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By Robert L. Hoss

The application of Muskat's differential equations for predicting the performance of a solution gas-drive reservoir to the Fullerton field indicates that a recovery may be expected of 14,030 bbl per acre under primary depletion, and 15,910 and I7,190 bbl per acre, respectively, under the two pressure-maintenance programs analyzed. In this analysis it is assumed that fluid properties are the same throughout the reservoir, that the core data used are typical of the Clear Fork limestone in the locality, and that injected gas is completely diffused through the pay zones. The economic study of the three recovery programs considered indicates that the one in which 60 pct of the produced gas is returned to the formation is the most profitable. Introduction The purpose of this paper is to consider the effect of pressure maintenance by gas injection on the ultimate recovery of oil from a solution gas-drive reservoir. This prediction of reservoir behavior is the result of calculations based on the equations presented by M. Muskat in the Journal of Applied Physics, March 1945. Reservoir The reservoir analyzed is the Fullerton field in Andrews County, West Texas. It is situated on a broad anticlinal structure with approximately 330 ft of closure, and extends approximately eight miles north and south and five miles east and west. The areal extent is taken as 16,642 acres. The producing horizon is the Lower Clear Fork limestone of Permian age, occurring at depths from 6650 to 7350 ft. It is divided into four zones. For the purposes of this study, the fluid characteristics in all zones are assumed to be the same. Therefore an equivalent zone is assumed of thickness equal to the sum of the thicknesses of the four zones, or an average of 216 ft. The reservoir contains 3,586,991 acre feet of producing limestone, with an initial volume of stock tank oil in place of 918,-403,100 bbl. The average connate water saturation is 24.0 pct. The permeability ranges from 6.7 md. to 12.6 md., and the porosity ranges from 7.7 pct to 11.4 pct, except for occasional cavernous streaks. Based on these values, the limestone may be considered intergranu1ar.l Production histories and material-balance studies have indicated that the driving mechanism is solution gas. Water levels have been established. Theory It is possible to express mathematically the change in residual oil saturation with pressure decline in a solution gas-drive reservoir as being equal to the change in the physical properties of the fluids present in the reservoir as this pressure decline occurs. Essentially these equations, in differential form as presented by M. Muskat,2 express quantitatively the instantaneous net effect

Jan 1, 1948

By S. Floreen, H. W. Hayden

The effects of additions of iridium, rhodium, ruthenium, and platinum on the mechanical properties of Fe-C alloys were determined. Each alloying element significantly improved the toughness. The results support the general correlation that substitutional alloying elements that stabilize austenite are beneficial to toughness, but the reason for this improvement is not obvious at this time. The effects of substitutional alloying elements on the toughness of steel has long been a subject of both practical and theoretical interest. Despite the obvious importance of this subject, there has been little progress toward understanding the mechanisms by which alloying elements influence the fracture behavior. In some cases the deleterious effects of alloying elements have been shown to be due to mechanisms such as embrit-tlement of prior austenite grain boundaries or inhibition of cross slip in the ferrite lattice. In other cases, however, the reasons for the change in properties are not clear. This is particularly true for elements, such as nickel, that improve the resistance to brittle fracture. Several investigators'-3 have pointed out that there is a correlation between an alloying element's phase diagram with iron and its effect on toughness. Those substitutional alloying elements that stabilize austenite generally are beneficial to toughness, while ferrite-stabilizing elements generally are detrimental to toughness. The word "generally" should be emphasized, because exceptions to this rule can be found. Nevertheless, this correlation does offer a starting point at which to try to understand the effects of alloying elements on toughness. Thus far only two austenite-stabilizing elements, manganese and nickel, have been considered. In order to test the validity of this correlation several other austenite-stabilizing elements were evaluated. The noble metals, iridium, rhodium, ruthenium, and platinum, have binary phase diagrams with iron similar to the Fe-Ni and Fe-Mn diagrams. That is, each element expands the austenite field, and also higher concentrations of each element produce martensitic transformations at low temperatures. Presumably then, each of these elements should improve the toughness of steel. The present study was conducted to determine if this were so. EXPERIMENTAL PROCEDURE The alloys were made as l-lb air-induction melts using electrolytic iron and commercially pure noble metals. Each heat was initially deoxidized by a carbon boil, and further carbon was added to attempt to produce a 0.05 wt pct C content in each alloy. Before pouring, a final refining addition of 0.2 wt pct A1 and 0.1 wt pct Ti was made to each heat. The alloys were cast in a copper mold to produce ingots approximately 1 in. in diam and 5 in. long. The chemical compositions of the alloys tested are given in Table I. The residual nitrogen, aluminum, and titanium contents were all relatively constant at 0.003, 0.03, and 0.02 pct, respectively. The carbon

Jan 1, 1968

By N. B. Wittman

Among the objects of interest which the members of the Institute are invited to examine in connection with this meeting is the Brown segmental wire-gun, which will be seen in process of construction at the works of the Pennsylvania Diamond Drill and Manufacturing Company, at Birdsboro. This is a 5-inch breech-loading (highpower) rifle, 19 feet long, constructed upon the system of Mr. J. H. Brown, an inventor of recognized genius in many branches of mechanical industry, and under the engineering direction of Lieutenant G. N. Whistler, Fifth U. S. Artillery. The system consists essentially of the subdivision of the inner core or tube of the gun, which takes up the initial compression, into longitudinal segments of such size that a higher physical condition and degree of special elasticity may be set up therein than it is possible to produce in the larger masses of metal heretofore used for the tube of the modern high-power cannon. The process consists in winding layers of square steel wire, subjected to a constant tension of 130,000 pounds per square inch, around these segments, which, when so held together, form the tube of the gun. A lining-tube may or may not be used. The steel segments used in the gun now under construction are 18 feet 4 inches long, and 3 inches thick at the breech, from which they taper to 0.8 inches at the muzzle. The physical condition of the segments has been determined by test-pieces, cut from each end of each segment, which show the following characteristics: Tensile strength, 165,000 pounds per square inch. Elastic limit, 105,000 pounds per square inch. Elongation at rupture, 14 per cent. in 2 inches. They are of crucible chrome steel, made by the Carpenter Steel Works, at Reading, Pa. The wire which holds them together has 0.005 square inches sectional area and is wound under a constant tension of 650 pounds on each strand, equivalent to 130,000 pounds per square inch. The winding has been done by a machine designed

Jan 1, 1893

By E. J. Longyear

The rapid development of the Mesabi range has been a matter of much wonder to those familiar with ore-deposits elsewhere, and much skepticism was shown when " millions of tons of ore on the Mesabi" was first reported. Now, however, with over 8,000,000 tons to its credit at the close of 1896, a prospect of 3,000,000 more this year, and more ore " in sight" than ever before, it is evident that the first claims for the range were not so greatly exaggerated as perhaps even those who made them thought they were at that time. An explanation of the ease with which these deposits have been explored is found in their mode of occurrence. Lying in flat beds and near the surface, and only exceptionally occurring under a taconite " capping," the prospector had only to sink a few vertical test-pits on a fortyacre tract down to the rock to be reasonably sure whether his property contained ore or not. If he found ore in one or more of these preliminary pits, he would then fill in with more pits until the ore-area was entirely outlined by test-pits from 200 to 400 feet apart. In the early days of the range the testing was almost entirely done by digging pits with pick and shovel. When water was encountered, work had to be stopped, unless a steam pumping-plant was put in, resulting in greatly-increased expenses. Latterly, drills have been used with great success in continuing the exploration after water has been struck in the pit, rendering further progress with pick and shovel impracticable. There are several kinds of drills in use. The diamond-drill is largely used, and possesses the advantage of being in readiness to drill rock if thought advisable, the taconite being very hard and almost impossible to drill except by the use of diamonds. Some form of churn-drill has been much used. This may be either a steam- or a horse-power-drill. The principle is the same in each, the cutting being done by percussion instead of by rotation, as in the case of the diamond-drill. A churning motion is given by passing a rope from the top of the

Jan 1, 1898

By H. E. Crum, W. E. Hubbard

This review covers the northern 32 counties of the Texas Panhandle, an area 180 miles square. The westerly three-fourths of the district lies wholly within that great area known as the Llano Estacado or "staked plains." Six of the counties produce oil and gas and three produce gas alone. All of the production is associated with the Amarillo arch, a huge anticline superimposed upon a buried mountain range which is undoubtedly a continuation of the Wichitas of southwestern Oklahoma. Oil Production The production of the Texas Panhandle up to Jan. 1,1930, was slightly over 157 million barrels, 90 per cent. of which came from Hutchinson and Gray counties. About 33,000,000 bbl. was produced during 1930. Though this was about 9 per cent. above the 1929 production, it was over 8,000,000 bbl. less than was produced during the peak year, 1928. The present daily production is slightly over 40,000 bbl., which is the allowable production under state-wide proration. The assumed potential for the purpose of proration is 124,500 bbl. and the actual capacity of the wells probably would be in the neighborhood of 100,000 barrels. The total initial production of the oil wells completed in 1930 was 157,289 bbl. from 308 wells, or 511 bbl. per well, as compared to a 734-bbl. average from the 350 oil wells drilled during the preceding year. The completions in Gray County numbered 232, with an average initial of 614 barrels. Completions During 1930, 526 wells were completed in the Panhandle as compared to a total of 503 during 1929. Of the year's completions, 308 were oil wells, 169 produced gas and 49 were dry holes. Of the 3027 wells drilled in the Panhandle to date, 2780 have produced oil, gas or both, making the ratio of dry holes to producers about 1:11.3. Ignoring the 63 dry holes drilled in nonproductive counties, the ratio becomes 184:2780 or 1:15.1 which is slightly less favorable than that which obtained at the end of 1929.

Jan 1, 1931

By Carl Beal

THE most important factors that should be given consideration in valuation of oil land are: (1) the amount of oil the property will produce; (2) the amount of money this oil will bring (based upon the future prices of oil) ; (3) development and production costs; (4) the rate of interest on the investment; (5) the retirement or amortization of invested capital; and (6) the salvage or "scrap" value of the equipment when the property is exhausted. These factors are of varying importance, and some of them may not enter all valuation problems, but most of them should be given consideration in any valuation even though only a rough estimate of the value of the property is desired. The value of a property may be changed over-night by the completion of important test wells, by the sudden water flooding, or by a change in the price of oil. The best a petroleum engineer can give is the value of the property under the conditions existing at the time the appraisal is made with a fair forecast of future action of the wells and of the price of oil. Our experience in the scientific valuation of oil lands is not broad and there is very little published information on the subject; it, therefore, becomes necessary in studying such problems to form comparisons with the factors involved in the valuation of mines-the closest parallel. One of the reasons for the lack of substantial progress in oil-land valuation methods has been the necessity of making an estimate of the future production of the oil property to be valued. Oil men and accountants have not generally conceded that such estimates could be made with any degree of accuracy. It has been shown, however, in several recent publications that with certain data available reasonably close estimates can be made. The accuracy of an appraisal depends chiefly on the accuracy of the estimates of future production and of the future price of oil. The accuracy of the former is sometimes necessarily based on geological inferences. Geology is not an exact science and geological data in connection with oil production cannot always be mathematically evaluated.

Jan 9, 1919

By W. T. Bishop

FOR many years pine oil has been used extensively as a frother for the flotation of minerals, particularly sulphides, yet the published information available to the average user on its composition, chemical and physical properties, has been rather meager. It is the purpose of this paper to discuss these points and their relationship to the frothing properties of pine oil used in flotation processes. Pine oil, as the name implies, is a liquid obtained from the processing of wood of the longleaf and other southern pines. It is a complex mixture of naturally occurring terpene derivatives, primarily alcohols, and a smaller amount of terpenes, which has found many uses in various industries. Its use as a frother in flotation processes was the first large-scale application in industry and today the mining industry still consumes large quantities of pine oil but the textile and disinfectant industries consume comparable volumes. Much is used in soap manufacture and laundry operations. The surface-active properties of pine oil are in a large degree responsible for this versatility. HISTORY The name "Naval Stores" goes back to the days when pine tar and pitch were used to caulk leaky ships and coat their ropes and rigging. Today this term is still used to include not only the oleoresinous products of the pine tree-rosin and turpentine-but other products such as pine oil, pine tar, and the many terpene and resinous compounds obtained by extracting the pine wood or tapping the tree. That part of the industry known as "wood naval stores" dates from about the beginning of this century and today produces a large part of the country's rosin and turpentine by processing pine wood. In addition, all of our natural pine oil is, supplied by the wood naval stores industry, as tapping of the live tree gives only rosin and turpentine. This latter phase is known as the "gum naval stores" industry. The first successful commercial operation of the steam and solvent process of the wood naval stores in industry was carried out by Yaryan at Cadillac, Mich., in 1909.1 This operation did not prove profitable, so Yaryan went south to utilize the longleaf pine, and built a plant at Gulfport, Miss.2 Soon after, another plant was built at Brunswick, Ga., which is still in operation, and in 1914 was reported to have processed about 500 tons of wood per day.1 In 1921 Hercules Powder Co. acquired the Yaryan interests, at which time the production of pine oil was only 3 to 5 million pounds per year and flotation was the largest customer. As time went on, technological advances were made, other companies entered the field, and the production of pine oil increased many fold. The growth of the industry was especially marked during the past 10 years, and in

Jan 1, 1946

By C. A. Edwards

Following a brief introduction, an outline is given of the four main conditions in which gases may be associated with metals; namely, (1) adsorbed gases, (2) dissolved gases, (3) gases in chemical combination, (4) gases entrapped in blowholes or cavities. Adsorption is essentially a surface phenomenon and is regarded as the attachment of outside molecules or atoms to the exposed free valencies of the atoms comprising the surface layers. In many cases where adsorbed films of gas are formed this is accompanied by a process of diffusion of the gas into the metal itself. This is particularly true in respect to iron and hydrogen, and experiments have shown that there is no difference between the rate at which hydrogen diffuses through a single crystal of iron arid through the same material after it has been recrystal-lized into a mass of small crystals. This does not prevent a somewhat greater concentration of gas at the boundaries of adjacent crystals, nor does it mean that the effect of the gas will be the same at the boundaries as it is within the body of the crystals. Indeed, under certain conditions, iron is rendered very brittle at the crystal boundaries, as shown in experiments by Pfeil with samples of almost pure iron. Much work has been done by many investigators concerning the temperature and conditions under which dissolved hydrogen, in particular, can be at least partially removed from different metals. With iron, the hydrogen that has diffused into the metal as a result of acid attack by pickling or by electrolytic deposition of the gas on the metal is partly removed by exposing the metal to the atmosphere at ordinary temperatures. Considerably more can be eliminated by raising the temperature, and even greater quantities by jointly raising the temperature and reducing the pressure. Annealing at suitable temperatures completely removes the bad effects of excessive mounts of hydrogen dissolved in or associated with iron. This is shown by the data plotted in Fig. 1, giving values for electrolytic iron sheets after annealing at temperatures between 250" and 950" C. The hydrogen brittleness is rapidly diminished at

Jan 1, 1935

By A. M. Nicholas

WHEN attempting to lift mill pulp containing a considerable percentage of wolframite, in an ordinary bucket elevator, difficulty was encountered from the tendency of the tungsten minerals to settle, on account of their high specific gravity. Lifts not exceeding 20 ft. (6m.) could be accomplished without particular difficulty, because there was insufficient time for consolidation of the heavy minerals in the bottom of the bucket; but with higher lifts, the heavy tungsten minerals would settle so solidly that when the bucket turned over at the top of the elevator the contents could be only partially dumped. In this case it ,was necessary to lift the material a distance of 34 ft. (10m.); hence some means had to be adopted to prevent settling, at least to such an extent that the material could be dumped from the buckets. To reduce the carrying time to a sufficient extent would have required a belt speed of 475 ft. (144.7m.) per minute, which was not feasible. It was decided to try, by vibrating the belt about midway of its span, to keel) the material sufficiently agitated during elevation to prevent settling. Underneath the rising side of the belt was placed a 12-in. (30.48-cm.) idler pulley, 18 ft.-(5.5 in.) up in the total lift of 34 ft. The idler pulley was set eccentric by 3/4 in. (19 mm.) and it was hoped that the vibration thus imparted to the belt, running at a speed of 280 ft. (85 m.) per minute, would prevent settling in the buckets. It was found that the pressure of the belt on the idler, due to the small inclination of the elevator, was not sufficient to overcome sliding on the idler, and the agitation was insufficient to accomplish the desired purpose. The idler was then connected to the drive shaft of the elevator through an intermediate pulley, gearing down to a speed of 20 r.p.m., so that a positive vibration was imparted to the belt; this imparted enough motion to the belt to prevent settling and the contents of buckets clumped satisfactorily.

Jan 2, 1918

By C. A. Edwards

Following a brief introduction, an outline is given of the four main conditions in which gases may be associated with metals; namely, (1) adsorbed gases, (2) dissolved gases, (3) gases in chemical combination, (4) gases entrapped in blowholes or cavities. Adsorption is essentially a surface phenomenon and is regarded as the attachment of outside molecules or atoms to the exposed free valencies of the atoms comprising the surface layers. In many cases where adsorbed films of gas are formed this is accompanied by a process of diffusion of the gas into the metal itself. This is particularly true in respect to iron and hydrogen, and experiments have shown that there is no difference between the rate at which hydrogen diffuses through a single crystal of iron arid through the same material after it has been recrystal-lized into a mass of small crystals. This does not prevent a somewhat greater concentration of gas at the boundaries of adjacent crystals, nor does it mean that the effect of the gas will be the same at the boundaries as it is within the body of the crystals. Indeed, under certain conditions, iron is rendered very brittle at the crystal boundaries, as shown in experiments by Pfeil with samples of almost pure iron. Much work has been done by many investigators concerning the temperature and conditions under which dissolved hydrogen, in particular, can be at least partially removed from different metals. With iron, the hydrogen that has diffused into the metal as a result of acid attack by pickling or by electrolytic deposition of the gas on the metal is partly removed by exposing the metal to the atmosphere at ordinary temperatures. Considerably more can be eliminated by raising the temperature, and even greater quantities by jointly raising the temperature and reducing the pressure. Annealing at suitable temperatures completely removes the bad effects of excessive mounts of hydrogen dissolved in or associated with iron. This is shown by the data plotted in Fig. 1, giving values for electrolytic iron sheets after annealing at temperatures between 250" and 950" C. The hydrogen brittleness is rapidly diminished at

Jan 1, 1935

By S. B. Sargent, V. J. Collins, Lester C. Uren

[The conclusions arrived at by authors in paper read before the Petroleum Division and the California Sections of the Americam Institute of Mining and MetallurgicaI Engineers and the Standardization Division of the American Petroleum Tnstitute, at a joint session held at Los Angeles, Cal., Jan. 21, 1926, are presented below.] From the theoretical discussion and experimental evidence presented in this paper, the following conclusions may be drawn: 1. The efficiency of the oil-well plunger pump is dependent to an important degree upon the submergence provided. 2. Ample submergence must be secured in order to provide sufficient static pressure to force the oil through the restrictions interposed in the oil path at the standing valve and at the plunger nut surrounding the garbutt rod. These restrictions should be no smaller than is structurally necessary, in order to reduce resistance to oil flow to a minimum. 3. A part of the static pressure developed below the standing valve by submerging the pump is dissipated in overcoming the inertia and in providing upward acceleration for oil left between the pump valves at the conclusion of the down-stroke of the plunger, and of oil below the standing valve in the gas anchor above the oil inlet. This loss in effective static pressure can be reduced to a minimum by dispensing with the garbutt rod and placing the working valve at the lower end of the plunger. The valves should be as near together at the conclusion of the down-stroke of the plunger as is consistent with security in avoiding striking of the lower end of the plunger on the standing-valve crown. Gas anchors should be short, and oil inlets should be as near the standing valve as is consistent with proper gas exclusion. 4. Because of the presence of gas in solution in the oil, which tends to escape from solution under the reduced pressure conditions above the standing valve, the effective length of stroke of the plunger is reduced, and the suction effect of the rising plunger is largely nullified. The influx of oil through the standing valve is therefore chiefly dependent on static pressure developed by submergence.

Jan 1, 1927

By Joseph Jensen, J. B. Stevens

The history of the normal oil field is supposed to show an oil graph starting high in flush production, descending more or less steeply into the curve of settled production and dropping gradually to the vanishing point of economical operation. Together with this, somewhere in the early history of the field, there appears from a vanishing point a graph showing the production of water. During the period of settled production this graph rises higher and, toward the close, unless extensive work is done in the line of correction, rises far above the oil graph to the point at which the cost of operation terminates profitable pumping. Fields that start out with a high relative content of water are generally very short-lived. Fields that never develop a water problem are exceedingly rare. The McKittrick oil field, Kern County, California, with 840 acres of proved ground, 300 wells and a present recovery per acre of 94,598 bbl. from 1898 to Aug. 1, 1930, presents a study which is an apparent reversal of the outlined normal history. Though the history of the field now covers over 30 years of operation, it is still too early and the conditions too unique to project the graph of production to completion. The present conditions and directions of change are most interesting, in that the curve of oil production is remarkably flat and the curve of water invasion, after reaching an appalling height, has shown a definite reversal and a continued decline for 10 years. Early drilling in the McKittrick field was in or prior to 1898. Development continued steadily to 1918 when the present limitations of the field were determined. Shut-offs, according to accepted practice of the time, were made by driving the shoe into a shale stratum or into a tamped-in bridge of sand, rosin and clay. Records of early days speak of three waters: (1) surface water which was fresh; (2) an intermediate sulfur water, encountered below the top oil or tar sand; (3) bottom salt water. In different portions of the field any one of these waters let into a well by faulty completion might require immediate correction to obtain satisfactory production. In many wells,

Jan 1, 1931

By E. V. Foran

TheRe are many factors which control the ultimate production of oil and gas from a producing formation and the rate at which this production is obtained from any of the producing wells in the formation. The most important of these, and the one over which the greatest control can be exercised, is the differential pressure existing between the formation and the well bore. In producing any well by means of the gas-lift, it may be possible to change the flow tubing in a number of ways or vary the volume of circulating gas or air used for flowing the well, but if these operations, regardless of their magnitude, do not change the differential pressure between the producing sand and the well bore, they will in no way change the production of the well. If this statement is accepted as a fact, then all gas-lift or air-lift installations should be designed with but one object in view; namely, a means by which we can economically control very wide ranges of differential pressures between the formation and the well bore. Factors of Production In gas-lift production from any given formation, there are four major factors which govern the magnitude of the differential: (I) the depth of the well; (2) type and size of flow tubing; (3) volume of the circulating air or gas, and (4) physical properties of the oil-gas mixture after it has reached the well. The first of these factors is uncontrollable and does not vary. The other three are controllable within certain limits. The degree to which the last three factors can be controlled will cntircly govern the length of life of the well while on the lift, the lifting cost, and the daily production. It will also govern to some extent the ultimate production from the wells or leases producing by this method. These four factors will be discussed in detail in another part of this paper. Before proceeding further, a review of the present general practice in Texas, elsewhere than in the Gulf Coast region, will be given.

Jan 1, 1928

By Alfred H. Hesse, Edwin T. Myskowski

The development by the U. S. Bureau of Mines of a process for purifying manganese by electrolysis has stimulated interest in manganese alloys. While recent publications have shown some alloys of manganese and copper to possess rather unusual properties, none have included information on tensile properties, which have an important bearing on the usefulness of the alloys. Manganese-copper alloys can be heat-treated, since the single phases that exist at high temperatures may be retained by quenching. According to Persson,1 when quenched alloys containing from about 30 to nearly IOO per cent manganese are reheated, alpha manganese is precipitated (Fig. I). Calculations based on Persson's X-ray data indicate that this decomposi-tion is accompanied by a change in volume of as much as ; per cent. The reason that this large volume change has not been noted probably is the slow rate at which equilibrium is reached by these alloys. In an investigation on hardening by cold-work and heat-treatment, Dean and Anderson3 found that quenched alloys increase in hardness with manganese content and that high-manganese alloys harden very slowly with cold-work, while high-copper alloys harden much more rapidly. Heat-treatment has little effect on manganese-copper alloys containing less than 40 per cent Mn, and affects those alloys containing more than 40 per cent in accordance with their manganese content and heat-treating temperature. Dean and Anderson4 also found that cold-work increased electrical resistance of alloys containing from 50 to 80 per cent Mn, and that heat-treatment of alloys containing from 40 to 96 per cent Mn altered the electrical resistance considerably. Dean, Anderson and Potter6 have shown that the high vibration damping capacity that characterizes manganese-copper alloys containing 40 to go per cent Mn is affected by cold-work and heat-treatments. Highest vibration damping capacity at low stresses was obtained by heating for 2 hr. at 450°C. (842°F.) after quenching from solution temperatures. Preparalion of Alloys.—The alloys for these tests were melted in a 17-lb. basic-lined high-frequency induction furnace using electrolytic manganese, grade A ingot copper and a 70-30 CU-Mn master alloy (69.80 per cent Cu, 0.12 Fe, 0.04 Si, 0.006 S, 0.07 C, balance Mn). The manganese was heated slowly to expel excess dissolved gases and melted before the addition of copper. No fluxes or covers were used. The melts were cast in tapered iron molds and the ingots were reduced go per cent when forged to 1/2-in. rounds. These rods were given 2-hr. solution treatments at temperatures that depended upon the composition (Table I). Tensile Tests.—The tensile specimens, 0.313-in. diameter (1.25-in. gauge length),

Jan 1, 1942

By Edwin T. Myskowski, Alfred H. Hesse

The development by the U. S. Bureau of Mines of a process for purifying manganese by electrolysis has stimulated interest in manganese alloys. While recent publications have shown some alloys of manganese and copper to possess rather unusual properties, none have included information on tensile properties, which have an important bearing on the usefulness of the alloys. Manganese-copper alloys can be heat-treated, since the single phases that exist at high temperatures may be retained by quenching. According to Persson,1 when quenched alloys containing from about 30 to nearly IOO per cent manganese are reheated, alpha manganese is precipitated (Fig. I). Calculations based on Persson's X-ray data indicate that this decomposi-tion is accompanied by a change in volume of as much as ; per cent. The reason that this large volume change has not been noted probably is the slow rate at which equilibrium is reached by these alloys. In an investigation on hardening by cold-work and heat-treatment, Dean and Anderson3 found that quenched alloys increase in hardness with manganese content and that high-manganese alloys harden very slowly with cold-work, while high-copper alloys harden much more rapidly. Heat-treatment has little effect on manganese-copper alloys containing less than 40 per cent Mn, and affects those alloys containing more than 40 per cent in accordance with their manganese content and heat-treating temperature. Dean and Anderson4 also found that cold-work increased electrical resistance of alloys containing from 50 to 80 per cent Mn, and that heat-treatment of alloys containing from 40 to 96 per cent Mn altered the electrical resistance considerably. Dean, Anderson and Potter6 have shown that the high vibration damping capacity that characterizes manganese-copper alloys containing 40 to go per cent Mn is affected by cold-work and heat-treatments. Highest vibration damping capacity at low stresses was obtained by heating for 2 hr. at 450°C. (842°F.) after quenching from solution temperatures. Preparalion of Alloys.—The alloys for these tests were melted in a 17-lb. basic-lined high-frequency induction furnace using electrolytic manganese, grade A ingot copper and a 70-30 CU-Mn master alloy (69.80 per cent Cu, 0.12 Fe, 0.04 Si, 0.006 S, 0.07 C, balance Mn). The manganese was heated slowly to expel excess dissolved gases and melted before the addition of copper. No fluxes or covers were used. The melts were cast in tapered iron molds and the ingots were reduced go per cent when forged to 1/2-in. rounds. These rods were given 2-hr. solution treatments at temperatures that depended upon the composition (Table I). Tensile Tests.—The tensile specimens, 0.313-in. diameter (1.25-in. gauge length),

Jan 1, 1942

By Clarence Zener

The heat-treatment of steels will not pass from the stage of an art into that of a science until the mechanism of the phase transformations associated therewith is thoroughly understood. Such an understanding will involve two distinct types of inquiry: (I) the direction of the transformation, (2) the speed of the transformation. The first type of inquiry, which involves only the equilibrium relations between the various phases in steel, is the subject of the present and of a succeeding article; the second type, which involves the kinetics of transformations, will be the subject of a later article. In order that a theory of equilibrium relations may give useful information, certain experimental data must be put into the theory. It is customary for these data to be of a thermal nature. In the system discussed herein—steel—such thermal data are very scarce. In medium-alloy steels another type of data might possibly be used. In these steels the concentration of solute is so low that it may be possible to use the approximation of dilute solutions, an approximation that leads to linear relationships. The unknown functions, or constants, may then be determined in some cases from the binary iron-alloy system and in other cases from the ternary iron-carbon-alloy system. From the functions, or constants, so determined may then be computed the equilibrium relations in more complex medium-alloy steels. In the present article this second approach is used, the necessary experimental data 'being obtained from the simple binary and ternary equilibrium diagrams. Fundamental Equations In this article are derived the equilibrium relations between the gamma, alpha and cementite phases. In these three phases all important alloying elements except carbon form substitutional solutions, each alloying atom occupying a potential site for an iron atom. Carbon, on the other hand, forms an interstitial solution. In the face-centered cubic gamma phase, the interstitial positions are at the center of the unit cube and at the centers of the cube edges. There are therefore four interstitial positions per unit cell, or one per iron atom. In the body-centered cubic alpha phase, the interstitial positions are probably at the face centers, and also at the centers of the edges, which are crystallographically equivalent to the face centers. There are therefore six interstitial positions per unit cube, or three per iron atom. In cementite, (Fe, Alloy)3C, the carbon atoms may. be regarded as filling all the lattice positions of a given type. The introduction of the fundamental the of equilibrium has presented the author with a quandary. These equations are formally so similar to other equations that have been derived1,2 for related systems that they may appear to some readers

Jan 1, 1947

By Clarence Zener

The heat-treatment of steels will not pass from the stage of an art into that of a science until the mechanism of the phase transformations associated therewith is thoroughly understood. Such an understanding will involve two distinct types of inquiry: (I) the direction of the transformation, (2) the speed of the transformation. The first type of inquiry, which involves only the equilibrium relations between the various phases in steel, is the subject of the present and of a succeeding article; the second type, which involves the kinetics of transformations, will be the subject of a later article. In order that a theory of equilibrium relations may give useful information, certain experimental data must be put into the theory. It is customary for these data to be of a thermal nature. In the system discussed herein—steel—such thermal data are very scarce. In medium-alloy steels another type of data might possibly be used. In these steels the concentration of solute is so low that it may be possible to use the approximation of dilute solutions, an approximation that leads to linear relationships. The unknown functions, or constants, may then be determined in some cases from the binary iron-alloy system and in other cases from the ternary iron-carbon-alloy system. From the functions, or constants, so determined may then be computed the equilibrium relations in more complex medium-alloy steels. In the present article this second approach is used, the necessary experimental data 'being obtained from the simple binary and ternary equilibrium diagrams. Fundamental Equations In this article are derived the equilibrium relations between the gamma, alpha and cementite phases. In these three phases all important alloying elements except carbon form substitutional solutions, each alloying atom occupying a potential site for an iron atom. Carbon, on the other hand, forms an interstitial solution. In the face-centered cubic gamma phase, the interstitial positions are at the center of the unit cube and at the centers of the cube edges. There are therefore four interstitial positions per unit cell, or one per iron atom. In the body-centered cubic alpha phase, the interstitial positions are probably at the face centers, and also at the centers of the edges, which are crystallographically equivalent to the face centers. There are therefore six interstitial positions per unit cube, or three per iron atom. In cementite, (Fe, Alloy)3C, the carbon atoms may. be regarded as filling all the lattice positions of a given type. The introduction of the fundamental the of equilibrium has presented the author with a quandary. These equations are formally so similar to other equations that have been derived1,2 for related systems that they may appear to some readers

Jan 1, 1947

By Robert I. Jaffee, Bruce W. Gonser, Eugene M. Smith

There has been little investigation of the gold-germanium binary alloys. Haughtonl does not mention any work on the system. In a review article commemorating the fiftieth anniversary of the discovery of germanium, E. Einecke2 mentioned a gold-germanium eutectic at 24 atomic per cent Ge (10.4 weight per cent) melting at 359°C., but did not give the source of his information. From measurements of electrical conductivity, J. 0. Linde3 estimated that at least 0.6 weight per cent germanium is soluble in gold. The recent availability of germanium in this country in commercial quantities has led to interest in its properties and its alloys. This study is part of a program of investigation on germanium alloys; work on ternary alloys involving germanium and gold will be reported later. In this investigation, the composition and melting point of the Au-Ge eutectic reported by Einecke has been found to be substantially correct. Eutectic composition has been placed at I2.0 per cent germanium, however. An alloy of 10.4 per cent Ge, Einecke's value, was found to have a few gold dendrites in it. The cutectic temperature has been determined as 356.0 6 ± 0.5°C., slightly less than the temperature of 359°C. reported by Einecke. The liquidus curves and the solid solubility of ger- manium in gold have been determined, and are shown in Fig. I. Materials and Alloying The germanium used in this investigation was prepared by the Eagle-Picher Lead Co. from pure germanium oxide, by reduction in clay crucibles with sodium cyanide. The regulus is quite pure, assaying over 99.9 per cent Ge. High-purity gold obtained from Handy and Harmon was used. Alloying was carried out in graphite crucibles in an atmosphere of purified hydrogen. The temperature was brought up to 1050" to iioo°C., and the metal was allowed to freeze in the crucible. Prepared in this way, the gold dendrites in hypoeutectic alloys were somewhat segregated at the bottom and sides of the ingot, and on the hyper-eutectic side the lighter primary germanium tended to gather at the top. Most of the alloys were made from virgin metal. Low-germanium heats were made by alloying pure gold with the eutectic. Melting losses were consistently a few milligrams or less, and the composition could safely be taken from the intended analysis. The 30 per cent and 50 per cent germanium heats for thermal analysis were made in part from remelted higher germanium heats, and they may be OR composition as much as one per cent. Because of the high cost of materials, the weight of heats for thermal analysis were 15 to 20 grams and heats for metallo-graphic, X-ray, and hardness specimens were 2 to 4 grams.

Jan 1, 1945

By M. P. Tixier, M. Gondouin, G. L. Simard

In the quantitative interpretation of the SP logs, the electrochemical component is generally taken equal to — K log Rm /Rw where K has the theoretical value corresponding to solutions of pure sodium chloride. This method may be misleading when relatively large quantities of salts other than NaCl are present in form-rrtion waters—as is generally the case for low salinities —or in gyp-base muds. In such cases recourse is made in the field to changing the K value or to adding a correction term to the equation on the basis of local experience. An investigation has been made in the laboratory of the influence of HCO3, SO4=, Ca++, and Mg++ on the amplitude of the SP deflection, which included in par-ricular determinations of the activity coefficients of Ca++ and Mg++. The theory, the experimental techniques and a tentative method for applying the results are described. So far, applications to actual field cases where chemical analyses of waters were available have provided an excellent confirmation of the proposed method. The case of the SP in very salty brines is also considered and it is shown that the use of activity data for sodium gives satisfactory results. HISTORICAL In early times of electrical logging, the SP curve was used exclusively as a tool for the location of permeable beds and the definition of their boundaries. Later, with the introduction of methods of quantitative analysis, attention was called to the possibility of deriving from the SP log some information on the formation water resistivity, which constitutes one essential element for the computation of water saturation from log data. The first laboratory experiments' in 1932 had shown that, as a result of electrochemical phenomena arising at the contact of the niud and the formation, the amplitude of the deflection of the SP curve was, at least partly, a function of the salt concentration of interstitial water and accordingly of its resistivity. It was indicated that the amplitude of the electrochemical component of the SP should be equal to K log R1/R2, R1 and R2 being the resistivities of the mud and of the formation water respectively. However, the exact value of the K coefficient was not determined at that time because the surface clay used for a laboratory model was far from an ideal shale membrane. Consequently, the way was not yet open towards quantitative interpretation. In the early forties, Tixier reported2, on the basis of field log observations, the following equation for the case of NaCl solutions, SP = -71 log f1c1/f2c2, c1 and c2 being the concentrations and f1, f2 the mean activity coefficients. The local variations observed in the empirical values of K, chiefly in the Rocky Mountains, led him to advance the opinion that, besides the relative amounts, the nature of the salts present in the solutions had a bearing on the magnitude of the SP. At about the same time Mounce and Rust- ad published laboratory results which emphasized the part played by the shale in the generation of the SP. On the basis of laboratory tests and theoretical considerations, Wyllie in 1948' published the following equation of the electrochemical SP for the case of NaCl solutions, SP= - 71 log (a1)m/(a2)m

Jan 1, 1958

By R. Schuhmann, G. W. Powell

The concept of local equilibrium is examined and, in particular, the applicability of the concept to two-phase binary diffusion couples is discussed. It is concluded that, if binary solid solutions are treated thermodynamically as ternary solutions, vacancies being the third component, then recent experimental observations of nonequilibrium interface compositions (i.e., compositions different from the phase diagram values) are consistent with a state of complete dynamic equilibrium at the interface. CLASSICAL approaches to diffusion and to other irreversible processes often utilize a postulate of "local equilibrium". That is, one assumes even in the presence of gradients, fluxes, and time changes of properties, a) that the Second Law can be formulated locally, and b) that thermodynamic equations of state among intensive properties are identical with those for equilibrium phases. A direct consequence of this assumption, for example, is that one would calculate the total entropy of a nonequilibrium phase simply by integrating the entropy density (eu per unit volume) over the volume of the phase, assuming that entropy density is the same function of energy and particle density as for equilibrium phases. In the study of diffusion and of diffusion-controlled phase transformations, metallurgists take this concept of local equilibrium for granted and utilize it automatically. In fact, experimental evidence of all kinds is overwhelming that "local equilibrium" is a valid limiting law, approached more and more closely as gradients and rates of change approach zero. On the other hand, we have neither experimental nor statistical thermodynamic proof that this principle of "local equilibrium" should remain rigorously valid at high gradients and for rapid processes. Theoretically, in fact, one would expect deviations because interactions between adjacent volume increments of material affect the evaluation of entropy. Also one observes experimentally structural and small energetic differences between equilibrium and nonequilibrium phases. The purpose of this paper is to present a thermodynamic framework for the study and correlation of deviations from strict local equilibrium in isothermal diffusion and related processes. This procedure, in effect, preserves the principle of local equilibrium by thermodynamically assigning the deviations from static equilibrium properties to a defect component. Although this theory is entirely phenomenological, the possibility does exist of correlating the theory with experimental observations of defects under favorable circumstances. The most immediate application appears to be to the equilibria at the interfaces in two-phase binary diffusion couples. A recent pertinent work by Eifert et al.1 has shown that the concentrations of aluminum in the a(fcc) and B(bcc) phases at the 0-8 interface in Cu:Cu-12.5 wt pct A1 diffusion couples are greater than those given by the phase diagram. It is postulated by these authors that the supersaturation of the o phase at the interface provides the driving force for the a-to-B lattice transformation; the excess free energy of the a phase, ?Gaxs, arising from the greater-than-equilibrium aluminum concentration is about 3 cal per g-atom. On the basis of the schematic free energy-composition diagram shown in Fig. 1, Eifert et al. concluded that the thermodynamic situation at the interface is one of the partial equilibrium; that is, = for the more mobile aluminum whereas will be reexamined in the latter part of this paper. THERMODYNAMIC PROPERTIES OF DEFECTS A rigorous analysis of the thermodynamics of defects requires an added degree of freedom in the Phase Rule sense, because the standard formulations of solution thermodynamics (partial molal properties of components, free energy minimization, equality of chemical potentials, and so forth) involve the implicit

Jan 1, 1970