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By G. A. Alers, J. H. Bechtold, R. W. Armstrong

The plastic flow of .molybdenum was studied in compression at temperatures below the ductile-to-brittle transition in tension. It was found that molybdenum is ductile in compression at all temperatures down to —196°C. The yield strength continues to increase with decreased test temperature below the tensile ductile-to-brittle transition temperature range. Difficulty was encountered in correlating the experimental data obtained with existing theories of plastic flow. THE body-centered-cubic metals as a group show a rapid and very large increase in yield strength with decreasing test temperature.' It is of fundamental importance to the understanding of the mechanism of plastic flow that this general characteristic be examined carefully. Unfortunately, brittle fracture in low-temperature tensile tests prohibits the measurement of flow properties at very low temperatures. By using compression tests, fracture can be suppressed and the plastic flow of the bcc metals can be studied far below their tensile ductile-to-brittle transition temperatures. Molybdenum was chosen for this experiment and plastic-flow data were obtained down to —196°C.

Jan 1, 1959

By Hans Conrad, W. D. Robertson

FORMAL theories of yielding and flow have been developed to describe thermally activated plastic flow in metal crystals.'-" hey are all based on Becker's' original idea that thermal fluctuations aid the applied stress in overcoming internal barriers to flow and lead to the following relation. where j is the strain rate; C is a constant which includes a frequency factor, the entropy, the number of flow units, and the amount of strain associated with each successful fluctuation; E(T) is the activation energy associated with flow, and is a decreasing function of the applied stress, 7; k is Boltzmann's constant; and T is the temperature in OK. The various theories differ mainly in the model chosen and in the nature of the relationship between the applied stress and the activation energy. Beckerl and Orowan' suggest a relationship of the form E a(Ti — t)2, where .ri represents the stress required for flow without the aid of thermal fluctuations; Kauzmann,3 Cottrel1,5 and Seeger6,7 suggest E a(t — t) ; Fisher8 suggests E while Cottrell and Bilby4 suggest a more complex relationship between E and 7. Additional data are needed to test these various theories., esweciallv- in view of Dorn's9 ork. which indicates that the activation energy for creep is independent of the stress and strain. The present paper presents the stress-strain data derived from incremental loading of magnesium single crystals in tension and direct shear, in the temperature range of 78" to 364°K. Incremental loading was employed in order that the creep component of the strain could be determined. Stress-strain curves of aluminum10-13 and copper" single crvstals. derived from incremental loading tests, have been found to be in agreement with those obtained by the more conventional constant strain rate or loading rate tests. Two types of tests were conducted in the present investigation: 1) tests in which the temperature was maintained constant throughout the entire

Jan 1, 1958

By Carl H. Schmuck

The terms "cable bolting," "extended ground support," and "grouted cable" are synonymous, and they have been popping up with much more regularity in the mining engineer s vocabulary. In simplest terms, lengths of u itensioned cable up to 18.3 m (60 ft) are grouted in drill holes prior to mining. This permits radical departures from mining practices that rely on conventional rock reinforcement. For example, by placing a pattern of cable bolts in the back of an open stope, ore can be mined in successive slices. After each slice is taken the protruding cable; are simply cut off and mining proceeds. When about 4.6 m (15 ft) of reinforced back remains, a crew places a new par tern of cable bolts in the ore.

Jan 12, 1979

By A. R. Elsea, C. C. McBride

HIGH-TEMPERATURE alloys, that is, alloys that are strong at high temperatures, have become increasingly important with the development of modern aircraft engines. Many alloys of this type are available. However, metallurgists do not have a clear understanding of the phases or structures which are responsible for these high-temperature properties. If these basic factors were understood, it might be possible to make better or cheaper alloys for service at high temperatures. For this reason, an investigation of the fundamental factors promoting high-temperature strength in alloys was started at Battelle Memorial Institute. This was to have included a study of the relationship between the structure and properties of cobalt-chromium base alloys of the vitallium type. It soon became clear that the structure of vitallium is quite complex and that the equilibrium diagrams which should explain these structures were unreliable. As a result, the cobalt-chromium binary diagram was determined as the first phase of this investigation1. This diagram is shown in fig. 1. During the study of the cobalt-chromium binary system, it was learned that these alloys may pick up considerable nitrogen when melted and heat treated in air. The extent to which nitrogen affects the various reactions in cobalt-chromium base alloys was not known, but there were indications that this impurity might be responsible for some of the erratic test results obtained for vitallium. Consequently, nitrogen was the first ternary addition studied. Thereafter the work was extended to ternary additions of iron and of nickel. This paper describes the investigation of the effects of nitrogen, iron, and nickel upon the reactions in cobalt-chromium alloys with 80:20 and 68:32 cobalt-chromium ratios. Experimental Work Alloy Preparation: A series of cobalt-chromium base alloys containing various amounts of the third element being studied were made for both the 80:20 and the 68:32 cobalt-chromium ratios. Electrolytic chromium, cobalt, and iron, and reagent-grade nickel powder were used as melting stock. Table I contains the chemical analyses of these materials. The charges were melted in alun-dum thimble crucibles which absorbed chromium oxide and effectively deoxidized the melts. These crucibles were supported by close-fitting graphite sleeves so that if they cracked during melting the metal would not be lost. Carbon increases, during

Jan 1, 1951

By Harry L. Brown, James M. Dickinson, Philip E. Armstrong

The elastic stiffness coefficients of niobium have been rneaslrred from -150°C to over 650 C and ave in accord with the anomalous temperature dependence previously observed for Young's modulus. This unusual behavior has been shown to be the result of changes in the relative values of the shear elastic coefficients. The bulk modulus remained essentially constant over the temperature range studied, while changes in the shear coefficients produced a more nearly isotropic behavior as the temperature increased. A number of investigators have reported data on the temperature dependence of Young's modulus of polycrystalline niobium. The values cited for the room-temperature modulus ranged from 0.71 to 1.17 x 10" dynes-cm-' (10.3 to 17.0 x lo6 psi) and in each case the modulus was observed to decrease with increasing temperature. In our recent study,8 both polycrystalline and single-crystal samples of essentially strain-free high-purity niobium showed a Young's modulus whose temperature dependence as well as magnitude was strongly dependent on specimen orientation. This was shown to be the result of changes in the relative magnitude of the two shear moduli, C and C'. Young's modulus of polycrystalline samples with strong [110] textures and Young's modulus of single crystals whose orientations were away from the [loo] actually increased as much as 12 pct between room temperature and 1000°C. While studies on the residual effects of previous fabrication, thermal treatments, and impurity contents will probably resolve the problem of the widely differing Young's modulus values observed in polycrystalline niobium, a more complete description of the elastic properties requires an evaluation of the single-crystal elastic constants. A knowledge of these constants can provide a clearer picture of the nature of the temperature dependence, as well as establish a basis for predicting the modulus behavior of polycrystalline niobium, both in the randomly oriented condition and with various fabrication textures. The effects of residual strains on the elastic behavior then can be separated from orientation effects. EXPERIMENTAL METHOD Thin rod-resonance techniques were used to obtain both the Young's modulus and shear modulus of single-crystal specimens. The determination of these moduli as functions of the crystallographic orientation of the specimen axis provided sufficient information to permit calculation of the single-crystal elastic constants. The necessity for torsional as well as longitudinal measurements led to the design and assembly of a vertical-tube vacuum furnace incorporating probes for the simultaneous determination of both longitudinal

Jan 1, 1967

By R. G. Knickerbocker, W. H. Yarroll, P. E. Churchward, J. W. Hunter, J. H. Jacobs

THE present paper records a chapter in the history of the development of an electrolytic manganese industry in the United States.1 A relatively large pilot plant at Boulder City, Nev., for the production of electrolytic manganese was conceived as part of the national defense program to make this country independent of foreign importation of manganese ore. The first authorization, in November 1940, however, was for a plant of only several hundred pounds capacity. Improvements in process and subsequent additions to some sections authorized by subsequent appropriations have enabled the plant to produce as much as 2000 lb. of manganese a day for substantial periods of time. Since in pilot-plant operation frequent changes are made in the flowsheet, the electrolytic manganese plant was constructed so that equipment could be rearranged with a minimum of expense and time. Several different kinds of the various types of equipment were installed for many of the operations, so that the one most suitable for the process might be chosen. Pilot-plant operations were begun in November 1941 and have been continuous except for brief shutdowns for installation of new equipment. More than one-half million pounds of manganese have been produced. The improvements in process, selection of equipment, and operational procedure developed are recorded here. DEVELOPMENT OF THE PROCESS The work of early investigators on the electrolysis of manganese solutions has been reviewed by Shelton.2 Until the method of continuous production of manganese by electrolysis was perfected by Shelton2-4 and coworkers, no practical procedure had been devised. The method as originally developed by the Bureau of Mines will be described here only briefly. The manganese dioxide ore was reduced in a rotating kiln-type furnace at 650°C. in an atmosphere of "city" gas. The calcine was leached with spent electrolyte and enough sulphuric acid to produce a neutral leach solution containing 25 grams manganese per liter as manganese sulphate and 200 grams per liter of ammonium sulphate. Arsenic was removed from the solution by the addition of 0.05 gram iron per liter as ferrous sulphate followed by oxidation

Jan 1, 1944

R. Culver, Colorado School of Mines I appreciated Professor Starfield's presentation, because his approach to blasting research reflects my feelings that a lot of practical work can be done toward making short-term advances that can be used by the blasting industry. We should not forget this in our attempt to obtain solutions to such idealized problems as a mathematical theory of cratering. The blasting industry would like very much to have the efficiency of the basic blasting processes improved from the range of 20 percent up into the range of 50 percent. And many of these problems should be approached and attacked in the laboratories. Blasting research at the Colorado School of Mines for the past two or three years has been aimed at improving the pre-splitting process, because we feel it will become increasingly important to the construction industry. We have attempted to develop a unified theory of how pre-splitting works; and the more we investigate, the more variables we find. We may never obtain an entirely satisfactory theory of pre-splitting, but we have developed a tentative explanation. One of our first conclusions was that we are making very poor use of the explosive in current pre-splitting practice. But to appreciate this we must first consider how pre-splitting works. A series of parallel boreholes are loaded with low density charges which are detonated simultaneously. (Delayed detonation has been tried, but most people agree that simultaneous detonation is best, and this is what we found.) Stress waves traveling out from each borehole interact with the stress waves from the two adjacent boreholes influencing the direction of the fractures that occur and propagate from each borehole. It has been suggested in private communication with Mr. Wilbur Duvall of the U. S. Bureau of Mines, that the fracture between the adjacent boreholes is a result of the net particle velocities above and below the pre-split plane which tend to set up a net tension along the pre-split plane. Regardless of what the exact mechanism is that causes the fracture to propagate from one borehole to the next, we know that it, in general, relies upon an interaction of the stress waves. However, if there is a large compressive stress normal to the pre-split place, it can practically eliminate any possibility of obtaining the desired pre-split by preventing the desired fractures from getting started. Aside from obtaining a fracture along the pre-split plane, the other major aim of pre-splitting is to minimize the fracturing that occurs around the borehole. We do this by drilling a large hole and putting a small charge in the middle of it. This results in a badly decoupled charge which is very inefficient; most of the energy is used in compressing the air in the borehole. Out of discussions about how pre-splitting works, we decided that perhaps there was some other explosive geometry which would make more efficient use of the explosive, and result in optimizing the pre-splitting process. Starting in the laboratory with small plexiglas blocks, we found that a fully-coupled explosive charge of 5 grains/in. of PETN gave random fractures extending about I in. from the borehole. A 1/4 in. plexiglas plug fit into a 1/4 in. hole in a similar block with the same fully coupled charge gave random fractures extending out only about 1/2 in. due to the energy absorbed in fracturing the plug. If the plug was split longitudinally but otherwise using the same geometry, it was possible to drive a fracture about 2 in. in either direction from the borehole, with an even smaller amount of fracturing around the borehole.

Jan 1, 1967

By G. W. Jones

THIS paper describes experiments in which eight test samples of gelatin dynamite were fired in three different types of apparatus and the quantity and composition of the gaseous products of detonation determined. The special dynamites were so prepared that the oxygen balance of the samples varied from -35.0 to +6.0 g. per 100 g. of explosive, including the wrapper. By means of this graded series of explosives, the relation between oxygen balance and gaseous products of detonation could be studied explicitly. The effect of varying oxygen balance on explosive strength has been discussed in another paper.1 The apparatus employed in the work described in the present paper included (1) the Bichel gage, a steel bomb of 15-1. volume; (2) the Crawshaw-Jones confined detonation apparatus, a steel cannon from which the explosive is fired into a pipe of 90-1. volume; and (3) the Hercules tank, an apparatus in which the explosive is confined in a quartz block which is placed in a steel tank of about 4500-1. volume. A full description of the apparatus is given later. VARIABLES AFFECTING COMPOSITION OF DETONATION PRODUCTS The character of the detonation products of commercial explosives is governed in part by the same factors that affect the combustion products from explosive mixtures of air with gases or vapors. In either case, combustible materials-namely, carbon, hydrogen, and sometimes sulfur-are present and combined variously. In an exploding gas mixture the combustibles are oxidized by oxygen in the admixed air, whereas with explosives the necessary oxygen is provided by oxygen-carrying materials in the explosive ingredients.

Jan 1, 1928

By Kenneth P. Katen

INTRODUCTION Though the use of continuous mining machines consolidated the operations of cutting, drilling, blasting, and loading in one machine that would theoretically provide uninterrupted production, it was soon realized that the face haulage and roof support operations remained as major impediments to continuous production. The ability to provide not only continuous cutting and loading, but also continuous haulage and roof support (see Fig. I), was the basis for the introduction of mechanized longwall systems in this country from Europe in 1951. The early systems employed friction props for roof support, but were to become obsolete shortly after introduction of the first hydraulically powered, self-advancing supports in 1960. Since then, use of the longwall technique has grown to the point where it is currently providing more than 5% of the annual output of underground coal mines in the United States. The shortwall system had its origin in Australia, but was first introduced into this country in 1962 following the development of powered roof supports. It, too, provides for continuous cutting, loading, and roof support (see Fig. 2), but has not experienced the widespread popularity of longwall due to its inherent inability to easily provide for continuous haulage. While there are in the neighborhood of 100 longwall systems currently in operation in this country, there are only a handful of short- wall operations providing production of slightly more than 907 184.7 t/a (1,000,000 stpy). Both of these systems provide uninterrupted roof support for face operations by means of hydraulically powered steel roof supports. In each case, the coal removal consists of open-end cuts made from the narrow end of a large rectangular pillar (panel) which has been blocked out by continuous miners developing entries around its perimeter. However, this is the extent of the similarities between the two systems. It is hoped

Jan 1, 1981

By A. N. Diehl

IT is the object of this paper (1) to deal with the elements in blast-furnace gas from the standpoint of their importance, and the part they are to play in future consumption, and (2) to give detailed information about the construction and operation of a plant designed among the first in this country for washing gas on a large scale.

Jan 5, 1914

By F. R. Hensel

THE absorption of oxygen by molten metals is a quick and convincing method to determine the metallurgical characteristics of various types of furnaces.1 The investigation was restricted to the use of coreless induction furnaces. A major variable in induction furnace practice is the frequency and its influence was studied by comparing melts made in a 5000-cycle and a 60-cycle induction furnace respectively.2 The authors are not aware that such a comparative study has been made before and therefore present this paper in the belief that the results will be of general interest. ANALYTICAL METHODS FOR DETERMINATION OF OXYGEN IN NICKEL An analytical procedure for determining NiO by a quick and simple, laboratory method has been worked out in collaboration with Dr. Herty, of the Pittsburgh Station of the Bureau of Mines. It was found that Dr. Herty's aluminum method as used for the. determination of FeO in iron and steel was very suitable for use with nickel if instead of hydrochloric acid a 10 per cent solution of nitric acid is used for bringing the metal into solution. Essentially this method involves deoxidizing the nickel-oxygen alloy with aluminum (2Al + 3NiO = Al203 + 3Ni) and determining the resulting Al203 by a residue analysis. The original oxygen content can then be calculated from the amount of Al-20,. The method as suggested by Dr. Herty3 is referred to in the present paper as method B. A slight modification of method Bled to the application of method A, a description of which is given below according to F. W. Beiter?:3

Jan 1, 1932

By Lawrence K. Jetter, Robert F. Mehl

SOME advances have been made recently in the theory of the kinetics of precipitation from metallic solid solution despite the complexities of the problem, but there is surprisingly little quantitative information available on rates of precipitation with which to test present theory or upon which to build new theory.‡ Attempts to measure rates of precipitation have been beset with difficulties which originate both in the anomalies that attend the changes in the properties selected for measurement, as, for example, in electrical conductivity or mechanical properties, and also in the complexities in the structural changes in some systems, as in the aluminum-copper system. If the functional relationship between the quantity of precipitate and the value of the selected property is uncertain, measurements of that property are obviously of uncertain utility in determining absolute rates of precipitation. If the precipitating system passes through one or more transition stages, the interpretation of measured rates lacks definiteness; in such cases, it is necessary to measure the rate of reaction in each separate stage, if the rate measurements are to have any significance from the kinetic point of view.* These difficulties cannot be wholly avoided, for at least in some measure they are characteristic of the process of precipitation from solid solution, but they can be minimized both by the selection of a simple system and by the use of a method of measurement relatively free from anomalous behavior. The present paper reports dilatometric measurements on the rate of precipitation of silicon from the aluminum-rich solid solution in the aluminum-silicon system-a study that approaches the desiderata of simplicity. The aluminum-silicon system offers advantages from these points of view: there are no known anomalies in the property changes accompanying precipitation; 2.3,4 there are no known transition stages; the precipitate is an element, not a compound, and both matrix and precipitate are cubic, and while the structures are not identical (the solid solution is face-centered cubic and the precipitate is diamond cubic), the system at least approaches the ideal case of a crystal precipitating from a matrix of the same crystal type-the ideal case which Becker5 assumed in treating the precipitation process theoretically. The dilatometric method, while not free from disturbing effects, as the subsequent dis-

Jan 1, 1942

By Philip Davidson, Wm. B. Price

The object of this paper is to present, a survey of some of the physical properties of sheet nickel silver when subjected to cold rolling and when annealed at temperatures extending from 350" C. throughout the coininercial annealing range.. A number of alloys were taken from stock and analyzed. Four of these, representing low nickel and high nickel both with and without lead, were chosen for the tests. The analyses were as follows: Alloy Copper, Lead. Iron. Nickel, ManGanese, Zinc, PeR Cent. Per Cent. Per Cent. Per Cent. Per Cent. PEr Cent. A................ 64.68 Trace 0.194 6.73 0.06 remainder B................ 65.82 1.27 0.227 6.17 0.06 remainder C................ 65.44 Trace 0.345 17.83 0.08 remainder D................ 65.60 1.08 0.238 17.77 0.06 remainder These alloys were lolled in accordance with regular mill practice to approximately No. 6 R. & 6. gage. The bars (which were then coiled) were annealed together in a mill muffle and afterwards pickled in a 10 per cent. sulfuric-acid solution and cold rolled in stages of approximately one number (B. & S.) at a time to No. 18 B. & S. gage. After each stage, suitable samples were set aside for physical tests. Additional samples were chosen for tests after the bars were rolled to Nos. 8, 10, 12, and 14 gage. These samples were annealed together in the mill muffle and, after pickling, were finished on 0.050-in. gage, yielding a series of specimens 2, 4, 6, and 8 numbers hard for the subsequent annealing tests. Tensile test pieces 9 by 1 in. (22.9 by 2.5 cm.) were cut from both lots and the central portion was milled to give a test section 2 1/2 in. long by 1/2 in. wide. A distance of 2 in. was marked off on the edge of each specimen with light punch marks. In the case of the annealed alloys, Erichsen test pieces 4 by 235 in. were also taken.

Jan 1, 1921

By Hugh Rose

THE properties of the company lie within the Pachuca district, State of Hidalgo, Mexico, connected by three railway lines with Mexico City, 55 miles southwest, and by two lines with Vera Cruz, 250 miles southeast. The ores were formerly divided by sorting into two classes, smelting and milling, the former averaging about 2 oz. gold and 335 oz. silver, the latter 0.12 oz. gold and 23 oz. silver. The smelting ores were sold to custom plants, principally the American Smelting & Refining. Co. at Aguascalientes. The milling ores were treated by the patio process at the Guadalupe Hacienda, at Pachuca. This patio was probably the largest in existence at the time and continued in active operation up to March, 1910. In January, 1910, the mines and patio were sold to English interests, represented by Camp Bird Limited. Two new companies were formed, the Compañia de Santa Gertrudis, S. A., to operate the mines, and the Compañia Beneficiadora de Pachuca, S. A., to build and operate a custom cyanide milling plant. (Fig. 1.) GEOLOGY The historical geology of the Pachuca district is described by Fred J. Pope as follows: 1. The most recent sedimentary rocks in the district belong to the Cretaceous period. 2. The Cretaceous rocks were penetrated by large intrusions of ande-site (referred to hereafter as primary andesite) which occur as elliptical dome-shaped masses, striking northwest-southeast. These andesite bodies are from 8 to 15 miles long and from 6 to 10 miles wide. 3. A period of erosion during which the contour of the andesite domes was changed. 4. Andesite flows (secondary andesite) which rest unconformably on the primary andesites.

Jan 8, 1916

By E. V. d’Invilliers

The position of these magnetic ore-mines, with reference to the county-seat, is shown in Fig. 1. They are situated on the south margin of the Great Valley, five miles south of Lebanon, and about midway between Reading on the Schuylkill River and Harrisburg on the Susquehanna River, in three prominent, contiguous hills, standing in front of the Mesozoic red shale arid sandstone hill country of northern Lancaster and southern Lebanon counties, and overlooking the great limestone plain to the north. The three hills, named respectively Big, Middle, and Grassy Hills, and separated from each other by two branches of Furnace Creek, range in a nearly east and west direction for a distance of about one mile. Their summits are respectively 870, 715, and 700 feet above tide. The railroad line opposite the base of Middle Hill is 575 feet above tide at Cornwall and 471 feet at Lebauon. These features are all distinctly illustrated in the contour-line map accompanying this paper, but are made still more clear in the relief. map, Fig. 2, comprising, as it does, about six square miles of territory contiguous to the ore-mines. This is a photographic plate of a model made by Mr. A. E. Lehman, from surveys of my own and Mr. W. F. Shunk. The model was built in layers of cardboard, each layer representing one 10-foot contour-carve line. The scale was the same as the original map, 400 feet= 1 inch, without any vertical exaggeration. The lowest contour-line is 530 feet above ocean level; the highest, 1075 feet. The center of the model was made the focusing-point of the view, which was taken—according to scale—51/2 miles north from and 24 miles above the focusing-point, looking southward. When first mined in the last century these hills exhibited smoothlyrounded surfaces, composed of soft weathered ore of great parity, beneath which lay the great mass of hard ore, constituting the whole

Jan 1, 1886

By C. L. Mantell

ALTHOUGH SO common and well known a metal, tin is really a less abundant element than many of those less familiar and usually ranked with the scarce or rare elements, such as cerium, yttrium, lithium, beryllium., titanium, zirconium and vanadium. The color of tin is white, with a slightly bluish tinge. When it is compared with nickel, the latter metal is brown. When placed alongside of tin, chromium is definitely blue. Tin is whiter than silver or zinc. Exceedingly thin films of tin show various shades of brown by transmitted light. The metal has a brilliant luster, and when mirror-polished, has high light reflectivity. The luster depends to a large extent upon the pouring temperature at which the metal is cast. If the temperature be, too high, iridescent colors may show on the surface. These are the result of oxide film formation. If the pouring temperature be too low, the surface is dull. Small amounts of foreign metals, such as lead, arsenic, antimony and iron, decrease the luster of tin and impart a yellowish tinge to the metal. The structure is decidedly crystalline. The cast metal is a mass of crystals. When a bar of tin is bent, it emits a characteristic creaking sound. This is called the "cry" of tin, resulting from the grinding of the crystals one against the other during the bending of the metal. Tin metal may lose its crystalline structure by cold working, but grain growth occurs rapidly under the influence of heat. Metal which has been cast at a low temperature may become amorphous as the result of mechanical work. If such material be heated to temperatures well. below the melting point, say at 110° C. for a half hour or for a few minutes at 150° C. recrystallization occurs. If the surface of tinned plate, tin foil, or tin metal in cast form be etched with hydrochloric acid containing a little free chlorine, attack occurs at the intercrystalline faces. The surface shows patterns resembling the frost flowers on window panes in winter. The etched appearance is called moiré metallique. Fine dendritic surface crystals of tin may be obtained by casting the metal on a surface of polished steel. In commercial tin plate, the intercrystalline boundaries are shown by fine grooves or channels, which result from the method

Jan 1, 1929

By G. C. Wallick

Since the appearance of the paper, "Solution of the Equations of Un-steady State Two-Phase Flow in Oil Reservoirs," by W. J. West, W. W. Garvin, and J. W. Sheldon,' a two-fold investigation of this subject has been carried out. One objective of the investigation has been to deter-mine the feasibility of solving such problems 7on a medium-size com-puter such as the Datatron*, and the other objective has been to in-vestigate the application of such cal-culations to experimental and theo-retical petroleum reservoir research. In the first Datatron calculations, the fluid and rock properties published by West, et al, were used, together with the published equations describ-ing the system. Details of the formu-lation not given in the original paper are discussed in the Appendix to this note. Reference should be made to the subject paper for the complete equations and defintion of symbols. An unexpected result of this in-vestigation was the discovery that the linear solution published by West was in error. Thus, in addition to describing the Datatron solutions and to discussing certain numerical diffi-culties which will be encountered if one uses the published method of solution, the purpose of this note is to indicate the nature of this error. LINEAR FLOW Since the linear case requires a minimum amount of scaling, a fixed-decimal point Datatron program was written for the one-dimensional flow problem and an attempt was made to duplicate the solution described by West. In the case described, fluid was produced at a constant rate, Q, until such time as well pressure reached 0.04. Production was then continued at constant pressure. From the constants and curves given by West it was determined that the ini-tial constant production rate could be approximated by Q = 0.007. An ini-tial dimensionless time step ?t = 0.434 X 10 - "as used, and each suc-cessive time step was doubled until a value of = 0.444 was reached. This constant interval was then used for the remainder of the solution. In subsequent solutions, several varia-tions in the time schedule were em-ployed, including smaller time steps and slower rates of increase in the time steps. In all cases, almost identical results were obtained regardless of the time schedule employed. However, as described below, it was noted that the time schedule had some influence on the rate of convergence of the solutions. As a check on the accuracy of the solution, the cumulative production at each time step was calculated using the two methods described in the Appendix. Satisfactory agreement was observed with the differences in these two values of the order of two parts in 50,000. It should be noted that the mass balance check as described is of questionable value, particularly with regard to the well pressure and saturation. This is especially true in the radial solution where pressure and saturation values near the wellbore would make only a negligible contribution to the numer-ical integration. It is believed, how-ever, that such a comparison is ot value in determining the over-all accuracy of a solution. In comparing the Datatron solu-tion with that published by West it was discovered that in the later stages of depletion, the pressures near the well declined more rapidly in our solution than in the West solution, and that the limiting well pressure of 0.04 was reached at an earlier time than that originally reported. It thus became evident that it would be impossible to duplicate the production schedule described by West and a constant rate of production was maintained until the well pressure was equal to 0.0. A representative comparison of the results published by West with those obtained in this investigation is shown in Fig. 1, which is a plot of GOR as a function of cumulative recovery. These two curves should be in agreement until a cumulative recovery is reached which corresponds to a well pressure of 0.04 — for the Datatron solution, a recovery of approximately 5.6 per cent. Actually, a major disagreement is evident. Subsequent correspondence

Jan 1, 1958

By J. D. Wood, J. T. Smith

ALLOYS with a dispersed second phase in a metallic matrix are generally much stronger than the matrix itself. Plastic deformation in dispersion-strengthened alloys is usually confined to the matrix phase when recovery processes are active, while in the absence of recovery both phases may yield.' The alloy system studied in the present research was WC-12 wt pct Co and consisted of noncoherent WC particles dispersed in the cobalt matrix. Some particle-to-particle contact existed but not enough to produce a continuous WC skeleton. The microstruc-ture of the WC particles was characterized by very straight edges, forming a trapezoidal shape in any plane of polish. Previous investigations with WC-Co alloys at room temperature have shown that fracture of the WC particles occurs in transverse rupture testing.' Room-temperature slip was reported for WC particles after indentation for hardness measurements.3 Elevated-temperature deformation of WC particles in a WC-12 pct Co alloy was suggested by recent electron microscope studies of specimens deformed at 900' to 1000°C.4 In highly deformed alloys, the WC edges were serrated in contrast to the usual straight or smooth appearance. WC-12 pct Co and WC-15 pct Co alloys have been previously studied under elevated-temperature com-pressive-creep conditions by the present authors. Electron microscope studies of two-stage replicas from deformed specimens showed no evidence of slip or fracture of the WC particles. These specimens were brought to temperature and allowed to equilibrate prior to the application of the creep load. It was believed that the load-application rate, a crosshead speed of 0.005 in. per min on an Instron universal testing machine, was sufficiently low that recovery within the cobalt matrix was sufficient to limit the deformation to this matrix. A series of experiments was performed to evaluate the influence of loading rate on the deformation of WC-Co alloys. A WC-12 pct Co alloy was selected for these determinations. The average WC particle size was 4.45 p with an average linear separation between particles of 0.59 p. The selected temperature was 800°C and was monitored with a Chromel-Alumel thermocouple attached to the specimen. Testing was conducted in an argon-atmosphere chamber to prevent oxidation of the WC-Co specimens. This chamber was mounted on an Instron universal testing machine equipped to apply the load at a fixed rate. Each specimen was loaded to 110,000 psi compression stress at 0.05 and 0.5 in. per min. The loading rate was monitored prior to insertion of the test chamber and was found to be almost precisely the nominal rate selected. The specimens were raised to temperature and held to equilibrate with the surroundings, and then the load was applied and held for 4 hr to duplicate the exposure time utilized for the creep specimens. The time to reach full load at a crosshead speed of 0.005 in. per min was some 500 sec and was reduced to 50 and 5 sec as the loading rate was increased to 0.05 and 0.5 in, per min, respectively. The model developed by Ansell,' when recovery processes do not occur, considers that fracture or deformation of the dispersed particles is necessary to relieve back stresses on dislocation sources and allow dislocations piled up against particles to sweep out in the matrix to cause plastic deformation; he further states that, even at elevated temperatures, the dispersed-particle deformation is necessary for yielding in the absence of recovery. For the case of straight dislocation segments piled up against a straight barrier, such as the straight-sided WC particles, the shear stress, 7 exerted on a particle is: where h is the spacing between particles (0.59 p), a is the applied stress (110,000 psi), p, is the shear modulus of the matrix (6.7 X lo6 psi at 80O°C), and b is the Burgers vector of the matrix dislocation. From Eq. [I], the shear stress, 7, exerted on the WC particles when no recovery occurs is of the order of 6 X lo6 psi at 800°C. The limiting stress, F, that will

Jan 1, 1969

By W. W. Eckles

This paper is presented as a suniniary report of the use of well gas composition correlations obtained from mass spectrometer recordings as a means of identification and determination of reservoir continuity. Conventional methods for detecting composition differences are en-pensive, elaborate, and difficult to obtain. This excludes the use of extensive composition data for most applications. During recent years the mass spec-trometer has come into general use as an analytical tool in petroleum refineries. The use of mass spectrometer composition patterns ir~ characterizing or "finger-printing" the produced gas from a reservoir, presents a novel method for correlatitlg gas samples from well to well. The mass spectrometer provides a trace similar to an electric log. having peaks which represent the abuntlnnce of certaitz hydrocarbons in the well gas sample. Without going further into the detailed analysis the idea has been advanced that these traces or patterns could be used as a means of identifying a particular natural gas. This theory has proven to be essentially correct. The mass spectrometer pattern method is simple and cheap as COi?7pared to other standard methods. It greatly facilitates the solution of reservoir and geological problems in which correlation of well gas Com-positions is a factor. Specific field applications have been made. This paper concerns the results obtained in 465 individual gas analyses from 35 fields and 77 res- ervoirs. In a number of cases it has been found that such data have been extremely valuable in the determination of reservoir continuity. In at least one case, the method was a valuable contribution in tracing a reservoir from sand to sand in a coinplex fnulted field involving n11rnerous gas reservoirs. Field applications are presented to illustrate the possibilities of the method at the present stage of developnient and to stimulate the ernployrnent of this new approach by geologists and petroleum engineers in the industry. INTRODUCTION Identification of producing horizons and the determination of reservoir continuity are often a problem in those areas where dome structures and highly faulted sands are encountered. To complicate the picture further, there may be numerous sands, one on top of the other which dip and diverge in different directions. Even though it may be possible to develop some solutions to the preceding problems on the basis of the geological and reservoir data on hand. it is readily recognized that substantiating data based on independent methods would he extremely valuable. It has been found through field studies that correiation of well gas composition can be used to advantage in the geological and engineering study of a complex reservoir identification problem. METHOD FOR COMPARISON AND CORRELATION OF WELL GAS SAMPLES Since a large number of well gas samples are required in a gas identification or reservoir con- tinuity problem, it is necessary that a method of analysis be employed which can detect differences in composition readily and inexpensively. Although detection would be possible by means of low temperature fractional distillation (POD) analpsis, the method requires a relatively large sample and is comparatively slow and expensive to run. The mass spectrometer affords an inexpensive and precise analysis of small well gas samples taken at the surface which are about 1/300 as large as a POD sample. These samples can be obtained by regular field personnei and shipped to the spectrometer for analysis. It is, therefore, a practical approach to the problem. A typical record from the mass spectrometer is illustrated in Fig. I. The peaks on the record represent the abundance of ions produced from the different hydrocarbon molecules making up the gas sam-ple. In well gas comparisons only five peaks are employed, since the other peaks are formed from the same gas molecules and furnish no additional information. The five peaks used represent the abundance of methane, propane, ethane, butane and heavier, and oxygen. They are referred to respectively as the 16, 29, 30, 43, and 32 peaks. The oxygen peak is used to correct for air content in

Jan 1, 1958

By E. S. Machlin, W. R. Yankee

IN a previous study1 of the effect of heating com-mercial titanium in air on its subsequent friction coefficient against other metals, as well as itself, it was found that the friction coefficient markedly decreased from a value of about 0.7 to about 0.3. A tentative explanation was given that surfaces normally produced at room temperature are not contaminated sufficiently to prevent seizing or welding of the titanium to the softer mating metals. The latter tend to cleanse themselves during rubbing over the harder titanium. It was thought that the lack of a contaminant protective film on the titanium was due to the high solubility of titanium for oxygen and nitrogen and hence an inability to form a contaminant oxide or nitride. This explanation requires the ratio of the surface absorption rate to the diffusion rate to become much lower at room temperature than it is at high temperatures. In order to check the phenomenon further, commercial titanium specimens were nitrided or oxidized at 800°C for 20 hr in flows of prepurified N2 and 01, respectively, at about 1/2 in. H2O above atmospheric pressure. Friction runs were made in argon using a freshly cut copper hemisphere (cut in argon) on surfaces cut successively into the diffusion layers in the titanium (cut in argon) using the techniques described in a previous publication.' DPH values (100 gram load) were made as a function of depth into the diffusion layer using a Tukon tester. Also, micrographs were taken at separate cross sections to indicate the diffusion layers. The results obtained are presented in Figs. 1 and 2, which show the "static" friction coefficient vs hardness for the nitrided and oxidized specimens, respectively. A separate measurement of the friction coefficient of clean copper vs iodide titanium also was made. From results reported in the literature' giving the oxygen and nitrogen contents as functions of the hardness, cross plots were made showing the friction coefficients as functions of the amount of interstitial solute. These plots are given in Figs. 3 and 4. From micrographs of the diffusion layers and the phase diagrams, it was deduced that the data in Figs. l through 4 correspond to the single phase a region. The points observed on the compound regions have been excluded from the figures. It is apparent that nitrogen or oxygen in solution in the a titanium markedly affects the friction coefficient against a softer mating metal. Discussion of Results These results are extremely interesting from both a practical and theoretical viewpoint. The theoretical implications will be discussed first. According to Bowden, the friction coefficient should be given to a good approximation by the relation where a is the fraction of contact area that has welded, a is the shear strength of weaker component, and H is the hardness of softer component. Using this relation alone, it is difficult to understand the results because none of the terms should be affected by a variation in the oxygen or nitrogen content of the harder and stronger metal, titanium. Even if the ratio of S/H for titanium is used in Eq. 1, the ratio has been shown to be independent of oxy-gen or nitrogen content.' If a more rigorous equa-tion is used combining Eq. 1 and a result given pre-viously" for the case where welding is absent, then the relation obtained is µ = a S/H + (1-a) a W aß/H where a is constant and Waß is the work of adhesion between the two metals comprising the friction couple. This relation states that if a is less than 1/2 or so, variation in the work of adhesion Waß between copper and the titanium should affect the friction coefficient markedly. It is reasonable to expect that the work of adhesion will depend on the oxygen or nitrogen content of the titanium. Available data4 show that clean metals and oxides have much lower works of adhesion than the same metals against the

Jan 1, 1955