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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 W. R. Hibbard

Although extensive pole figure studies have been reported by Brick1 and others2,3 showing preferred orientations in rolled and annealed 70-30 alpha brass, and by Hermann and Sachs4 in 70-30 alpha brass cups, comparatively little information has been published on textures in drawn 70-30 alpha brass tubes. Crampton5 reported a (110) , [111] texture in drawn brass tubes based on selected individual X ray photograms following the method of Norton and Hiller,6 but the extent and ease of developing this texture and the annealing texture have not been reported and pole figures of these structures were not found in the literature. The present investigation was further stimulated by the possible influence of textures on the mercury stress-corrosion cracking of brass tubes. According to Snoek,7 iron-nickel alloy sheet with a strong cubic texture was more resistant to corrosion than a randomly oriented sheet. Crampton5 reported that single crystals of 70-30 alpha brass drawn into tubes did not crack after 24 hr in a standard mer-curous nitrate test. Edmunds12 found that single crystals of 70-30 alpha brass did not crack in a standard mercurous nitrate test but did crack when subjected to ammoniacal vapor. Wasserman11 reported a similar failure of a single crystal of brass in ammonia. A tube with a strong texture might approach single crystal behavior and tend to resist mercury cracking if the differences in orientation between adjacent grains were sufficiently slight. Preparation OF Specimens Crampton's5 tubes drawn 28 pct reduction in area developed a slight degree of preferred orientation while in tubes drawn 48 pct it was more marked. Based on this information, in order to obtain specimens with markedly different degrees of preferred orientation but with the same final draw, two sets of 70-30 alpha brass tubes were made following the mill schedules shown in Table I. The final draw involved a large reduction in outside diameter, and a ratio of reduction in area to reduction in outside diameter similar to that reported by Crampton,5, 10 to cause mercury cracking of brass tubes. The brass contained 71.31 pct copper, 0.01 pct lead, 0.01 pct iron and zinc by difference. Determination of Pole Figures A 6-in. length from each tube was rotated rapidly by an electric stirrer in 25 pct nitric acid until the gauge was reduced to 0.003-0.005 in. The tubes were carefully cut longitudinally and the walls gently flattened. They were further etched in 25 pet nitric acid to 0.0015 in. thickness and (111) pole figures were determined using copper K-alpha radiation in the manner described by Brick.' The three general types of pole figures

Jan 1, 1949

By W. R. Hibbard

Although extensive pole figure studies have been reported by Brick1 and others2,3 showing preferred orientations in rolled and annealed 70-30 alpha brass, and by Hermann and Sachs4 in 70-30 alpha brass cups, comparatively little information has been published on textures in drawn 70-30 alpha brass tubes. Crampton5 reported a (110) , [111] texture in drawn brass tubes based on selected individual X ray photograms following the method of Norton and Hiller,6 but the extent and ease of developing this texture and the annealing texture have not been reported and pole figures of these structures were not found in the literature. The present investigation was further stimulated by the possible influence of textures on the mercury stress-corrosion cracking of brass tubes. According to Snoek,7 iron-nickel alloy sheet with a strong cubic texture was more resistant to corrosion than a randomly oriented sheet. Crampton5 reported that single crystals of 70-30 alpha brass drawn into tubes did not crack after 24 hr in a standard mer-curous nitrate test. Edmunds12 found that single crystals of 70-30 alpha brass did not crack in a standard mercurous nitrate test but did crack when subjected to ammoniacal vapor. Wasserman11 reported a similar failure of a single crystal of brass in ammonia. A tube with a strong texture might approach single crystal behavior and tend to resist mercury cracking if the differences in orientation between adjacent grains were sufficiently slight. Preparation OF Specimens Crampton's5 tubes drawn 28 pct reduction in area developed a slight degree of preferred orientation while in tubes drawn 48 pct it was more marked. Based on this information, in order to obtain specimens with markedly different degrees of preferred orientation but with the same final draw, two sets of 70-30 alpha brass tubes were made following the mill schedules shown in Table I. The final draw involved a large reduction in outside diameter, and a ratio of reduction in area to reduction in outside diameter similar to that reported by Crampton,5, 10 to cause mercury cracking of brass tubes. The brass contained 71.31 pct copper, 0.01 pct lead, 0.01 pct iron and zinc by difference. Determination of Pole Figures A 6-in. length from each tube was rotated rapidly by an electric stirrer in 25 pct nitric acid until the gauge was reduced to 0.003-0.005 in. The tubes were carefully cut longitudinally and the walls gently flattened. They were further etched in 25 pet nitric acid to 0.0015 in. thickness and (111) pole figures were determined using copper K-alpha radiation in the manner described by Brick.' The three general types of pole figures

Jan 1, 1949

By R. S. Moehlman

IN recent years, exploration and development by diamond drilling has become a popular attack on the problem of finding new ore shoots and developing extensions of known shoots. Diamond drilling has been used in recent years in extensive sampling of disseminated copper deposits, in preference to churn drilling. At the Harvard gold mine, near Jamestown, California, Philip R. Bradley, Jr., general superintendent, reports that: "The Harvard work was a singular example of the reliance that can be placed on diamond drilling in evaluating an ore body." Drilling at the Harvard mine will be discussed in a subsequent section of the paper. So popular has diamond drilling become, indeed, that many who have had slight experience with drilling are inclined to regard it as a cheap cure-all. This paper proposes to show some of the limitations on the application of drilling and some of the steps that should be followed in drilling programs to obtain reliable results. COST OF DRILLING Drilling has the advantage, over shaft sinking and drifting, of lower cost and greater speed. As compared with churn drilling, the advantage of bringing up a coherent sample instead of fine cuttings for a sample is obvious. Diamond drilling is generally more expensive, however, and more engineering effort is required in combining the average of core and sludge samples. Exploration of drift walls by hammer drills to a depth of less than 50 ft. is generally cheaper than diamond drilling, but beyond this depth the diamond drill is cheaper and more efficient. The principal factor in determining cost of drilling is the character of the ground drilled. Broken ground with many fissures is most expensive to drill. Hard ground is less of a problem with diamond drills than with ordinary machine drills. Hardness or softness affects only the speed of drilling. Caving, easily washed, sandy or clayey ground requires continual cementing and casing, which is the greatest cost problem. Thus, soft, incompetent ground is more costly to drill than hard, massive ground. Cost of drilling per foot in good to fair ground varies from less than $1 per foot, achieved in some districts in Ontario, the Mother Lode, and Missouri, to $5 per foot in many western states. In bad drilling ground, costs may range from $5 to $15 or more per foot, thus approaching the cost of drifting. Other factors that increase the cost per foot are: I. Short total length of hole drilled, so that the cost of moving in crews and equipment must be spread over a relatively few feet. 2. Cost of drilling per foot increases with depth beyond about 500 ft., as more time is consumed in pulling rods. 3. Cost of preparing drilling stations, getting air underground to stations, etc. 4. Inaccessibility and lack of water on the job make for higher costs.

Jan 1, 1946

By Daniel R. Hull

IN 1026 Genders' reviewed the existing theories of this subject and stated his views in support of the gas-pressure theory. Again, in 1937, the subject was thoroughly reviewed by N. B. Vaughan,3 and by Phillips and Brick,2 so that no resume is called for here. The purpose of this paper is to describe certain observations made in the course of mill work, and to point out that they mostly tend to confirm the gas theory of Genders. VAPOR SEGREGATION There is, however, one type of inverse segregation that can be accounted for by considering the volatility of one of the constituents of an alloy. The most familiar case is ordinary brass, which is subject to a zinc enrichment of a few tenths of a per cent at the surface of a chill casting. This has been noted in 70-30 brass by Genders, and a typical example of it is given in Table I, which represents a [ ] cylindrical billet 7 in. in diameter by 5; in. long. After lathe-turning 1/32 in. from the surface, the remaining distance to the center was sampled at six equally spaced intervals. The lead, which is essentially the same throughout, will be mentioned later. Consider a brass-mill mold, either round or rectangular in cross section, standing several feet high. It may require a minute or two for pouring. Before it is full, the metal in the lower end has partly solidified and contracted somewhat away from the mold. The initial shell of solidification follows not far behind the top of the column, even if the central portion is liquid for a long way down. There is, then, a space between metal and mold that is filled with zinc vapor. The vapor has no exit, because the liquid at the top of the rising column is not only in contact with the mold but keeps up a fresh supply of zinc vapor, which has, perhaps, already begun to condense in the lower portion. The cycle is short. Within a minute or two after the mold is full the bar has cooled enough to condense all the zinc. Some of it may condense on the mold; it might be expected that most of it would condense there, but the mold at that time is well coated with a velvety carbon residue from the oil dressing, overlain by fluffy zinc oxide that commenced covering the inside of the mold as soon as pouring began. The clean skin of the freshly cast brass offers a preferred surface for condensation. Reabsorption is quick and inevitable. A simple experiment indicates that a surprisingly large quantity of zinc vapor is trapped in the space between mold and

Jan 1, 1941

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

THERE has been little investigation of the gold-germanium binary alloys. Haughton1 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 o.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 12,0 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 eutectic temperature has been determined as 356.0 ± 0.5°C., slightly less than the temperature of 359°C reported by Einecke. The liquidus curves and the solid solubility of germanium 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 1100°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 hypereutectic 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 off 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 metallographic, X-ray, and hardness specimens were 2 to 4 grams.

Jan 1, 1945

By John T. Eash

During the course of the war the supply of tin in this country has steadily decreased and a continued effort has been made since the beginning of the emergency to use alloys that are either tin free or contain appreciably lower quantities of it. Even with the use of emergency materials, the tin supply has become particularly acute, and it is estimated that after recovery of the far eastern mines probably one to two years will be required before our normal annual supply is attained. One of the major tin-consuming fields is the bronze industry. Recommendations were made several years ago by the War Production Board toward the use of bronzes of lower tin content and manganese bronze and yellow brass for the customarily used tin-bronze alloys. The substitution of 88-5-5-2 copper-nickel-tin-zinc for composition G received considerable attention before the war, and consequently this alloy and modifications of it have been adopted for some current structural and pressure castings requiring high mechanical properties. Another of the commonly used bronzes is the 10 per cent tin 10 per cent lead copper alloy for heavy-duty bearings. It has been known for some time that about 2.5 per cent nickel could be substituted for an equal amount of tin with retention of equivalent casting and tensile properties; however, it was desirable that a still greater conservation of tin be made. Consequently the present paper deals with the development of an alloy of low tin content that could be used for bearings. Selection or Composition While the final criterion of the suitability of an alloy for a bearing must of course be determined by practical applications where all the ramifications of service conditions are encountered, certain short cuts in the initial selection of compositions are necessary to avoid an extensive and time-consuming investigation. The present program has been to match certain metallurgical properties of the 80-10-10 bronze that have been shown by previous investigations to be related to good bearing qualities. Such properties as microstruc-ture, hardness, compressive yield strength, ductility, and castability have been considered, and certain simple wear tests have been made. Of the readily assessed characteristics desired in a good bearing alloy, one can be certain that a uniform distribution of lead is required in a leaded bronze. It has generally been found that segregation of lead is one of the chief difficulties with this type of material. Tin has a powerful effect on lead distribution, and with 10 per cent present produces a random distribution of chunky particles, such as are shown in Fig' 1. I' In the tin bronze contains the hard alpha + delta

Jan 1, 1946

By John T. Eash

During the course of the war the supply of tin in this country has steadily decreased and a continued effort has been made since the beginning of the emergency to use alloys that are either tin free or contain appreciably lower quantities of it. Even with the use of emergency materials, the tin supply has become particularly acute, and it is estimated that after recovery of the far eastern mines probably one to two years will be required before our normal annual supply is attained. One of the major tin-consuming fields is the bronze industry. Recommendations were made several years ago by the War Production Board toward the use of bronzes of lower tin content and manganese bronze and yellow brass for the customarily used tin-bronze alloys. The substitution of 88-5-5-2 copper-nickel-tin-zinc for composition G received considerable attention before the war, and consequently this alloy and modifications of it have been adopted for some current structural and pressure castings requiring high mechanical properties. Another of the commonly used bronzes is the 10 per cent tin 10 per cent lead copper alloy for heavy-duty bearings. It has been known for some time that about 2.5 per cent nickel could be substituted for an equal amount of tin with retention of equivalent casting and tensile properties; however, it was desirable that a still greater conservation of tin be made. Consequently the present paper deals with the development of an alloy of low tin content that could be used for bearings. Selection or Composition While the final criterion of the suitability of an alloy for a bearing must of course be determined by practical applications where all the ramifications of service conditions are encountered, certain short cuts in the initial selection of compositions are necessary to avoid an extensive and time-consuming investigation. The present program has been to match certain metallurgical properties of the 80-10-10 bronze that have been shown by previous investigations to be related to good bearing qualities. Such properties as microstruc-ture, hardness, compressive yield strength, ductility, and castability have been considered, and certain simple wear tests have been made. Of the readily assessed characteristics desired in a good bearing alloy, one can be certain that a uniform distribution of lead is required in a leaded bronze. It has generally been found that segregation of lead is one of the chief difficulties with this type of material. Tin has a powerful effect on lead distribution, and with 10 per cent present produces a random distribution of chunky particles, such as are shown in Fig' 1. I' In the tin bronze contains the hard alpha + delta

Jan 1, 1946

By Robert E. Cuthbertson

IT is the purpose of this paper to describe in detail the laboratory development and mill application of an unusual combination of flotation reagents employed in the concentrator of the Climax Molybdenum Co., on the Continental Divide, near Leadville, Lake County, Colorado. This development originated in an ore-dressing research laboratory maintained by Climax at the experimental plant of the Colorado School of Mines, which is staffed by men directly employed by the Climax Molybdenum Co. Mill-scale testing of laboratory developments was supervised by a representative from the testing laboratory, working in close cooperation with the operating staff at the mill. General milling practice at Climax is ably described in a paper by E. J. Duggan,1 mill superintendent. Other aspects of the Climax project have been described in papers by W. J. Coulter,2 by Butler, Vanderwilt and Henderson3 by Allen Kissock,4 and by Leo H. Glanville.5 Consequently, this paper will be confined to the metallurgical aspects of recent reagent developments, avoiding, as much as possible, repetition of material covered in these earlier publications. BRIEF HISTORY OF REAGENT PRACTICE AT CLIMAX Prior to the year 1937, the only reagents employed at Climax for froth production and collecting action in the flotation of molybdenite were steam-distilled or destructively distilled pine oils. The only exceptions to this practice were brief periods of mill testing, when reagents of various types were tried on an experimental basis. None of these experimental runs was sufficiently encouraging to justify its continuation as regular practice. Sodium, cyanide has been employed since the very early days of milling at Climax as an inhibiting agent for control of pyrite and chalcopyrite. Alkaline reagents such as lime or soda ash have been used in recent years to minimize the detrimental effect of iron salts on flotation of molybdenite. The presence of these harmful salts is attributed to the decomposition of fine metallics abraded from liners and balls in the first stage of regrinding rougher concentrate. Flint pebbles are used in subsequent regrinding, since alkaline reagents are not entirely adequate to offset the inhibiting effect of iron salts as the grind becomes progressively finer and the grade of concentrate progressively higher. Climax metallurgists were familiar at an early date with the use of petroleum products such as kerosene and gas oil as promoters of flotation of molybdenite. Charles C. Oliver6 discussed the use of pine oil and kerosene as early as 1920, in connection with the milling practice at Dominion Molybdenite Co., Quebec. Never theless, the early attempts to apply this knowledge in the Climax concentrator were complete failures. In the light of recent experience, it may seem strange that the early mill tests with petroleum

Jan 1, 1944

By Walter E. Duncan

THE ores treated at the concentrating plant largely come from the blanket replacement deposits of the northeastern part of Hardin County, Illinois, and consist of complex mixtures of galena, sphalerite and fluorspar in a gangue of quartz, limestone and sandstone. The several minerals are so intimately intergrown that they are not liberated at the sizes usually treated by gravity concentration in the usual fluorspar plant. For this reason, an all-flotation method of concentration was developed in cooperation with the station of the U. S. Bureau of Mines at Rolla, Mo.1 This flotation separation made possible the commercial production of four concentrates: (I) lead concentrates, (2) zinc concentrates, (3) acid-grade fluorspar concentrates and (4) metallurgical-grade fluorspar concentrates.2,3 Although fluorspar had been floated in Canada in 1921 4 and a plant at Rosiclare had been floating fluorspar since March 1929, fluorspar flotation was given considerable impetus by the Mahoning developments, since some features of the separation were quickly adopted by other fluorspar companies. The Bureau of Mines5 reports that in the 10 years preceding 1938 only 50,552 tons of fluorspar flotation concentrates were produced in the United States. The rise from this almost nominal figure to 153,750 tons (largely acid grade) in one year (1944)6 is indicative of the activity in fluorspar flotation occasioned by the war. The industry thus proved to be in a position to expand and keep up reasonably well with the requirements imposed upon it by such developments as occurred in high octane aviation gasoline alkylation, in the use of Freon as a refrigerant and as carrier in the Aerosol "bug bomb," and in the atomic bomb project as well as in the expansion of other activities requiring hydrofluoric acid; such as, for example, the aluminum industry. Despite the fact that the greater portion of acid-grade fluorspar produced in the last few years went directly into war uses, the future of the acid-grade field still appears bright. As a result of the activity in fluorine chemistry during the war, it seems likely that in the relatively near future almost every phase of human endeavor will find some fluorine compound involved. The other three concentrates produced deserve some attention in these introductory remarks. The lead concentrates first produced contained both zinc and fluorspar but these did not interfere with their marketing. As will be pointed out later, the quality has steadily improved until today it is a relatively high-grade product. Although some zinc smelters accept concentrates containing limited quantities of fluorspar, it is a very objectionable impurity. Since flotation methods fail in the complete removal of the fluorspar, chemical methods were developed for

Jan 1, 1946

By M. C. Leverett

Knowledge of the theory underlying the behavior of mixtures of fluids in reservoir rocks is essential to the proper solution of certain types of problems in petroleum production, but is as yet incompletely developed. The object of this paper is to show the application of well established thermody-namic and physical principles to these problems, and thus to assist in the development of the basic theory. For convenience the problems to be considered here may be divided into two groups: 1. Static problems, involving only the static balance between capillary forces and those due to the difference in densities of the fluids; i.e., gravitational forces. 2. Dynamic problems, involving analysis of the motion oi mixtures of immiscible fluids in porous media under the influence of forces due to gravity, capillarity, and an impressed external pressure differential. Capillary Equilbrium in Sands Under this heading the static type of problem will be discussed and the results of experimental investigations on the capillary properties of unconsolidated sands will be presented. Although the discussion of this section is, in a sense, prefatory to the treatment of problems of mixture flow, the concepts developed here have considerable intrinsic importance apart from their ap-plication to flow problems. For, it is reason-able to postulate that the reservoir fluids are, owing to their long existence in undis- turbed mutual contact prior to exploitation, in substantial equilibrium. It follows that their distribution in the reservoir at the time of tapping should be entirely predictable from the theory of capillary equi librium, provided certain experimentally measurable properties of the reservoir rock are known. Knowledge of the distribution of the several fluids in the reservoir is, ol course, helpful in the estimation of reserves and in other problems. It is to be emphasized that throughout the discussion of capillary statics it is assumed that the fluids are in equilibrium from the capillary standpoint. Thus, water, where it is referred to as being in a reservoir, will be understood to be interstitial water, present at the time of drilling the reservoir, commonly termed "connate" water. The theory developed here is perfectly general for any porous solid, whether a carefully prepared unconsolidated sand or a natural sandstone from an oil reservoir. At present, however, only problems involving clean, unconsolidated sands can be made to yield numerical solutions, since only such sands have been adequately investigated experimentally. Experimental evaluation of the pertinent properties 01 natural reservoir rocks will permit the extension of the numerical treatment to problems involving these materials. We shall now consider in some detail the static equilibrium of fluid mixtures in porous solids: that is, the manner in which the reservoir fluids are distributed vertically whell the Forces due to capillarity are just balanccd by those due to gravitation.

Jan 1, 1941

By M. C. Leverett

Knowledge of the theory underlying the behavior of mixtures of fluids in reservoir rocks is essential to the proper solution of certain types of problems in petroleum production, but is as yet incompletely developed. The object of this paper is to show the application of well established thermody-namic and physical principles to these problems, and thus to assist in the development of the basic theory. For convenience the problems to be considered here may be divided into two groups: 1. Static problems, involving only the static balance between capillary forces and those due to the difference in densities of the fluids; i.e., gravitational forces. 2. Dynamic problems, involving analysis of the motion oi mixtures of immiscible fluids in porous media under the influence of forces due to gravity, capillarity, and an impressed external pressure differential. Capillary Equilbrium in Sands Under this heading the static type of problem will be discussed and the results of experimental investigations on the capillary properties of unconsolidated sands will be presented. Although the discussion of this section is, in a sense, prefatory to the treatment of problems of mixture flow, the concepts developed here have considerable intrinsic importance apart from their ap-plication to flow problems. For, it is reason-able to postulate that the reservoir fluids are, owing to their long existence in undis- turbed mutual contact prior to exploitation, in substantial equilibrium. It follows that their distribution in the reservoir at the time of tapping should be entirely predictable from the theory of capillary equi librium, provided certain experimentally measurable properties of the reservoir rock are known. Knowledge of the distribution of the several fluids in the reservoir is, ol course, helpful in the estimation of reserves and in other problems. It is to be emphasized that throughout the discussion of capillary statics it is assumed that the fluids are in equilibrium from the capillary standpoint. Thus, water, where it is referred to as being in a reservoir, will be understood to be interstitial water, present at the time of drilling the reservoir, commonly termed "connate" water. The theory developed here is perfectly general for any porous solid, whether a carefully prepared unconsolidated sand or a natural sandstone from an oil reservoir. At present, however, only problems involving clean, unconsolidated sands can be made to yield numerical solutions, since only such sands have been adequately investigated experimentally. Experimental evaluation of the pertinent properties 01 natural reservoir rocks will permit the extension of the numerical treatment to problems involving these materials. We shall now consider in some detail the static equilibrium of fluid mixtures in porous solids: that is, the manner in which the reservoir fluids are distributed vertically whell the Forces due to capillarity are just balanccd by those due to gravitation.

Jan 1, 1941

By E. H. Kelton, R. D. Grissinger

In designing structural members of steel and some other materials the design engineer has available recognized values of elastic modulus and safe working stress that may be substituted in well-known engineering formulas to give him desired cross-sectional areas and deflections for a particular part. Zinc, on the other hand, has no generally recognized modulus. It flows under continuously applied loads. Therefore, the designer of structural members must use a range of working stresses depending on the continuous load and the amount of permissible distortion. The only method of obtaining these values is by creep testing. Creep testing of zinc has been carried on for some 20 years by this laboratory, covering a wide range of zinc and zinc alloys. Types of test included tension, compression, and simple and cantilever beams at temperatures ranging from o to I50°C. Specimen conditions ranged from as-cast or as-rolled to accelerated aged in steam or dry air. Effects of plating were investigated also. It is not the intention of this paper to expound all these factors but rather to present the final data on well-known zinc die-casting alloys and to suggest means of applying these data to engineering design. Early Work In the early work on creep testing of zinc, the direct-loading tension method was used. However, direct loading of die castings was unsatisfactory because of the high loads required. For instance, a standard die-cast tension bar having a cross-sectional area of about 0.049 sq. in. would require a direct load of about 1000 lb. for a unit stress of 20,000 lb. per sq. in. Also, tests were made at nominal room temperature, but normal variations caused fluctuations greater than those due to experimental error or other causes, so that control of this variable within ±1/2°C. seemed essential. These two factors led to the development of an apparatus described by J. Ruzicka,' in which the specimens were loaded by means of a lever and were held at constant temperature by means of an oil bath. While Ruzicka's apparatus yielded excellent check results, it seemed desirable to have some setup by which literally hundreds of die-cast specimens could be tested at the same time. This would permit the conducting of a number of low-load tests designed to run 10 years or longer and still leave capacity for current high-load work. Beam testing in a constant-temperature room was the answer. Test Method Preliminary work indicated that die-cast beams of various lengths and cross scctions yielded the same result within reasonable limits regardless of whether they were tested as simple beams, uniformly loaded beams, or cantilevers. Accordingly, the simplest type was adopted. This was a,

Jan 1, 1945

By J. H. Hollomon, J. C. Fisher

THE fundamental problem concerning the fracture of both crystalline and noncrystalline solids is the divergence between the actual and the theoretically computed fracture stresses; the stress required for fracture, computed from the forces between atoms, is many times that actually observed with commercially available materials. Computations have been made1, 2 indicating that the theoretical fracture stress should be from 100 to 1000 times that actually observed. There are other incidental problems that have arisen, perhaps the most important of which is the problem of size effect often observed in the measurement of the fracture stress of non-metallic solids, such as glass. Another effect concerns the relation between deformation and the stress required for fracture. Experiments recently made with pearlitic steels indicate that the tensile fracture stress increases with increasing tensile deformation and decreases with increasing prior compressive deformation. This marked anisotropy of the effect of deformation on the fracture stress is in contrast with the essential isotropy of the flow stress. Early experiments on rock salt crystals by Joffé, et a13 have illustrated the effect of tensile strain in increasing the tensile stress required for fracture. A consistent theory must be constructed that will explain not only the divergence of the measured fracture stress from the theoretical value, the size effect, and the effect of deformation; but will also explain and predict the effects of combined stress, of temperature, of strain rate, and of metallurgical structure. With respect to this last variable, it has now been relatively well established that the carbide particle is the element of structure controlling the fracture of steels. In steels carbide particles vary in shape from plates to spheroids. It has been found that not only does the magnitude of the fracture stress depend upon the size and shape of these particles, but also its dependence upon strain is affected by changes in shape and size of the particles. The precipitate resulting from the age hardening of duralumin also modifies the fracture stress of this alloy. Nonmetallic inclusions greatly lower the fracture stress of all metals. The magnitude of the lowering depends on the size and shape of the included particles. In glass, the major source of the low fracture stress has been fairly conclusively demonstrated by Griffith4 to arise from real flaws or cracks present in the material. He showed that the stress concentration at the end of a defect was of sufficient magnitude to raise the stress at this location to a value comparable with the theoretical strength of the material. If the cracks were reduced in size, Griffith showed that the observed fracture strength increased by virtue of the decrease in stress concentration. He also pointed out that cracks disposed perpendicularly to the applied tensile stress would be more effective in lowering the fracture

Jan 1, 1947

By R. J. Borg, C. E. Birchenall

Vapor pressures of eight compositions of Mg-Cd have been determined by the Knudsen effusion technique. Measurements are made at several temperatures for each alloy and the results interpolated to a common temperature for the calculation of the activities. It is not possible to obtain values for the partial molar enthalpies because of the narrow temperature range spanned by the measurements. The results show less precision than those obtained for pure Cd which are also reborted. These alloys are extremely susceptible to corrosion which provides a possible explanation for the lack of precision. Nevertheless, the values of the activity are in good agreement with the results of electromotive force measurements previously reported for the Mg-Cd system. MAGNESIUM and cadmium are mutually soluble in all proportions in the solid state and form a single phase which has the hexagonal close-packed structure. X-ray investigations of this system1,2 have revealed a rapid variation in the relative dimensions of the unit cell occurring at approximately 50 at. pct. The rate of change of the c/a ratio with composition increases markedly for alloys containing more than 50 at. pct Cd. The purpose of this investigation was to determine the activity of Cd in the neighborhood of 50 at. pct and to discover whether or not the thermo-dynamic properties undergo a similar rapid change. The activities are calculated from vapor pressure data obtained by the Knudsen effusion method. Unfortunately the precision of the data from which the thermodynamic values are calculated is insufficient to establish unequivocally a departure from the normal trend. The results are reported primarily because they substantiate the only previously reported activity measurements3 and because they include values for pure Cd which in contrast to those of the alloys show excellent precision. The Cd-Mg system is known to contain several ordered phases. However, this investigation was made at temperatures considerably above the transition temperatures, and the alloys may be regarded as nearly random solid solutions. EXPERIMENTAL Apparatus—The effusion cells are machined from solid tantalum rod. The lids consist of threaded, flanged rings of tantalum onto which are welded shallow cups of 4 mil molybdenum foil. The orifice, which is located at its center, is made by grinding off a small dimple produced with a sharpened punch. Such an orifice has been mounted in plastic, sectioned, and the thickness of the orifice edge measured in a microscope. The maximum thickness is 0.00016 in., and the Clausing factor is consequently equated to unity. The area of the orifice is determined by tracing its projection on the screen of the metallograph at a known magnification and measuring the area of the tracing with a planimeter. Excellent temperature control is achieved with a 4 by 18-in. alundum core, gradient-wound, furnace

Jan 1, 1960

By A. A. Jr. Smith, J. S. Smart

Numerous investigations of the effects of the various impurities common to commercial coppers have been published, and the data have found wide use in industry. Naturally, emphasis has been placed on the oxygen-bearing coppers of the tough-pitch variety, but need is now evident for data covering the oxygen-free condition as well. Furthermore, relatively few of the important reactions between oxygen and the various impurities are well understood, and often the data at hand are not applicable to the low concentrations encountered in commercial coppers. This paper presents the changes in conductivity and softening temperature derived from individual additions of the group VIII triad, iron, cobalt and nickel, to high-purity copper, and constitutes a portion of the copper-research program being conducted at the Central Research Laboratory of the American Smelting and Refining Co. The method of preparation of high-purity copper and its alloys in either the oxygen-free or oxygen-bearing form has been described previous1y.l The purity of this material, and the methods developed to produce it, provide the means for direct investigation of the very low concentration range in which the various impurities generally exist in commercial coppers. The usual necessity for extrapolation to this range using the results obtained from higher concentrations, and the interfering effects of extraneous impurities, are thus simultaneously circumvented. Since previously published data have adequately presented the effects of higher concentrations of iron, cobalt and nickel, the present investigation has been confined to the composition range o to 0.05 per cent. All alloys were initially prepared in the form of oxygen-free continuous cast rod, the weighed alloying additions in suitable form being charged with the pure copper to the continuous casting crucible. The best of the available high-purity alloying materials were used, and spectrographic analyses confirmed the absence of interfering elements from the alloys formed. Each series was compounded in the direction of increasing concentration, starting with pure copper in a new crucible and finishing with the 0.05 per cent alloy. Composition was closely controlled by adding the alloying element in the form of a carefully compounded and analyzed master alloy rendered uniform by continuous casting. The accuracy of this method of synihesis was proved by chemical analysis of the more concentrated alloys, and, accordingly, there is every reason to credit the stated composition of the very dilute alloys in the range where chemical analysis becomes highly uncertain. Oxygen-free samples for measurements of conductivity and softening temperature Were obtained by drawing the continuous cast rod to wire of 0.08I-in. diameter. employing a number of intermediate anneals to refine the grain structure. The

Jan 1, 1942

By Tell Ertl

THE Piceance Creek Basin in northwestern Colorado is believed to contain the richest large deposit of oil shale in North America. The major portion, about 1650 sq miles, is bounded by the White River on the north, the Grand Hogback, which runs from Meeker to Rifle, on the east, the Colorado River to the south, and the drainage basin of Salt and Douglas Creeks on the west. The Basin is a plateau 7000 to 9000 ft high, composed of 3000 ft of the Green River series of Eocene age and surrounded by a steep escarpment of 1000 to 3000 ft. From the escarpment the beds dip gently toward the center. Although oil shale is found in all members of the Green River series, the rich thick beds are found chiefly in the Parachute Creek member. This is normally capped by 100 to 200 ft of the Evacuation Creek, the youngest member of the Green River series. Actually the Piceance Creek Basin oil shale is not a shale, nor does it contain oil. It is magnesium marlstone holding solid organic matter capable of being broken down by heat into gases, some of which can be condensed into oil. The marlstone is resilient nonporous rock, difficult to sample by pick or hammer and moil. Many companies and individuals prospected the Colorado oil shale shortly after the first World War,' see Fig. 1, but because of the discovery of large quantities of petroleum in the late 1920's in Cali- fornia, Oklahoma, and East Texas, interest in oil shale development waned and did not revive until World War 11. In 1944 the writer, employed by the Bureau of Mines, prospected the high grade oil shale in numerous places along the southern outcrop of the Piceance Creek Basin. Several channel samples about 100 ft in length were cut, see Fig. 2. An eight-man crew needed a week to cut a satisfactory channel 80 ft long in the cliff face. The Phillips Petroleum Co., the Union Oil Co. of California and others also prospected the oil shale outcrop. In 1945 the Bureau of Mines initiated a core drilling program for the purpose of obtaining accurate samples from the Piceance Creek Basin. The U. S. Geological Survey set up a program for the geological study of the Basin that is still going on." Until the end of 1951 a total of 31 holes was drilled for core with diamond drills, and, in addition, cuttings through the oil shale have been obtained from 4 gas wells drilled by standard rotary oil well rigs. The Bureau of Mines drilled 12 of the holes, the Union Oil Company of California 8, the Standard Oil Company of California 6, the Sun Oil Company 3,

Jan 1, 1953

By R. Schumann

THE expression "unit process " comes up with increasing frequency in discussions among metallurgists and mineral engineers, especially among those concerned with training the next generation. The unit process approach characterizes a significant advance along the road from metallurgy as an empirical art to metallurgy as a branch of engineering. The purposes of this paper are to define and list the unit processes in specific terms, to indicate the scientific and engineering principles basic to all the unit processes, and finally to show how these ideas have been applied to a reorganization of instruction in chemical metallurgy. UNIT OPERATIONS AND UNIT PROCESSES Metals are extracted from ores and other raw materials by stepwise procedures. In general, each metallic element is extracted by a different procedure. For many of the metals there is a choice of several flowsheets. However, the procedures all have steps in common. In fact, the many different flowsheets are all made up of a relatively small number of steps which are combined in different groups and sequences. For example, crushing, screening, roasting, sintering, melting, and gaseous reduction are steps which each appear in the flowsheets for extracting the majority of the metals. The individual steps or flowsheet units can be designated as unit operations or unit processes. These terms are well established in the field of chemical engineering, as the American Institute of Chemical Engineers' definition of chemical engineering shows: " Chemical engineering is that branch of engineering concerned with the development and application of manufacturing processes in which chemical or certain physical changes of materials are involved. These processes may usually be resolved into a coordinated series of unit physical operations and unit chemical processes. The work of the chemical engineer is concerned primarily with the design, construction, and operation of equipment and plants in which these unit operations and processes are applied. Chemistry, physics, and mathematics are the underlying sciences of chemical engineering, and economics its guide in practice."1a In this definition, the distinction between unit operations and unit processes is that the unit operations are physical while the unit processes are chemical. Table I gives a list of the principal unit operations and unit processes of chemical engineering, taken from Shreve. lb Table 2 lists the principal unit operations and unit processes used for metal extraction. The division between unit operations and unit processes is similar to the chemical engineers' distinction and also corresponds approximately to the division of labor between mineral dressing and chemical metallurgy which has been customary in the past. Furthermore, it will be noted that in the proposed classification the unit processes primarily involve chemical reactions and/or changes in state of aggregation; the unit operations, primarily do not involve either bulk

Jan 1, 1948

By L. B. Ticknor, M. B. Bever

An isothermal calorimeter suitable for measurements of heats of solution in liquid tin as solvent is described. Measurements of the heats of solution of gold, silver, copper, and a gold-silver alloy are reported. The heat of formation of this gold-silver alloy is also reported. HEATS of solution in liquids can be determined directly, but few such data have been published for metals as solvents. Knowledge of heats of solution is desirable because it contributes to the general understanding of energy relations in metallic solutions. Thermochemical measurements of this type also furnish answers to specific problems: For example, from the heats of solution of an alloy and of a mixture of its constituent elements in a given solvent, the heat of formation of the alloy may be found. Similarly, differences in the energy content of samples of the same metal in two different states, such as the annealed and cold worked states, may be determined. In the work reported here, gold, silver, and an alloy of gold and silver were dissolved in liquid tin at 240°C and gold, silver, and copper were dissolved in tin at 300 °C. The experiments yielded the heats of solution of these metals in tin. The heat of formation of the gold-silver alloy was also determined. The same calorimetric method is being used to measure the energy stored in metals during cold working and preliminary results have been published.' Equipment and Experimental Procedure The isothermal calorimeter used in this work, Fig. 1, consisted of a Dewar flask completely immersed in a constant-temperature salt bath. A long neck provided space for thermocouple leads and a stirrer shaft and permitted the injection of solute samples. The metal bath in the calorimeter flask was stirred at about 100 rpm by a small glass impeller driven by a constant-speed motor. The shaft of the stirrer passed through a Wilson vacuum seal.2 All measurements were made under vacuum in order to eliminate temperature disturbances resulting from gas convection and to prevent the oxidation of tin. The calorimeter flask was joined by an all-glass connecting line to a gas-control system which made possible the use of a protective atmosphere of deoxidized and dried hydrogen. At the operating temperature of the calorimeter tin oxide was not reduced by hydrogen, presumably because the reaction rate was too slow. Part of the closed system was a removable side tube through which the solute sample could be introduced and in which it was held at a temperature of 0°C prior to injection into the metal bath. The salt bath containing a mixture of sodium, lithium, and potassium nitrates was similar to that described by Beattie3 and was equipped with a stir-

Jan 1, 1953

By Arthur Phillips, E. N. Skinner

DURING the course of an experimental program concerned with the hydrogen embrittlement of copper containing oxygen in concentrations within the solubility limits it became necessary to make a critical appraisal of the literature dealing with the solubility relationships of oxygen and solid copper. The latest determinations, and perhaps the only data obtained on "spectroscopically" pure copper, are those of Rhines and Mathewson1 who reported that the solid solubility increases from 0.007 per cent oxygen at 600°C. to about 0.015 per cent at 1050°C. Hanson, Marryat and Ford2 had previously placed the solubility limit at less than 0.009 per cent oxygen at 1000°C. and Allen and Street3 had suggested, on the basis of an unpublished research by T. Hewitt, not over 0.005 per cent oxygen at 500°C. In the introductory stages of the investigation indirect evidence accumulated to suggest that the solubility limits were significantly lower than those previously reported. For this reason it was deemed essential to clarify this point before proceeding with a program intended to establish a quantitative relationship between hydrogen embrittlement and oxygen concentrations positively known to be within the solid solution range. Furthermore, the increasing production and the highly selective applications of the commercial "oxygen-free" coppers inevitably direct attention to the practical necessity for exact knowledge regarding the effects of minute concentrations of the elements ordinarily found in the high-purity coppers now available. Of these elements oxygen occupies a unique position, not only by virtue of its specific effects on copper but more particularly in view of its important reactive tendencies toward the other impurities with which it is associated. Rhines and Mathewson considered several methods for measuring the solubility of oxygen and finally adopted the simple plan of saturating the specimens, obtained from redeposited cathode copper, by heating at the desired temperature in air. After the removal of surface oxide by mechanical and chemical means, the oxygen content was determined in the underlying metal. In general, this process of saturation, with a few modifications, was followed by the present writers. Although the procedure is direct and has obvious advantages, its effectiveness, unfortunately, is reduced by an excessive scaling of the copper, particularly at the higher temperatures. After saturation treatments above 900°C. the writers found that the specimens, necessarily rather thin in the original condition, consisted largely of scale and yielded too little metal for a satisfactory analytical sample. Furthermore, great difficulty was experienced in effecting complete removal of the scale. Needless to say, it is necessary to exercise extraordinary care in the preparation of the surface of the analytical sample in order to eliminate submicroscopic fragments of cuprous oxide which ordinarily are lodged in the crevasses and

Jan 1, 1941