observations were made at fairly high pressure gradients, no attempt being made to detect a variation of the relative permeabilities with pressure gradient. It should be pointed out also that since most of the data were taken on one sand size only, it call Only be assumed at present that changes in

Jan 1, 1941

By W. B. Lewis, M. C. Leverett

The dynamic behavior of a multiple fluid system is completely describable in terms of driving forces and resistances to flow. The latter are proportional to the viscosity of the fluid under consideration and inversely proportional to a property of the system termed the " effective permeability " to that fluid, a property therefore defined by this relation. Since three phases are usually present in oil reservoirs, it is essential to know the effective permeabilities to the several fluid phases, and the relationship between the composition of the fluid in the pore space and that of the flowing stream, in order to handle satisfactorily certain problems of oil production. In this regard, there are many unknown factors and parameters, and many that can be evaluated only indirectly. However, it is expected that work along lines similar to this present undertaking will help materially in solving these problems. .. . . Previous workers in this field have investigated the two-phase systems, water-gas,' water-oil2 in unconsolidated sands, and water-gasg in consolidated sands. The extension of the study of the flow of heterogeneous fluid systems from two to three phases involved only slight changes in technique. The apparatus used in the present work, except for slight changes to be described, was that used by Leverett in his water-oil experiments.~ Correlation and interpretation of data were made by methods analogous to those used in two- phase work. The relative permeability to a phase—the effective permeability divided by the permeability of the system to a homogeneous fluid—was employed throughout in correlating the rate of flow of that phase with the composition of the pore space. Quantitative measurements of two independent physical properties of the system were required to determine the composition of the pore space. As in the two-phase work, the fraction of water was determined electrically, The gas fraction was determined by measuring changes in volume accompanying measured pressure changes. Suitable account was taken of the solubility of the gas in the liquid phases, and of the vapor pressure of the water phase. Since this work was exploratory in nature, no attempt was made to obtain highly accurate numerical results. Reasonable precision and reproducibility were sought. Experimental Procedure variables Considered.—Of the properties of the fluids, the oil viscosity is most likely in practice to vary widely. Variations in oil viscosity were therefore included in this work, but variations in other properties of the fluids are as yet unexplored. It appears unlikely that the normally encountered variations will produce significant changes. ~h~ observations were made at fairly high pressure gradients, no attempt being made to detect a variation of the relative permeabilities with pressure gradient. It should be pointed out also that since most of the data were taken on one sand size only, it call Only be assumed at present that changes in

Jan 1, 1941

Edgar Archibald Collins was born at Truro, Cornwall, Nov. 16; 1877. He was the fifth (and youngest) son of J. H. Collins, a well known Cornish geologist and engineer, who died in 1916. Edgar Collins spent part of his childhood at Rio Tinto, in Spain, and after returning to England was educated at Alleyne's School at Dulwich, near London. His technical training was acquired by practical experience in Cornwall, supplemented by private study and by his father's teaching. This method of training for the work of a mining engineer was preferred by his father to that of the technical schools then available, and judging by its result, was not unsuccessful. It is,-however, noteworthy that all members of the Collins family who were products of this system later sent, or planned to send, their own sons to technical schools. Edgar Collins came to Gilpin County, Colorado, in 1894, and returned there in 1898, after several intermediate years spent in Cornwall. In Colorado he worked, under his brother Arthur, in the California and other mines of the Gilpin County district, and thereby gained a practical skill and experience as a working miner, and a habit of minute observation of vein phenomena, which proved of the greatest value in later years. In 1899 he went to the Smuggler-Union it Telluride, as general assistant to his brother Arthur, and stood the brunt of 3 years of struggle with the Western Federation, gaining a reputation, for quiet courage and sound work under the most difficult conditions. After Arthur Collins' assassination in the Smuggler-Union office, in November, 1902, Edgar left Telluride, and shortly thereafter entered the employment of a syndicate headed by Arthur Winslow, of Boston, to search for and develop new mines. While so engaged he spent several unsuccessful months near Parral, in Mexico, and later visited and sampled the- newly discovered district of Grandpa, afterward known as Goldfield, in Nevada. This led to the acquisition by the Winslow syndicate of the Combination mine, at first under lease and option; and Edgar Collins was placed in charge. The Combination was really the starting point of Goldfield. It was a profitable mine before the discoveries at the Jumbo were made; and while the Combination, being a "Company-account" mine, controlled by a few responsible men, never attracted the publicity that centered around the sensationally profitable leases on the Jumbo and Mohawk, which publicity was used to further the feverish stock-dealings that characterized the new district. The Combination was really the pioneer mine, made the first shipments of rich ore, constructed the first water-line, and built the first mill (designed by F. L. Bosqui, an old friend and associate); and while it pursued a quiet and unobtrusive. career up to the time of its sale to and incorporation with the Goldfield Consolidated, was probably, in ;proportion to the amount of money risked, the most profitable bonanza in the recent history of gold mining.

Jan 11, 1918

By Potts N. L., Eilerts C. K., Summer E. F.

The second-order, nonlinear, partial- dillerential equation representing the transient radial flow of gas - condensate fluids in reservoirs has been integmted by using finite -dillerence equations and electronic computers. Effect was given to pressure -dependent permeability, viscosity, and compressibility and to distance-dependent permeability. The influence of a second-degree velocity term in the Darcy equation was investigated. Implicit methods were used and practical, convergent solutions were obtained with material balance to less than 6 x 10-4 for recovery of one- hall the reserve at constant flow rate. Integration results provide the productive period of a reservoir for a given constant rate and the fraction of the fluid initially in place that can be recovered in that period. The properties of a lean and a rich fluid are represented in a set of integrations designed to demonstrate the effect of different constant-recovery rates and significant variables emphasized one at a time. INTRODUCTION A method is needed for computing the availability or reserve of a gas in a formation, making use of all technical and engineering information that is pertinent. As a step in this direction, a program for computing transient linear flow1 was developed that utilizes principles of earlier finite-difference computing for a similar purpose2-4 and gives effect to significant pressure- and distance-dependent properties of reservoirs and their contents. The present paper pertains to transient, radial flow of gas-condensate fluids. In the partial-differential equation of flow, effect is given to the variables viscosity and compressibility,5 and also to permeability. Included in the study is the quadratic form of the Darcy equation of flow that has been the subject of field tests6 and that has been applied to a gas with constant properties in transient flow computing. 7 Inclusion in the differential equation of variable coefficients to represent properties greatly complicates the higher derivatives of the equation. Because it was impractical to make a required improvement in certain of the finite-difference derivatives by Taylor-series expansion, five-term derivatives were used in the implicit computing. Related methods were developed that can improve general facility in manipulating finite-difference equations. BASIC EQUATIONS PARTIAL DIFFERENTIAL EQUATION The basic partial differential equation for transient radial flow in the direction of decreasing radius is l_ a(vpr) _? .......(1) r gr at where r = radius, L v = apparent velocity aIong radius, L/t p = density, M/L3 t = time, t Ø = porosity, dimensionless. In this equation, only the porosity is regarded constant. The density is where p = pressure, m/Lt2 M = molecular weight of fluid, m T = constant temperature of fluid, T z(p) = pressure-dependent compressibility factor, dimensionless R = gas Constant, mL2/t2t. The physical boundary of the reservoir is at re, and the producing boundary is defined to be at tq with rq = re /200. By definition,

Jan 1, 1966

By L. F. Coffin

Monotonic tension and controlled cyclic-strain tests have been conducted on an annealed steel at various strain rates and temperatures in the weep range. Evidence of a strain-induced precipitate reaction abozle 500°C was determined from pronounced cyclic-hardening effects, increase inflow stress, inter granular fracture, drastic decrease in low-cycle fatigue resistance, and loss in tensile fracture ductility, as well as through electron-microscopy examination. It was found that strain rate as well as temperature had a pronounced effect on these observations. A parameter of the form P = T(7.95 - log ip) was determined, which was directly related to the ductility, defined either as the true strain at fracture in the case of simple tension, or as 2N 1/2 ? E p in the case of cyclic plastic strain. A highly satisfactory comparison of the cyclic life as measured and as computed from the ductility predicted by this parameter was obtained for a range of temperatures from 400° to 650°C and for crosshead speeds of 0.002 to 0.2 in. per min. MANY metals subjected to sustained loading at elevated temperatures derive resistance to creep from solid-state reactions of various alloying constituents. These reactions can be many and varied, and occur as a consequence of time and temperature according to reaction-rate principles. Strong evidence exists that many of these reactions are influenced by plastic strain, the argument being put forth that dislocations act as sites for nucleation and growth for the new phase.' Many examples can be cited where plastic strain during transformation influences the structure, and as a consequence affects the properties.2 The low-alloy steels serve as particularly good examples for investigating the effect which aging reactions have on resulting properties. Alloying elements such as carbon and nitrogen, and carbide formers such as manganese, chromium, molybdenum, and so forth, can, by the particular aging reaction which occurs, produce strengthening effects at various temperatures, and so endow strength to the alloy over a broad range of temperatures. These effects have been systematically studied by Glen both during creep3 and for constant strain-rate tension testing.4,5 The work of Glen is of considerable interest in connection with the present study, particularly in regard to the effect of various alloying additions on the true stress-strain curve and on fracture ductility at various elevated temperatures. He has shown that strain-age hardening occurred during plastic straining, which was quite specific both to the temperature of the test and to the alloying element involved. When strain-age hardening was noted at a particular temperature, a .minimum in reduction of area was also obtained. Provided the temperature for the minimum reduction of area exceeded 300°C, all minimum ductility fractures were found to be inter-crystalline in nature. For carbon steels containing molybdenum, two minima in reduction of area were noted, one occurring at 200° to 250°C, the precise temperature depending on the percentage of molyb-

Jan 1, 1964

By Michael Perch, Charles C. Russell

Nearly 7 5 per cent of the total coke production in the United States in 1940 was consumed in blast furnaces. In 1939 the percentage was 69.9, and in 1938 it was 61.3. To produce a net ton of pig iron 1757 lb. of coke was required in 1940 and 1760 lb. in 1939. These figures indicate how dependent the production of pig iron is upon the production of coke. The rate of iron production is in some measure influenced by the physical and chemical characteristics of the coke. Blast-furnace operators believe that the physical properties of coke profoundly influence the operation of the furnace. Although it is true that coke of a wide variety of physical properties is used in American blast furnaces, the periodic fluctuation of these properties is one of the causes of irregularity of blast-furnace operation. The purpose of this paper is to present a broad picture of the physical properties of by-product coke that are generally considered to be important by coke-oven and blast-furnace operators. Effects of the kind of coal used, the preparation of the coal, the rate of coking, and other factors will be considered. Of all these variables, the kind of coal used is by far the most important. In this discussion use will be made of the method of coal classification by rank1 standardized by the American Society for Testing Materials. Although this method of classification has been an American standard for several years, it has not been given the attention it deserves, especially in connection with the selection of coal for production of coke. Despite the fact that many producers of blast-furnace coke are limited to some particular source or sources of coal, a good understanding of the principles involved in setting up the standard method of classification may lead to a better appreciation of the causes of changes in coke characteristics. Furthermore, where it is necessary to select new coals as a substitute for the original supply, this method of classification can be of great assistance. The data presented have been gathered from many sources, but no attempt has been made to cover the vast literature. Instead, some of the more important data have been selected to show how coals and their carbonization affect some of the physical properties of coke. It must be emphasized that generalizations concerning the behavior of coking coals are presented and that individual coals may vary widely from the specific behavior depicted. Nevertheless, it is believed that the data illustrate certain typical behaviors. Neither was it possible to cover completely all the factors involved; for example, the macroscopic constituents of coal are believed to have important effects on the physical properties of coke, but since there is little information available for such study, and since vitrain, clarain, and durain are neither

Jan 1, 1943

By Michael Perch, Charles C. Russell

Nearly 7 5 per cent of the total coke production in the United States in 1940 was consumed in blast furnaces. In 1939 the percentage was 69.9, and in 1938 it was 61.3. To produce a net ton of pig iron 1757 lb. of coke was required in 1940 and 1760 lb. in 1939. These figures indicate how dependent the production of pig iron is upon the production of coke. The rate of iron production is in some measure influenced by the physical and chemical characteristics of the coke. Blast-furnace operators believe that the physical properties of coke profoundly influence the operation of the furnace. Although it is true that coke of a wide variety of physical properties is used in American blast furnaces, the periodic fluctuation of these properties is one of the causes of irregularity of blast-furnace operation. The purpose of this paper is to present a broad picture of the physical properties of by-product coke that are generally considered to be important by coke-oven and blast-furnace operators. Effects of the kind of coal used, the preparation of the coal, the rate of coking, and other factors will be considered. Of all these variables, the kind of coal used is by far the most important. In this discussion use will be made of the method of coal classification by rank1 standardized by the American Society for Testing Materials. Although this method of classification has been an American standard for several years, it has not been given the attention it deserves, especially in connection with the selection of coal for production of coke. Despite the fact that many producers of blast-furnace coke are limited to some particular source or sources of coal, a good understanding of the principles involved in setting up the standard method of classification may lead to a better appreciation of the causes of changes in coke characteristics. Furthermore, where it is necessary to select new coals as a substitute for the original supply, this method of classification can be of great assistance. The data presented have been gathered from many sources, but no attempt has been made to cover the vast literature. Instead, some of the more important data have been selected to show how coals and their carbonization affect some of the physical properties of coke. It must be emphasized that generalizations concerning the behavior of coking coals are presented and that individual coals may vary widely from the specific behavior depicted. Nevertheless, it is believed that the data illustrate certain typical behaviors. Neither was it possible to cover completely all the factors involved; for example, the macroscopic constituents of coal are believed to have important effects on the physical properties of coke, but since there is little information available for such study, and since vitrain, clarain, and durain are neither

Jan 1, 1943

By P. Rama Rao, D. H. Sastry, T. R. Anantharaman

Deformation (a) and twin (a') stacking-fault densities in cold - wor ked filings of fcc silver alloys containing 2, 4, and 6 wt pct Sb have been estimated from Debye-Scherrer peak shifts and asymmetries, respectively. Evidence has been obtained for a possible strain-induced transformation in a two-phase alloy containing 9.0 zut pct Sb. Using Fourier analysis of X-ray line profiles, the effective particle sizes and root mean square strains have been determined for the three fcc alloys in the cold-worked condition. The values of the compound fault probability 0.5a + a') evaluated from peak shifts and asymmetries are in reasonable apeement with those derived from peak broadening. COLD work of fcc metals may produce both deformation and twin (also called growth) stacking faults, which can be detected and quantitatively estimated by X-ray diffraction techniques.' In addition to peak broadening, deformation faults produce a shift in peak positions and twin faults an asymmetry of the Debye-Scherrer reflections. Besides stacking faults, a reduction in the size of coherently diffracting domains and distortion within these also broaden the powder reflections of deformed fcc metals and alloys. Fourier analysis' of peak shapes provides quantitative infor- mation about the effective domain sizes, lattice strains, and also the compound fault probability (1.5a + a'), where a and a' represent deformation-and growth-fault density, respectively. The Paterson method2 for determination of a from peak shifts, the warren3 or wagner4 method for evaluation of a' from peak asymmetries, and the Fourier analysis for quantitative estimates of all the contributory causes of peak broadening have, in the course of the last decade, been extensively applied to obtain data for a number of deformed fcc metals and alloys. One of the useful results of earlier measurements of a in several solid solutions is a correlation between a and the solute valence as well as electron concentration per atom (p) in alloy systems based on a particular solvent. The work of Smallman and westmacott5 on Cu-Zn, Cu-A1, and Cu-Sn, of Foley, Cahn, and ~aynor' on Cu-Si and Cu-Ge, and of Rama Rao and Anantharaman7 on Cu-Si and Cu-Sb has revealed a common trend in the increase of a with p and also a with valency of the solute. Cahn and Davies' and Ad-ler and wagnerg have observed similar trends for silver alloys containing cadmium, indium, and tin. Data on a for silver alloys with a pentavalent solute element are not, however, available. It is primarily to fill this need that the present investigation on Ag-Sb alloys was undertaken. Utilizing the Patersonand Warren methods, values of a and a', respectively, have been determined in three silver alloys containing 2, 4, and 6 wt pct Sb. By Fourier analysis of the broadening of Debye-Scherrer peaks, effective particle sizes, lattice strains, and the compound fault probability (1.5a +a') have also been evaluated.

Jan 1, 1967

By E. S. Machlin, C. W. Chen

THIS investigation is concerned with the origin of the intercrystalline voids and cracks formed in metals and alloys subjected to stress at elevated temperature. There have been many suggestions in the recent literature relating to this problem. Greenwood' suggested that the voids may be produced by vacancy condensation. Zener has stated that shear-stress relaxation across grain boundaries could initiate high tensile stresses at the regions blocking grain boundary slip and thereby cause the formation of cracks. Chang and Grant3 have described the formation of cracks at grain boundary triple points and have experimentally verified Zener's mechanism for the grain boundary regions in the vicinity of a triple point. Subsequent to the completion of this investigation, Gifkins4 developed a model which made use of Stroh's5 mechanism of fracturing to produce sub-microscopic fractures that subsequently grow by grain boundary slip. Chen and Machlin,6 in answer to Gifkins, described a model deduced from the present investigation, in which grain boundary slip provides both the stress to fracture at grain boundary jogs and the deformation required to separate fractured jog surfaces. The possibility of gas condensation to form intercrystalline voids and cracks is eliminated as a basic mechanism because such voids and cracks are developed in vacuum melted material containing minute amounts, if any, of gaseous impurities. In a theoretical evaluation of this problem, Machlin7 concluded that void nucleation by vacancy condensation during creep-rupture is improbable but that vacancy condensation on supercritical sized voids to produce growth is probable. This investigation was begun to evaluate the suggested mechanisms for intercrystalline fracture. In particular, in order to correlate vacancy supersaturation ratios produced in creep with those determined by Bal-luffi and Seigle8 as critical for , the nucleation of voids, specimens were obtained from the same heat of brass as used by the latter authors, through the courtesy of Dr. Seigle. The experiments conducted in this investigation fall into the following categories: 1) Brass—observation of voids produced under a variety of conditions, including creep under compression, to evaluate the mechanisms of void nucleation and growth. 2) Bicrystal experiments to check the mechanism of void nucleation deduced in this investigation. 3) Morphology of intercrystalline voids produced in a variety of metals. Each set of experiments will be described and discussed separately. Experimental Techniques A special creep-rupture test rack was constructed which made it possible to apply the stress to the specimen in a controlled atmosphere of inert gas, reducing gas, or vacuum. All the creep-rupture tests on a-brass (30 pct Zn) were conducted in nitrogen under a pressure slightly above atmospheric. Either dead weight loading or constant elongation rate loading could be applied with the load measured by means of a strain gage dynamometer. In order to obtain a coarse-grained crystal structure stable at

Jan 1, 1958

By Ramesh Malhotra, Hubert E. (Deceased) Risser

THE WORLD Coal, as a source of energy and as a source of coke for the smelting of iron ore, has contributed significantly to the development of every major industrial nation of the world A number of other materials-oil, natural gas, wood, waste materials, water, and, in some applications, nuclear materials -can be used satisfactorily for the generation of heat and energy, but no generally acceptable and economic substitute has been found to supplant coke in iron ore smelting in conventional blast furnaces. In the development of many nations, coal provided the initial source of energy for industrialization Although coal provided more than 60% of the world's energy each year between 1902 and 1929, oil and natural gas have surpassed it as a source of energy in more recent years (Ref. 38, pp. 439, 441). Despite the rapid rise in importance of other fuels, a considerable amount of the total energy consumed is still supplied by coal. In 1972, coal supplied 32.1 % of the total world energy (Ref. 49, pp. 2-3). To produce this energy, 2.4 billion metric tons of coal were consumed-a 16.0% increase over the amount consumed in 1962. A further worldwide increase in the amount of coal used to supply energy is projected. According to Dr. Karlheinz Bund (Ref. 37, p 145), by the year 2000 world coal consumption could amount to 5 billion mt. Coal Resources and Production The world's coal resources are estimated to be about 10,872 billion mt. Of this amount, 1,297 billion mt are classified as measured reserves (Ref. 50, p. 57). In Table 13.A.1 the estimates of measured reserves and total resources, recent production, and the ratio of measured reserves to production of major coal-producing countries are shown. About 90% of the world's total coal resources are estimated to be in the USSR, the United States, and China. The United States ranks second in the world in coal resources, but in measured reserves, it ranks first. Because of the difference in rate at which available coal resources are being exploited, the ratio of measured reserves to actual production varies widely among areas and countries. France and East Germany have the lowest reserve to production ratios, 49.5 and 60.1, respectively. In Mexico, where currently less than 5 million mtpy of coal are produced, the ratio is 1257 For all countries producing more than 200 million mtpy of coal (except East Germany), the ratio ranges from 350 to 670. For the United States, the ratio is 669.7. In Table 13.A.2, distribution of the world's coal resources by area is shown. More than 97% of the total resources lie in the northern hemisphere, with Asia, including European USSR, having 63.4%. Only 1.9% of the total coal resources are estimat-

Jan 1, 1976

By R. F. Decker, J. R. Mihalisin

Phase transformations in a series of relatively pure nickel-titanium-aluminum binary and ternary alloys were studied. The purpose was to clarify age-hardening mechanisms, especially in predominantly titanium-hardened compositions. The micro-structures, as determined on a tirne-temperature-transformation basis by light and electron microscopy and X-ray diffraction, were correlated with room temperature and hot hardnesses. The stability of the ? phase under nonequilibrium conditions was shown to be important in this system. MANY of the alloys designed for service in the temperature range of 1200oF (649°C) to 1800°F (980°C) are austenitic iron-.nickel base alloys hardened by titanium and aluminum. The control of high-temperature properties of these alloys has been advanced by the knowledge of microstructures provided by the equilibrium diagrams of Taylor and Floyd1 and Taylor.2, 3 However, there have been notable instances in the predominantly titanium-hardened alloys where the correlation of properties with microstructure and the equilibrium diagrams has been unsuccessful. Mihalisin and carrol14 have noted in electron microscope studies of commercial alloys of this type that a fee phase precipitates and transforms to 71 (hep Ni3Ti) in stress-rupture tests. Bieber5 found that this fee phase remained in nickel-chromium-titanium alloys even when aluminum was excluded. Age hardening in iron-nickel base alloys has been attributed to 71 by Craver, Aggen, and Dyrkacz,6 ? (fee phase based on Ni3Al) by Beattie and Hagel7 and both phases by Lena,8 Yet, on the basis of the nickel-titanium-aluminum equilibrium diagram of Taylor and Floyd shown in Fig. 1, it has been difficult to understand the presence of ? in low aluminum alloys. Furthermore, the characteristic coarse dispersion of 71 has not been commensurate with the marked aging response. Also there have been anomalous grain boundary transformations in the iron-nickel base alloys which have markedly reduced notched stress rupture properties.9 These have been related to boron content and residual cold work. Recently, Golubtsova and Mashkovich,10 Buckle and Manene11 and Bogaryatskii and Tyapkin12 have noted a transition fee Ni3Ti in titanium-hardened nickel-base alloys. It was apparent from the latter studies that a transition phase was important in the nickel-titanium-aluminum system. The purpose of this study was to identify this phase, measure its transformation characteristics and kinetics, and attempt to correlate these findings with age hardening. It was believed that time-temperature-transformation studies, because of their adaptability to transition phases, would be of most value for this investigation. Accordingly, this method of study was undertaken on relatively pure nickel-titanium-aluminum alloys with controlled variations in boron content and residual cold work. EXPERIMENTAL PROCEDURES Compositions were selected from the nickel-titanium-aluminum isothermal section of Taylor and Floyd.' These compositions are plotted in Fig. 1 and were selected to obtain equal aging potential of approximately 15 pet by volume of the equilibrium precipitate. The materials were vacuum melted from

Jan 1, 1961

By E. Brunner, G. L. Hassler, T. J. Deahl

The capillary effects in reservoir rock are discussed in terms of the pressures they cause in sandstones and dolomites. Data for the two-phase case (oil-gas or water-gas) and for the three-phase case (oil, water and gas in rock) are used to demonstrate that in one sense the wetting preference of a rock depends on its saturation. The nature of capillary hysteresis is described for partially stable conditions, and the concept is enlarged. Reproducibly measurable pressures include the "capillary pressure," which is the pressure difference between any two phases that are each interconnected; the "threshold pressure," necessary to force a nonwetting phase through partially saturated rock; the "displacement pressure," which is that special case of the threshold pressure in which both phases fully saturate separate portions of the rock. Displacement pressure is equal to the minimum value of the "capillary pressure." The theory of flow including capillary forces is developed at the producing surface of a well to reveal the presence there of a pressure discontinuity in the gas (or other nonwetting) phase that can be controlled to the end that more oil may be poduced from an oil field. Experiments with packed sand-flow tubes having artificial producing surfaces support the theory. Introduction The basic surface quantities acting in an oil field are two: namely, surface tensions and contact angles. These are the quantities, variously expressed, and particularized as spreading forces, adhesion tensions, heats of wetting, etc., which are measured in the laboratory by techniques mostly confined to flat or circularly cylindrical surfaces. Such measurements have not had the extensive engineering application they seem to deserve because in most practical cases they are unavoidably compounded with the complex and unapproached subject of the internal shape of the interstices of rock. In this paper it is intended that the pressure differences developed in rock by capillarity be examined, defined, and given some engineering use in terms of some new measurements that have been made. Such pressure differences—namely, the capillary pressure, the displacement pressure and the threshold pressure—seem to provide a proper contact between the basic molecular quantities and the oil field. While certain modifications of usage will be undertaken, the present effort rests upon the background of work by the U. S. Geological Survey,l by Versluys, and especially by W. 0. Smith, 3,4,5 which has been reviewed recently in papers by Leverett.=s7 The most important concept of pressure difference is the capillary pressure, a function of saturation that expresses the pressure difference between the interconnected phases in a rock. It is often measured when water and air are the fluids present, but it can be measured with other fluids. A number of curves of capillary pressure have recently been measured by a method which it is intended shall be published in a later paper. Since heretofore capillary-pressure measurements upon rock have not been

Jan 1, 1944

By G. L. Hassler, E. Brunner, T. J. Deahl

The capillary effects in reservoir rock are discussed in terms of the pressures they cause in sandstones and dolomites. Data for the two-phase case (oil-gas or water-gas) and for the three-phase case (oil, water and gas in rock) are used to demonstrate that in one sense the wetting preference of a rock depends on its saturation. The nature of capillary hysteresis is described for partially stable conditions, and the concept is enlarged. Reproducibly measurable pressures include the "capillary pressure," which is the pressure difference between any two phases that are each interconnected; the "threshold pressure," necessary to force a nonwetting phase through partially saturated rock; the "displacement pressure," which is that special case of the threshold pressure in which both phases fully saturate separate portions of the rock. Displacement pressure is equal to the minimum value of the "capillary pressure." The theory of flow including capillary forces is developed at the producing surface of a well to reveal the presence there of a pressure discontinuity in the gas (or other nonwetting) phase that can be controlled to the end that more oil may be poduced from an oil field. Experiments with packed sand-flow tubes having artificial producing surfaces support the theory. Introduction The basic surface quantities acting in an oil field are two: namely, surface tensions and contact angles. These are the quantities, variously expressed, and particularized as spreading forces, adhesion tensions, heats of wetting, etc., which are measured in the laboratory by techniques mostly confined to flat or circularly cylindrical surfaces. Such measurements have not had the extensive engineering application they seem to deserve because in most practical cases they are unavoidably compounded with the complex and unapproached subject of the internal shape of the interstices of rock. In this paper it is intended that the pressure differences developed in rock by capillarity be examined, defined, and given some engineering use in terms of some new measurements that have been made. Such pressure differences—namely, the capillary pressure, the displacement pressure and the threshold pressure—seem to provide a proper contact between the basic molecular quantities and the oil field. While certain modifications of usage will be undertaken, the present effort rests upon the background of work by the U. S. Geological Survey,l by Versluys, and especially by W. 0. Smith, 3,4,5 which has been reviewed recently in papers by Leverett.=s7 The most important concept of pressure difference is the capillary pressure, a function of saturation that expresses the pressure difference between the interconnected phases in a rock. It is often measured when water and air are the fluids present, but it can be measured with other fluids. A number of curves of capillary pressure have recently been measured by a method which it is intended shall be published in a later paper. Since heretofore capillary-pressure measurements upon rock have not been

Jan 1, 1944

By John W. Crutchfield, Emil F. Bowers

This paper presents the initial results of a pressure maintenance by water return project in the Lower Pawelek reservoir of the Falls City Field, Karnes County, Southwest Texas. Production is from the Lower Wilcox section at an average depth of 6,030 ft on the downthrown side of a "down to the coast" fault. Of particular interest is that the reservoir oil is high gravity and low viscosity but far undersaturated with gas at the original reservoir pressure and temperature. The early pressure and production history indicated only a partial or limited water drive, and this fact, coupled with the characteristics of the reservoir fluid and artificial lifting problem.. made advisable the water injection program to maintain reservoir pressure. The paper includes a description of the reservoir and reservoir fluids, the pressure and production history, a description of the water injection facilities, and the results of reservoir calculations involving Hurst's unsteady state flow and the material balance equations for calculation of water influx and prediction of the pressure-production relationship at various rates of withdrawal. The reservoir calculations and initial field results indicate that reservoir pressures in excess of 85 per cent of original pressure can be maintained by control of water injection even at very high rates of production. INTRODUCTION The purpose of this paper is to report the initial results of a pressure maintenance by water return program in the Lower Pawelek reservoir, Falls City Field, Karnes County. Texas, and to calculate an empirical relationship between pressure and production in this limited or partial water drive reservoir. Location The Falls City Field (Fig. 1) is located two miles north of the town of Falls City in Karnes County, Texas, and is approximately 50 miles south-southeast of San Antonio on U. S. Highway 181. Discovery and Development The initial block of leases was taken after a surface geological survey identified a major east-west fault and closure on the south or downthrown section. The discovery well, Southern Minerals Corporation's Joe F. Bartosch 1; was completed at 4,650 ft in the Lower Bartosch sand in December, 1944. Drilling was continuous until December, 1946, and resulted in the discovery of 12 oil reservoirs between 4,600 and 6,050 ft in the Middle and Lower Wilcox formations. These are shown on the cross-section (Fig. 2). As of the current date there are 64 oil wells completed as follows: Southern Gulfshore Magnolia Minerals Oil Petroleum Reservoir Corp. Co. Corp. Total Upper Bartosch 0 0 0 0 Lower Bartosch 16 0 0 16 Shulze 7 0 1 8 Upper Faires 2 0 0 2 Lower Faires 4 0 0 4 Upper Moczygemba 0 0 0 0 Lower Moczygemha 2 0 0 2 Olinick 2 0 0 2 Upper Martinez 0 0 0 0 Lower Martinez 5 0 0 5 Upper Pawelek 0 0 1 Lower Pawelek 27 1 3 31 Total 65 2 4 71

Jan 1, 1950

By L. Burris, G. A. Bennett, P. A. Nelson

Staznless steels ave rrzuch less seuel-ely attacketl by zinc lapov than by molten zinc systems. To determine the applicubility of stainless steels fov equipment items which would be exposed only to zinc vapor, the corvosion resistance of several stainless steels to zinc vapor was investigated in 500-hr- exposuves at 900° C. Two austenilic stainless steels, Types 304 and 3-17, suffered severe intergranular attack. Loss of nickel from these steels and micro-probe crnalyses indicated the probable formation of low-melting zinc-rich phases. Good vesistance to attack by zinc vapor, as determined by metallo-9-rpaphic excr)rtination and physical testing, Loas exhibited by Type 405 stainless steel, a jevvitic steel. Type 440C stainless steel, a tnartensitic steel, although suffering considevable loss in weight, was not structurally weakened. At Argonne National Laboratory liquid zinc and zinc-rich alloys are being employed as solvent media in pyrometallurgical processes under development for recovering and purifying discharged reactor-fuel materials.' Because of the high solubility of most metals in liquid zinc,' there are few metals which can serve as container materials for liquid zinc at temperatures much above the melting point. The poor corrosion resistance of the common metals and alloys to molten zinc has been discussed by Eldred.3 DeKany, Lavendel, and Burris4 tested some of the less-common alloys of the nonrefractory metals and found that they also have poor resistance to attack by liquid zinc and Zn-Mg solutions. Of the metallic materials, only some of the refractory metals such as tantalum, tungsten, and molybdenum and their alloys have shown resistance to attack by liquid zinc.4-7 In the process-development work at Argonne National Laboratory, tantalum and tungsten vessels have been used to hold liquid-zinc alloys. These vessels are housed in stainless-steel equipment, principally to permit maintenance of an inert atmosphere and operation at various pressures. In this experimental work, it has often been observed that Type 304 stainless steel suffers little attack by zinc vapor at temperatures up to about 800 °C. In contrast, severe attack occurs in areas where zinc condenses as a liquid. The extent of attack by zinc vapor on several stainless steels was investigated because there are possible useful applications of stainless steel for equipment items which would be exposed only to attack by zinc vapor. These applications include, for example, housings around processing equipment as indicated above and vapor lines leading from zinc stillpots or retorts to condensers. EXPERIMENTAL EQUIPMENT AND PROCEDURE The experimental procedure consisted in exposing stainless-steel test coupons to static zinc vapor for 500 hr at a temperature of about 900°C. The apparatus, shown in Fig. 1, consisted of a 12-in.-long closed tantalum tube jacketed in Type 304 stainless steel to prevent oxidation of the tantalum. A Zn-10 wtpct Mg* alloy charge of 293 g in the bottom of the

Jan 1, 1965

SEC. 1. The membership of the Institute shall comprise six classes, namely: 1. Members; 2. Honorary Members; 3. Senior Members; 4. Associates; 5. Junior Members; 6, Rocky Mountain Members. All shall be equally entitled to the privileges of membership, excepting that no member of any class whose residence shall be outside of the United States of America, except those residing in Mexico and Canada, shall be entitled to vote. SEC. 2. Members: A person to be eligible for election or transfer into the class of Member must be at least 27 years of age and must have had at least six years' employment in the practice of engineering, mining, geology, metallurgy, or chemistry, during at least three years of which he must have held positions of responsibility in one or more of these fields. This shall not apply to Rocky Mountain members. SEC. 3. Honorary Members: Each candidate for Honorary Membership must be recommended by at least ten Members and must be elected by ballot at a meeting of the Board of Directors by the unanimous vote of the Directors present; provided, however, that the number of Honorary Members shall at no time exceed twenty. Such election shall automatically act as a transfer of such member from any other class of membership to which he may belong. SEC. 4. Senior Members: The Directors may in their discretion place on the Honor Roll of Senior Members and transfer from any other class of membership other than Honorary Membership the name of any Member or Associate who has reached the age of seventy years and who has paid dues for thirty years, and for good reasons in • special cases may vary the age or number of years. SEC. 5. Junior Members: A person to be eligible for election to the class of Junior Member must be qualified through education or experience to hold a subordinate position in engineering, mining, metallurgical, geological or chemical work. He shall be not more than twenty-seven years of age at the time of election. The rights of the present Junior Associates shall continue until the same expire by limitation of time. SEC. 6. Associates: A person eligible for election or transfer into the class of Associate shall be one, who, in the opinion of the Committee on Admissions and the Board of Directors, is suitable for such election or transfer by reason of his interest in or connection with mining, geology, metallurgy, or chemistry. SEC. 7. Rocky Mountain Members: Membership in a special class of life memberships without annual or other dues and without right to receive the printed literature distributed to other members or the right and privilege of wearing the official badge of technical members, is given to all members of the Rocky Mountain Club at the time of consolidation. These special Rocky Mountain memberships shall be claimable by any member of the Rocky Mountain Club, not already a member of the Institute,

Jan 1, 1929

By William A. Johnson

The fundamental role of diffusion in many reactions occurring in solid metals has long been recognized, and there have been careful measurements of rates of diffusion in numerous alloy systems; but our understanding of the atomic mechanism by which diffusion occurs is scarcely in an advanced state.l-3 It is doubtful that this mechanism can ever be directly ascertained; rather, all imaginable mechanisms must be examined and the one that is in best accord with such data as can be obtained from suitably chosen experiments should be selected. Because of its relative simplicity, diffusion in a system containing only one kind of atomic species—commody called self-diffusion—is of considerable theoretical interest. It may be expected that diffusion theory will not be advanced appreciably until a wide variety of diffusion experiments—of which diffusion in a chemical concentration gradient and self-diffusion are two important types—are carefully performed and inter-compared. Aside from the purely theoretical interest in self-diffusion measurements, such studies will be of considerable engineering importance. The rate of any process in a pure metal requiring the movement of atoms, of which recrystallization and creep are two familiar examples, will be understood more readily with the aid of self-diffusion data.† Self-diffusion implies the diffusion of something into its exact counterpart; the detection of such a process is patently impossible, and it is necessary to substitute for it the diffusion of one isotope (in this case radioactive) into another isotope (in this case stable) of the same chemical element. There is, however, no reason to suppose that a radioactive atom will not diffuse at the same rate as its stable isotope, for all of the isotopes of the same element have exactly the same chemical properties; neither the difference in nuclear energy nor the difference in mass would be expected to exercise an important influence in this phenomenon. In this sense, self-diffusion may be thought of as the diffusion of radioactive atoms down a radioactivity concentration gradient, just as usual diffusion is the diffusion of one kind of atom down its chemical concentration gradient. The first measurements of self-difiusion were made by von Hevesy4-6 using the radioactive lead isotope thorium B in ordinary lead. The recent development of means for producing artificial radioactive elements has made possible similar measurements on gold,7, 8 copper,2, 9 and zinc.10, 11 Many of the data that have been obtained are rather poor, and no adequate reason has been given for their poorness; it appears, however, that the unsatisfactory results are characteristic of the particular experimental procedure employed, and not of self-diffusion measurements in themselves. The experimental technique that has yielded the poorer results is the deposition of a thin layer of radioactive atoms on the surface of a specimen and the determination of the rate of inward diffusion

Jan 1, 1941

By William A. Johnson

The fundamental role of diffusion in many reactions occurring in solid metals has long been recognized, and there have been careful measurements of rates of diffusion in numerous alloy systems; but our understanding of the atomic mechanism by which diffusion occurs is scarcely in an advanced state.l-3 It is doubtful that this mechanism can ever be directly ascertained; rather, all imaginable mechanisms must be examined and the one that is in best accord with such data as can be obtained from suitably chosen experiments should be selected. Because of its relative simplicity, diffusion in a system containing only one kind of atomic species—commody called self-diffusion—is of considerable theoretical interest. It may be expected that diffusion theory will not be advanced appreciably until a wide variety of diffusion experiments—of which diffusion in a chemical concentration gradient and self-diffusion are two important types—are carefully performed and inter-compared. Aside from the purely theoretical interest in self-diffusion measurements, such studies will be of considerable engineering importance. The rate of any process in a pure metal requiring the movement of atoms, of which recrystallization and creep are two familiar examples, will be understood more readily with the aid of self-diffusion data.† Self-diffusion implies the diffusion of something into its exact counterpart; the detection of such a process is patently impossible, and it is necessary to substitute for it the diffusion of one isotope (in this case radioactive) into another isotope (in this case stable) of the same chemical element. There is, however, no reason to suppose that a radioactive atom will not diffuse at the same rate as its stable isotope, for all of the isotopes of the same element have exactly the same chemical properties; neither the difference in nuclear energy nor the difference in mass would be expected to exercise an important influence in this phenomenon. In this sense, self-diffusion may be thought of as the diffusion of radioactive atoms down a radioactivity concentration gradient, just as usual diffusion is the diffusion of one kind of atom down its chemical concentration gradient. The first measurements of self-difiusion were made by von Hevesy4-6 using the radioactive lead isotope thorium B in ordinary lead. The recent development of means for producing artificial radioactive elements has made possible similar measurements on gold,7, 8 copper,2, 9 and zinc.10, 11 Many of the data that have been obtained are rather poor, and no adequate reason has been given for their poorness; it appears, however, that the unsatisfactory results are characteristic of the particular experimental procedure employed, and not of self-diffusion measurements in themselves. The experimental technique that has yielded the poorer results is the deposition of a thin layer of radioactive atoms on the surface of a specimen and the determination of the rate of inward diffusion

Jan 1, 1941