Search Documents

By C. E. Birchenall, W. Batz, H. W. Mean

AT temperatures between 1095' and 1347ºC, 13 runs have been made on the diffusion of silicon in iron. In two of the runs the couple compositions were entirely within the loop of the Fe-Si system; the base alloys contained 0.0 and 1.0 wt pct Si. The other runs in which the couples consisted of a 2.3 wt pct Si alloy welded to a 3.7 pct Si alloy were a phase throughout. The alloys were made by melting electrolytic iron and commercially pure silicon. Trace impurities were not determined. The butt welded couples were diffused in an inert atmosphere of argon or hydrogen. After cooling, cuts of two mils or greater thickness were machined parallel to the weld interface. The chips were analyzed for silicon. When the concentration and distance data were examined on the conventional probability plot,' no marked variation of the diffusion coefficient with concentration was indicated over the narrow composition ranges employed. Therefore, a single diffusion coefficient is recorded for each run in Table I. The temperatures and atmospheres of the diffusion anneal are listed along with the compositions of the base alloys. For a iron the silicon diffusion coefficient is given by the equation: D = 0.44 e-48,000/RT where R is the gas Constant and T, the absolute temperature. However, since the scatter in the data is fairly large, the activation energy may be in error by as much as 6000 cal per g-atom. The two ? iron points do not permit estimation of the activation energy with any reasonable certainty. They do indicate that the coefficients reported by Smithells2 and Jost,3 based on the work of Fry,4 are much too high. Although very dilute solutions in iron of manganese,5 nickel,8 cobalt,7 and molybdenum8 give dif- fusion coefficients quite close to those obtained for self-diffusion in iron, the silicon values are considerably higher, though of the same order of magnitude. This seems to be consistent with the fact that the silicon atom is the only one of those listed here which is appreciably smaller than iron. The authors are grateful to the Office of Naval Research for their support of this work under Contract N6ori-47, Task order IV, Project NR 031-184, to J. K. Stanley and the Westinghouse Research Laboratories for the silicon alloys used, to several steel companies for the silicon analyses, and to C. Wells, of the Metals Research Laboratory, Carnegie Institute of Technology, for numerous suggestions during the course of the work. References 'C. Wells: Atom Movements (1951) Chapter 2. A.S.M. 2C. J. Smithells: Metals Reference Book (1949) p. 405. Interscience. Pub. Co. 3W. Jost: Diffusion (1952) p. 223. Academic Press. 4 A. Fry: Stahl und Eisen (1923) 43, p. 1039. T. Wells and R. F. Mehl: Trans. AIME (1941) 145, p. 315. "C. Wells and R. F. Mehl: Trans. AIME (1941) 145, p. 329. 7M. F. Hawkes and R. F. Mehl: Trans. AIME (1947) 172, p. 467; Metals Technology (August 1947). .J. L. Ham: Trans. A.S.M. (1945) 35, p. 331.

Jan 1, 1953

By J. F. Wilson

An experimental investigation has been made of gas-driven slug displacements in a system of high gas saturation to evaluate the process for use in a California reservoir. Fluid compositions, temperature, pressure and core permeability duplicated reservoir conditions as closely as possible. The temperature was above the critical of the slug materials. The slug composition required for 100 per cent oil recovery in the linear flow systems was found to agree with that determined from equilibrium phase studies. A qualitative theory for the slug displacement of two-phase systems is proposed and found to be in general agreement with the observed flow behavior. The theory predicts that the length of the reservoir fluid-slug transition Zone will increase with increased initial gas saturation and decrease with increased oil swelling accompanying the composition change from reservoir oil to the critical composition. The precipitation of small amounts of an asphaltic phase during the formation of the transition zone had no adverse effects on the flow behavior of otherwise miscible systems. INTRODUCTION Despite the large number of recent publications relating to oil recovery by miscible displacement, little information is available concerning the behavior of crude oil-natural gas systems at conditions likely to be encountered in field application. The laboratory data reported here were obtained during an investigation of the possibility of using a gas-driven LPG slug in a partially depleted California reservoir. Seven gas-driven slug displacements employing slugs of different compositions and sizes were made in 26- to 27-ft long sandstone cores. The equilibrium phase behavior of the systems was also determined. The features of primary interest in this study are the following. 1. Data were obtained on the displacement of reservoir fluids at reservoir conditions. 2. A high gas saturation existed in the long cores at the start of the displacements. 3. The temperature of the studies was above the critical of the slug materials. 4. A comparison between the flow behavior and equilibrium phase behavior, as illustrated by a pseudo-ternary phase diagram, is afforded for a system of considerable complexity. THEORY Phase Behavior The use of the pseudo-ternary phase diagram to illustrate the phase behavior in miscible displacements has been discussed by Clark, Schultz and Shearin. Sie-vert, Dew and Conley and Arnold, Stone and Luffel' have presented both phase equilibrium and flow data for true ternary systems. For the true ternary, the application of the theory is straight-forward; for a reservoir system represented as a ternary, the theory undoubtedly gives a qualitatively correct picture. One purpose of this investigation was to see if the pseudo-ternary phase diagram could be used to predict with reasonable accuracy the conditions necessary for miscible displacements with actual reservoir systems. MiscIBLE Displacement of Two-Phase System A large number of papers "I3 have treated the miscible displacement of a single-phase fluid from both an experimental and a theoretical viewpoint. However, the normal field application of the process will be in a partially depleted reservoir. Often the state of the system will be such that the mobility of the gas phase is greater

By A. S. Koster, G. D. Rieck

X-ray experiments were carried out to show the occurrence of cylindrical texture in drawn tungsten wire. Only a small amount of (110) (110) cylindrical texture could he found in wires of intermediate thickness, i.e., of about 1.5 mm diameter. DRAWN wires of tungsten and other bcc metals like iron and molybdenum show a well-established (110) fiber texture. Now it might be conceivable that in drawing radial stresses remove the randomness of the crystallites around the [110} axis, thus giving a fiber texture of higher symmetry. In the resulting so-called cylindrical textures a specified plane normal coincides with the radius of the wire. Several authors discuss the occurrence of cylindrical textures in bcc metals. ~ieck' found no cylindrical texture in drawn tungsten wires of 165 n diameter. Leber~ states that in tungsten wires of 3 mm diameter a cylindrical {100)(110) texture is developed, which is gradually converted to a normal fiber texture by subsequent drawing. He also reported a definite cylindrical texture at the surface of iron wires. Peck and Thomas3 observed a nonuniform mode of deformation of the grains in transverse sections of heavily drawn tungsten and iron wires. According to Bhandary and cullity4 a swaged iron wire has neither a perfect (110) fiber texture nor a perfect {100}(110) cylindrical texture. It is clear that the concept of cylindrical texture in bcc metals still lacks a firm experimental basis. Leber's eviden~e,~ which seems to be the strongest, rests upon qualitative interpretation of photographs. The appearance of the 110 and 200 lines on the photograph of 3-mm wire, however, can be very well attributed5 to a normal ( 110) fiber texture superimposed on random background; our Fig. 1, giving a Debye-Scherrer diagram of etched tungsten wire of 180 p, is free of cylindrical texture according to all authors, but is quite similar to Leber's diagram. It was therefore decided to use a different method of X-ray texture determination on tungsten wires of diameters where cylindrical textures may be expected.

Jan 1, 1965

By Hugh M. Roberts, R. D. Longyear

Introduction ............................ 27 GEnERal Geology........................... 29 The ORebodY in Western Falco~ridgI TownsRip........... 31 Quartzite-Graywacke Formation................... 33 Greenstone............................ 33 Norite ............................. 33 Metamorphism.......................... 35 The Orebody........................... 36 Mineralogy ........................... 37 Grade of Ore........................... 42 Genesis oF tEe Ores . :....................... 43 Summary of Various Hypotheses.................. 44 Magmatic Segregation by Crystallization of Sulphides........ 44 Gravitational Segregation of Molten Sulphides at the Base of the Magma 45 Intrusion of Molten Sulphides after the Consolidation of 'he Nurite.. 45 Deposition by Hydrothermal Solutions.............. 46 Magmatic Segregation by Extraction from Crystallizing Norite... SO The Relationship between the Exploration and Theories of Origin .... 50 Volume Relations of Norite and Sulphides............... 62 Intimate Association of Norite and Sulphides............. 53 Granitic Material........................ 54 Uniform Content........................ 54 Sulphides in Walls......................... 54 Absence of Typical Hydrothermal Minerals.............. 55 SUmmaRY................................ 56 Introduction During 1916 and 1917. the E. J. Longyear Co. of Minneapolis. Minn., carried out a campaign of exploration for nickel-copper ore in the Sudbury District of Ontario. The work was initiated by W. E. Smith. a resident of Sudbury. who called the attention of W. J. Mead. Chief Geologist

Jan 1, 1918

By C. L. Warwick, A. B. Parsons

The papers and discussion appearing in this volume were presented at a symposium jointly sponsored by the American Society for Testing Materials and the American Institute of Mining and Metallurgical Engineers and held at Philadelphia, Pa., November 29, 30, and December 1, 1944. Late in January, 1944, Lieut. Col. C. H. Greenall, Officer-in-Charge of the Laboratory Division, Frankford Arsenal, Ordnance Department, U.S.A., suggested to the American Society for Testing Materials that it might be a propitious time to arrange for a symposium on stress-corrosion cracking at the Annual Meeting of the Society in June, and agreed to make available a number of papers relating to work being carried out at that Arsenal. The Society's Committee B-5 on Copper and Copper Alloys, Cast and Wrought expressed keen interest in the symposium, and other Society committees were contacted and agreed to cooperate. Since the subject is one of primary interest also to the American Institute of Mining and Metallurgical Engineers, it was arranged that the two organizations would jointly sponsor the symposium. A Symposium Committee was formed under the joint leadership, for A.S.T.M., of Carter S. Cole, then Chief of the Metals Branch, Conservation Division, War Production Board and now Engineer on the Headquarters Staff of the Society; and, for A.I.M.E., of E. A. Anderson, Chief of Metals Section, Research Division, New Jersey Zinc Co. (of Pa.) and chairman of the Program Committee of the Institute of Metals Division. The Symposium Committee was constituted as follows:

Jan 1, 1945

By M. Duclos, A. Sawatzky

A simple model has been developed which describes the steady-state solute distribution in Ti-H type systems above the eutectoid temperature in the presence of a temperature gradient. The solute distribution is dependent on the shape of the phase boundaries. An interesting result, and one that is not observed at steady state in thermal diffusion below the eutectoid temperature, is the existence of a two-phase region. The heat of transport for hydrogen in a titanium, Q*a, over the temperature range 275" to 650.C is determined to be 4500 * 230 cal per mole. The heat of transport for hydrogen in B titanium, QB* over the temperature range 320" to 590.C is found to be 630 ± 200 cal per mole. It is also shown that thermal diffusion provides a method by which phase bounduries above the eutectoid may be determined in Ti-H type systems. IN modern technology materials are being used at constantly increasing temperatures under greater temperature gradients. Thus atomic migration in metal alloys due to a temperature gradient (thermal diffusion) may in some cases occur to an observable extent. The thermal diffusion of hydrogen in zirconium has in recent years received considerable attention1-' because of the use of zirconium alloys in nuclear power reactors. The thermal diffusion kinetics below the eutectoid (547°C) are fairly well understood. At steady state the solid solution, a, and hydride, 6, phases are completely separated with the hydride precipitating at the lower temperatures. No experimental work has been carried out in the a + B region although Droege4 suggested that a complete separation of the two phases, as observed at temperatures below the eutectoid, might not always occur. In the present investigation a simple model has been used to determine the steady-state solute distribution under a temperature gradient in Zr-H type systems heated above the eutectoid temperature. The solute distribution is shown to be dependent on the shape of the phase boundaries in the constitutional diagrams and several typical cases are discussed. The model has been applied to Ti-H. This system was chosen in preference to Zr-H because of its much lower eutectoid temperature (-300°C as compared with 547.C), thereby reducing experimental errors due to oxidation and hydriding. The heats of transport for hydrogen in the a and B phases of titanium also have been determined since they were required to compare the proposed thermal diffusion model with experiment. THEORY In the presence of a temperature gradient the atomic flux in a single-phase region of a two-com-ponent system of which the atoms of only one component are diffusing is given by:' J = - U\dx + RT3 dx) which can be written as: j-D(dn/dt +Q*n/RT2)dt/dx [11 J - -D\dT + RT2)dx [1] where D = diffusion coefficient, n = solute concentration, T = absolute temperature, R = gas constant, dT/dx = temperature gradient, and Q* = heat of transport. At steady state (J = 0) Eq. [I] leads to the solute distribution: n = noexp Q*/RT where no = a constant depending on total solute content. The heat of transport Q* can be experimentally determined from the steady-state distribution. In the present paper we shall determine the solute distribution in systems having the constitutional diagram exemplified by Ti-H shown in Fig. l.' As shown, N,(T) and NB(T) are the equilibrium solute concentrations in the a and 0 phases at temperature T. Lines AA' and CC' define the region of interest to us. The following assumptions are made: 1) Steady-state conditions prevail. 2) In a single-phase region all points on an isotherm have the same thermodynamic potential so that the composition over an isotherm is uniform. If a two-phase region exists, thermodynamic equilibrium is found only at phase interfaces. However, we assume the component of the concentration gradient along an isotherm to be small so that the composition in each phase is approximately the same as at the interface and is given by the constitutional diagram, Fig. 1. 3) There is appreciable diffusion of only one component. 4) We shall consider only the case where Qa*, QB*, and Qg*, the heats of transport for solute diffusion in the a, B, and 6 phases, respectively, are positive. This has been observed for the thermal diffusion of hydrogen in zirconium3 and titanium.10 We will show that the steady-state solute distribution above the eutectoid is primarily determined by the heats of transport and the temperature dependence of Na(T) and Np(T). It may be quite different from the steady-state distribution below the eutectoid. For example, we will see that, under certain conditions,

Jan 1, 1970

By D. A. Flanagan, B. L. Landrum, P. B. Crawford, B. C. Norwood

Herern is described a heat conduction model which has been developed to predict the pressure distribution within a reservoir being subjected to rrnsteady-state depletion. Although potentiometric models have been widely used to study reservoir pressure distribution, their application is limited to the study of steady-state cases. Electrical analyzers may be used to study unsteady-state phenomena, but their application and simulation have certain limitations. Much of the now accepted theory of unsteady-state fluid flow in porous media has evolved from previous heat conduction knowledge. An analogy between the flow of fluid in an unsymmetrical reservoir and con-duct ion of heat in a similarly shaped unsymmetrical metal plate is made to show adaptability of the hear conduction principle to transient reservoir cases. A description of the model and necessary instrumenrarion is included. Data show influence of well location on pressure distribution during unsteady-state deple[ion. Application of results is made to a hypothetical reservoir and to a reservoir located in an irregular aquifer. INTRODUCTION Development of methods for predicting behavior of petroleum reservoirs has resulted partially from adaptation of electrical and thermal flow concepts to the flow of fluids through porous media. Extensive investigation of electrical and thermal flow problems has resulted in mathematical solutions applicable to many reservoir problems. The relative ease of measuring electrical flow has brought wide acceptance of the use of the potentiometric model to study certain field problems. Potentiometric models are restricted to the study of steady-state conditions because of the instantaneous response of electrical flow to changes in the applied potential. The electrical reservoir analyzer has been one of our most useful instruments for studying certain phases of unsteady-state behavior1. Other than approximation techniques, no method exists for determining pressure distribution in an irregular reservoir during primary depletion. Heat flow, like fluid flow, is inherently transient. The model described here was developed to use this transient nature of heat flow, measurable in the laboratory, to simulate transient flow of fluids in the porous medium of the reservoir above the bubble point. A metal plate shaped like the reservoir to be studied was heated by a "well" source. Temperature increase in the plate is analogous to pressure decline in the field if the field is being depleted, or pressure increase if fluid is being injected. This study is intended to determine the feasibility of using the transient nature of the heat flow to study the transient behavior of fluid flow. It is hoped that this new technique will aid in the understanding of one of the more complex phases of reservoir engineering. THE FLUID FLOW-HEAT CONDUCTION ANALOGY The similarity of the equations which describe the flow of fluids through a porous medium and the conduction of heat through a solid is well known2. Rate of flow of fluids is given by Darcy's law3. while the rate of flow of heat is given by Fourier', (I,, - KA 4T........(2) Combining Eq. 1 with the equation of continuity for a compressible liquid", i.e.,results in Expressing y in terms of the compressibility, i.e., pr = peey ,..........(5) and by expanding the exponential and neglecting higher orders of cp one can obtain

By William R. Hart

I was this morning an interested listener to the remarks of Mr. Ashbel Welch in regard to his designing a new section for steel rails, in 1866; and for the salze of the truth of history, and in order t:, give the credit to an American (and where it rightfully belongs) of higning the first section for steel rails, which was intelligently adapted to that material; I beg to state the following facts: On the 14th of August, 1866, Mr. Ashbel Welch gave me an order for 200 tons of steel rails, to be made bbr the Camden and Amboy Railroad, from a section designed by him. A copy of this section 1 append herewith.

Jan 1, 1881

By O. M. McRae

The Courtland-Gleeson area is in Cochise County about 15 miles east of Tombstone in southeastern Arizona. Rocks exposed in the area range in age from Pre-cambrian to Quaternary. The Precambrian is repre-sented by the Pinal schist. Paleozoic rocks include the Cambrian Bolsa quartzite and Abrigo limestone, Mississippian Escabrosa limestone, and the Permo-Carboniferous Naco Group limestones. Rocks believed to be of Triassic and/or Jurassic age include the Copper Belle monzonite porphyry, Turquoise granite, and Gleeson quartz monzonite. The Cretaceous is represented by andesitic volcanics and various sedimentary rocks. Tertiary rocks include the intrusive and extrusive Sugarloaf quartz latite porphyry and numerous dikes of various rock types. Quaternary conglomerates cover the northern and eastern part of the area. The geologic structure is extremely complex. All rocks as old as early Tertiary have been involved in either tilting, normal faulting, high angle reverse faulting, imbricate thrusting or folding and overfold-ing. Major deformation was initiated during the first half of the Tertiary. Northeast-southwest compres-sional forces caused thrust plates containing lower Paleozoic rocks to override Cretaceous rocks. Subsequently, two large slide blocks of lower Paleozoic rocks, acting under the influence of gravity, moved eastward. The imbricate structure and the gravity slide blocks were then broken by late Tertiary normal faults. INTRODUCTION The Courtland-Gleeson area, or Turquoise Mining District, has long been recognized as an area of extreme structural complexity. Gilluly 2 referred to the entire district as a "gigantic thrust breccia". In 1962, Bear Creek Mining Company completed a two year program of detailed geologic mapping supported by exploration drilling. The purpose of this paper is to present some of the results of this investigation and to provide a structural interpretation based on these results. The geologic map that accompanies this report is generalized and shows only the major and significant features. The area was initially mapped on aerial photographs on a scale of 1 in. equals approximately 500 ft. These data were transferred to a planimetric base using a vertical sketch master. LOCATION The Courtland-Gleeson area is in central Cochise County, about fifteen miles east of Tombstone, and about twenty-two miles northeast of Bisbee in southeastern Arizona (Fig. 1). The area is readily accessible over graded gravel roads from both Tombstone and Elfrida. GENERAL GEOLOGY Rocks exposed in the area range in age from Pre-cambrian to Quaternary. wilson3 and Gilluly2 have published very detailed descriptions of the principal rock units exposed in the area. Only a summary description is provided in Table I. A great number of previously unmapped narrow Tertiary dikes and small irregular masses of hornblende andesite porphyry, lamprophyre, and aplite intrude the Gleeson quartz monzonite in the western part of the map area. The scale of the map prohibits showing them. The aplite dikes are related to, and bear the same structural relationships as, the Sugarloaf quartz latite dikes found in this area. For that reason, and because both the hornblende andesite porphyry and the lamprophyre are post-mineral and post-thrusting, their omission from the map is not considered significant. Because so many of the contacts in the district are fault contacts, because bedding faults appear to be prevalent but are difficult to recognize and map, and because igneous intrusions are so common throughout the sedimentary section, it is virtually impossible to measure an exact total thickness of any of the sedimentary rock units. Nevertheless, neither the field mapping program nor the diamond drilling provided any basis for suspecting that the thicknesses of the sedimentary units are significantly greater or less than what might be inferred from surrounding districts.

Jan 1, 1967

The following is an incomplete list of members and guests who called at Institute headquarters during the period July 11, 1918 to August 11, 1918. John Carter Anderson, Tucson, Ariz. Edson S. Pettis, San Francisco, Cal. Lieut. Frank A. Ayer, Tyrone, N. M. Wm. H. Rettie, Yonkers, N. Y. W. R. Canton, McGill, Nev. J. T. Robertson, Port Richmond, S. I. Alden Crankshaw, Palmerton, Pa. Harry O. Robinson, Margarita, John Davenport, W. Norfolk, Va. Venezuela. A. Faison Dickson. C. K. Seng, Gilbert, Minn. F. A. Fahrenwald, Cleveland, C). E. S. Sheffield. L. Hall Goodwin, New York. H. G. Smith. W. H. W. Hamilton, Baker, Ore. Harry M. Spoor. Floyd D. James, St. Louis, Mo. H. H. Stoek, Urbana, Ill. George A. Laird. Arthur L. Tuttle, Copperhill, Tenn. J. W. McBride, Spokane, Wash. Thor Warner, Phoenix, Ariz. Arthur Notman, Bisbee, Ariz. Christopher G. Atwater, Manager Agricultural Dept., The Barrett Co., is in Washington serving the U. S. Navy Bureau of ordnance in connection with the Navy nitrate plant recently authorized by Congress. Edward Ludlam Blossom announces his marriage to Mabel Townsend, daughter of Mr. and Mrs. George Comings Mills, on Wednesday, July 17, 1918, at New York City.

Jan 9, 1918

By John H. Hollomon

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

Jan 1, 1945

By J. Chipman, M. N. Dastur

The importance of dissolved oxygen as a principal reagent in the refining of liquid steel and the necessity for its removal in the finishing of many grades have stimulated numerous studies of its chemical behavior in the steel bath. From the thermodynaniic viewpoint the essential data are those which determine the free energy of oxygen in solution as a function of temperature and composition of the molten metal. A number of experimental studies have been reported in recent years from which the free energy of oxygen in iron-oxygen melts can be obtained with a fair degree of accuracy for temperatures not too far from the melting point. Certain discrepancies remain, however, which imply considerable uncertainty at higher temperatures; also several sources of error were recognized in the earlier studies. It has been the object of the experimental work reported in this paper to reexamine these sources of uncertainty and to redetermine the equilibrium condition in the reaction of hydrogen with oxygen dissolved in liquid iron. The reaction and its equilibrium constant are: H2 (g) + Q = H2O (g); K1 _ PH2O / [1] Ph2 X % O Here the underlined symbol Q designates oxygen dissolved in liquid iron. The activity of this dissolved oxygen is known to be directly proportional to its concentrationl,2 and is taken as equal to its weight percent. The closely related reaction of dissolved oxygen with carbon monoxide has also been investigated:3,4,5 co (g) +O = CO?(g); K _ Pco2___ [2] K2= pco X % O [2] The two reactions are related through the wat,er-gas equilibriuni: H2 (g) + CO2 (g) = CO (g) + H2O (g); K2 = PCO X PH2O [3] PH2 X PCO2 and with the aid of the accurately known equilibrium constant of this reaction, it has been shown5 that the experimental data on reactions [1] and 121 are in fairly good, though not exact, agreement. Experimental Method Great care was taken to avoid the principal sources of error of previous studies, namely, gaseous thermal diffusion and temperature measurement. The apparatus was designed to provide controlled preheating of the inlet gases and to permit the addition of an inert gas (argon) in controlled amounts, two measures found to be essential for elimination of thermal diffusion. A known mixture of water vapor and hydrogen was obtained by saturating purified hydrogen with water vapor at controlled temperature. This mixture, with the addition of purified argon, was passed over the surface of a small melt (approximately 70 g) of electrolytic iron in a closed induction furnace. After sufficient time at constant temperature for attainment of equilibrium the melt was cooled and analyzed for oxygen. GAS SYSTEM A schematic diagram of the apparatus is shown in Fig 1. Commercial hydrogen is led through the safety trap T and the flowmeter F. The catalytic chamber C, held at 450°C, was used to convert any oxygen into water-vapor. A by-pass B with stopcocks was provided so that the hydrogen could be introduced directly from the tank to the furnace when desired. From the catalytic chamber the gas passed through a water bath W, kept at the desired temperature by an auxiliary heating unit, so that the gas was burdened with approximately the proper amount of water vapor before it was introdvced into the saturator S. All connections beyond the catalytic chamber were of all-glass construction. Those connections beyond the water bath were heated to above 80°C to prevent the condensation of water vapor. After the saturator, purified argon was led into the steam-hydrogen line at J, and finally the ternary mixture was introduced into the furnace. THE SATURATOR The saturator unit comprised three glass chambers, as shown in Fig 1, the first two chambers packed with glass beads and partially filed with water and the third empty. Each tower had a glass tube with a stopper attached for the purpose of adjusting the amount of water in it. The unit was immersed in a large oil bath, which was automatically controlled with the help of a thermostat relay to constant temperature, ± 0.05ºC, using thermometers which had been calibrated against a standard platinum resistance thermometer. The performance of the saturator over the range of experimental conditions was checked by weighing the water absorbed from a measured volume of hydrogen; the observed ratio was always within 0.5 pct of theoretical.

Jan 1, 1950

By Harold Margolin

The Ti-Al system certainly merits the investigative attention it has been receiving and this latest contribution by Blackburn is therefore to be welcomed. The titanium-rich end of the phase diagram shown here, as well as the diagram by crossley,17 Clark et a1.,18 and Tsujimoto and Adachi,29 reveal no other intermediate phase than Ti3A1, although a previous work by Ence and Margolin20 had reported an additional intermediate phase. Since then, Buerger Precession pictures of single crystals of 10.5, 11.5, and 12.5 wt pct A1 were made at New York university21 and the extinctions were found to be typical of a D6h a Ti structure. Some superlat-tice spots and/or streaks suggesting the presence of an Mg3Cd structure, i.e., Ti3Al, were also found. Since these specimens had been quenched from the y region20 and had revealed a Ti, it was concludedz1 that y does not exist and the structures interpreted as m + y could not be so considered. The absence of normal two-phase behavior in these structures had been indicated in the paper. Accordingly, the two-phase region y + 6 becomes a + Ti3Al and there is some agreement between the results of Blackburn and of Ence and Margolin20 as to both shape and existence above 900°C of an a + Ti3Al field. Crossley 17 proposed that Ti3Al is a line compound which decomposes congruently at 900°C. It is difficult to discount entirely the fact that clear two-phase structures, varying in amount with position in the two-phase field, could be detected above 900°C by Ence and Margolin.20 Precipitation during quenching could not have been so regular and the twin-phase syndrome17 does not apply. The heat treatment and quenching technique was essentially the same as was used by Crossley, whereas Blackburn, who used a rapid quenching procedure, also showed a two-phase a + Ti3A1 field above 900°C. If the two-phase field exists above 900° C, it is easy to picture a two-phase field which could account for the data of Crossley below 900°C without invoking a line compound existence of Ti3A1. All that would be necessary would be an 0 + Ti3Al/Ti3Al boundary which curved sharply to higher aluminum contents below 900° C. It is clear that the controversy must be solved by techniques which obtain data at elevated temperatures without quenching. It is conceivable that the difference in width of the a + Ti3N fields reported by Blackburn and by Ence and Margolin is due to the longer annealing times used by the latter investigators. The criterion for establishment of equilibrium in our work20 was the

Jan 1, 1969

By B. D. Lichter

The lattice parameters of zirconium and zirconium-oxygen solid solutions (hcp) were determined from measurements of back-reflection X-ray photograms obtained at 29°C using a symmetrical focussing camera. The following linear equations between parameters (c,a) in angstrom units (10-8 cm) and atom ratio (m) of oxygen to zirconium were obtained: c = 5.14764 + 0.2077m a =3.23168 + 0.1099m. The linear equations given are valid over the range 0 to 5 at. Pct 0. The accuracy of individual parameter measurements approaches the limiting accuracy determined by the spectral broadening of the incident characteristic radiation, and exceeds the accuracy of previously reported values. THE present work was undertaken in order to determine the lattice parameters of zirconium-oxygen solid solutions with an accuracy that allows quantitative determination of oxygen in zirconium. The results indicate that this is possible if very careful measurements are made, since the parameter change is only a few hundredths of a percent per at. pct 0.1, 2 In the present investigation the desired accuracy was achieved with large-grained samples using a back-reflection focussing camera and maintaining good temperature control during exposure. In addition a digital computer was used for calculation of the parameters by means of an analytical extrapolation.37 Suitable diffraction photograms were obtained from large-grained samples by using a modification of the technique described by Graf and Monteil.5 This consists of simultaneous rotation and oscillation of the specimen about two mutually perpendicular axes during exposure. Whereas, normally the upper limit of grain size is about 50 µ for useable diffraction photograms, this technique allows extending the upper limit of grain-size to exposure of a single crystal. EXPERIMENTAL Preparation of Alloys for X-ray Diffraction—Zir-conium, designated as hafnium-free, Westinghouse "Grade 1," was swaged from l/2-in.-diam crystal bar to 3/8-in.-diam rods. Substantially all of the hydrogen was removed from the zirconium by annealing at 1200°C in a high dynamic vacuum. The rods were then swaged to 0.2 in. diam without intermediate annealing, and 2 in. lengths were cut for alloying with oxygen. Samples for chemical analysis were taken from portions of the rods between each 2 in. length. Chemical analysis of the dehydroge-nated zirconium is given in Table I. Commercial tank oxygen (99.5 pct 0) was condensed in a liquid nitrogen-cooled trap, and part of the condensate was slowly reevaporated into 5-liter storage flasks. Nitrogen remained as a reactive impurity, and the calculated maximum increase in nitrogen content after a 5 at. pct 0 addition to zirconium was 50 ppm by weight. However, chemical analyses of several of the prepared alloys indicated that the maximum increase in nitrogen content was 10 ppm. The storage flasks, a Sieverts-type gas burette and manometer, and associated traps, pumps, and pressure gauges were connected through a glass high-vacuum manifold to comprise the gas addition system. A fused silica tube, connected to the mani-

Jan 1, 1961

By T. Egleston

The materials containing copper which are refined in the United Statrs, are, for the most part, the natiye noppers of Lake Superior. IJntil quite recently but little pig copper Was made for sale, and that came principally from the pure sulphorous ores of New England and the Sonth, and was generally sdd to reSneries not far from the ore filrnaceu. A stnall aiuoiint found its way into the'niarket which was produced either as the by-product of the treatment of gold and silver ores, or as the result of the treatment of impure copper ores; but both these grades, on account of the impurities they contained, were loolced on with stlspicion, and were not sought for. A11 the grtlGis of pig coppcr are sold by the unit of oopper contents, a great redtiction being made in the price when impurities are present. There are at the present time only three works which treat native copper, the two of the Detroit and Lake Superior copper Company, and the works of C:G. Hussey & Co., in Pittsburgh. There are a few works ivhich smelt sulphuroris ores and refine their pig; bo sides these t1le1-e arc a few siuall works where gig copper is refined uuly. Some of these purcIlase blscir copper, refine scrap, or simply refine such grades of ingot copper as are found in the market, but nlostly that from Lake Superior, for the purpose of getting it into swh shapes that can be handled cpmtriercially to advantage, such as in making large plates or high grades of wire fir electrical purposes. A nomher of such works are situated in the Xaugaturk Vatley aud elsewhcre in New England. The recent discoveryof vnlt~sblc ores in Ariarona makm it probable that within a few year8 the refining of capper In the United States will make great develupments. Up to the time of the discovery of the mines on Lake Superior, only a very small quantity of native copper had ever been foond, not sufficient to justify the erection of worlrs fbr its special treatment. It had, besides, never been found in very large maweq so that the discovery of greabblocks of it presented serious difficulties, not oolp in mining it,-I- but in bringing it into a merchantable condit'ion. It seemed a very simple process to melt these large maws,

Jan 1, 1881

By Thomas Leonard Watson

Jan 1, 1906

By C. E. Sims

THE following presentation is more a summation of observations made and conclusions drawn over a period of three to four years than a report of experiments made with a definite objective. Tests were made, of course, to verify hypotheses, but the large mass of data was collected incidental to other work. Lack of space forbids the presentation of more than a few of those data. On the other hand, it is unfortunate that some of the most illustrative examples are not available. The work is admit¬tedly incomplete but is presented in the hope that it will stimulate further work along a similar line. The answers to many of the questions left unanswered by this paper will be found only after long and painstaking study, such as is scarcely possible in a commercial laboratory where problems of immediate importance consume most of the time. It is also hoped that this study will in some measure throw light on some of the dark spots of steelmaking, and help to clarify some of the annoyingly vague references to "good practice." Only cast steel was studied and the conclusions apply to cast steel, but it is the authors' opinion that the quality of rolled or forged steel is largely dependent on the quality of the ingot, which is a casting. Although this discussion deals almost entirely with inclusions, it is important that the reader understand that only those natural inclusions which owe their origin to the solubility of certain materials in steel and to the chemical reactions of steelmaking are considered. Accidental inclusions, such as entrapped particles of slag, nozzle, runner, or mold are outside its province and are not considered. Such accidental inclusions are always dangerous and should be carefully avoided.

Jan 1, 1932

By J. H. Keeler

The tensile characteristics of Zr-Fe binary alloys containing up to 5 atomic pet Fe are reported for the temperature range —195o to 500°C. A linear relation between stress at constant strain and volume fraction ZrFe2 was found. The coincidence of data from unalloyed zirconium with zero volume fraction ZrFe2 indicated little or no solid solution in IL-zirconium, in agreement with Hayes, Roberson, and O'Brien.' The absolute increase in strength due to particle strengthening, although decreasing with increasing temperature, was a greater percentage at high temperature. ZIRCONIUM is of interest for use in nuclear reactors because of its low neutron absorption, good corrosion resistance, and high melting temperature. The alloying of zirconium with iron has been considered as a means of increasing the mechanical strength of zirconium without seriously increasing the neutron absorption " over that of unalloyed zirconium. The Zr-Fe system has a eutectic at 934°C and 23.7 atomic pet Fe and a eutectoid at 800°C and 4.0 atomic pet Fe. The zirconium-rich end of this system determined by Hayes, Roberson, and O'Brien' is shown in Fig. 1. The intermetallic phase coexisting with a and ß-zirconium has been reported as Zr2Fe3,1 with a,, - 7.04A, and as ZrFe2,2 face-centered-cubic, the phase being of the MgCu, type (C-15). It was more recently agreed to be ZrFe33 and face-centered-cubic. This intermetallic phase is essentially insoluble in a-zirconium, the hexagonal-close-packed modification; and the lack of solubility makes the system particularly interesting metallurgically. The system is strengthened almost exclusively by particles of in-termetallic phase, and there is very little solid solution strengthening to complicate the analysis. The Bureau of Mines, in its survey of zirconium-base alloys,' reported the tensile properties of Zr-Fe alloys made from chloride process zirconium, induction melted in graphite crucibles, and swaged at 850°C in iron sheaths. Additional data on these ZrFe alloys were given by Hayes, Roberson, and O'Brien.' Chubb and Muehlenkamp% have recently reported the strength of Zr-Fe alloys containing up to about 1.25 atomic pet Fe. These alloys were made from crystal bar zirconium, hot worked at 820°C, annealed at 700°C, and tested both at room temperature and at 316°C. Experimental Procedure The materials used in this investigation were high purity zirconium made by the iodide process and electrolytic iron. The composition of the zirconium as obtained by spectrographic analysis and the nominal composition of the iron are given in Table I. Alloy ingots weighing 100 g were made by are-melting under argon in water-cooled copper crucibles in a multihearth furnace."

Jan 1, 1957

By R. I. Jaffee, R. M. Evans

IN recent years, the interest in liquid metals as heat-transfer media for power plants has been very great. The possibility of the development of nuclear power plants has increased this interest and served as the impetus behind much research on low melting metals and alloys for such purposes. The principal reasons for consideration of liquid metals as heat-transfer media lie in their high thermal conductivity and consequent high heat-transfer coefficients, stability at high temperatures, and the high ranges of temperature possible. The element gallium possesses some of the requisite properties for a heat-transfer liquid. It is a unique material, having a low melting point and a high boiling point. Pure gallium melts at 29.78oC, and suitable alloying will produce a metal which melts below room temperature. The boiling point is about 2000°C. As it is a liquid metal, the heat-transfer characteristics would be good. Gallium is not now readily available, due in part to a lack of uses for the metal. Nevertheless, it is not a rare element, and a sufficient supply of gallium exists to permit its consideration for this use. Since gallium has some promise as a heat-transfer liquid, owing to its unique properties, research on the subject was carried on at Battelle Memorial Institute at the request of the Bureau of Ships, U.S.N. The research had as its objectives the determination of the effect of alloying on the melting point of gallium, and the study of the corrosion of possible container materials. In this research, alloys were found which had significantly lower melting points than pure gallium, but none which simultaneously fulfilled other additional requirements, chiefly the corrosion problem. Neither was it found possible to reduce the melting point of certain otherwise suitable alloys appreciably by small additions of gallium or gallium alloys. The results gave little hope that gallium alloys can be developed which enhance the good properties and minimize the undesirable characteristics of elemental gallium. Thus, gallium now appears less promising than other metallic heat-transfer media. The experimental thermal-analysis techniques used in this work have been described.' Experimental Results As a first approximation, the development of low melting gallium alloys was based on alloying elements suitable for use in a nuclear power plant, which also lowered the melting point of gallium. Information from the literature, summarized in Table I, indicates that. tin, aluminum, and zinc are the only suitable elements which cause a lowering of the melting point of gallium. Indium and silver also lower the melting point of gallium, but are of little interest for use in nuclear power plants. Of the elements reported not to lower the melting point of gallium, there is some ambiguity on the behavior of copper. Weibke3 obtained solidus arrest temperatures of 29°C for Cu-Ga alloys from 60 to 90 pct Ga, 0.8C lower than the generally accepted melting point. This may be the effect of a eutectic close to gallium, or, more likely, the result of impurities, or experimental error. The seven elements listed in Table I whose effects were not known were of potential interest if they lowered the melting point of gallium. Their effects were determined experimentally for this reason. Binary alloys containing nominally 2 pct of each of these elements were prepared in the form of 2-g melts by placing the components in a graphite crucible and holding them in an argon atmosphere at 370°C for 5 hr. These melts were then subjected to thermal analysis. In all cases. the solidus temperature was the melting point of gallium. Since these elements (As, Ca, Ce, Mg. Sb, Si, and T1) did not lower the melting point of gallium, they were not considered further as components of a eutectic-type alloy. Ga-Sn-Zn Alloys Preliminary considerations of this system for low-melting alloys were encouraging. All three binary systems were of the simple eutectic type. The composition and melting points of the eutectics were as follows: Sn-9 pct Zn (199°C), Ga-8 pct Sn (20°C), and Ga-5 pct Zn (25°C). Therefore, the probability of a ternary eutectic was high. For reasons to be discussed later, aluminum could not be used as an alloying constituent, leaving the Ga-Sn-Zn system as the only one of interest for low-melting gallium-

Jan 1, 1953

By R. W. Guard

ALTHOUGH etching techniques have been developed for revealing dislocation sites in several metals and ionic crystals,h t is valuable to extend the technique to new metals. An etch pit method for nickel has been developed on the basis some suggestions of Dr. John R. Cuthill of the National Bureau of Standards who had observed etch pits in creep specimens of nickel. The etchant used was proposed first by wensch2 for revealing grain size in nickel. The present paper describes the evidence that the technique can be used to reveal dislocations and gives the conditions under which etching can be carried out. The specimens examined were vacuum melted high-purity Ni (99.985 pct Ni) and commercial "A" nickel (99.8 pct Ni). Both materials contained greater than 0.008 pet C and had been annealed in nitrogen or dry hydrogen at 1100o to 1200°C. This gave a grain size of 1.5 mm in the high-purity nickel and 0.050 mm in "A" nickel. Tensile specimens (0.254 in. diam) were deformed from 0.25 to 10 pct at room temperature and then heated for 1/2 hr at different temperatures from 400" to 900°C. The specimens were sectioned longitudinally then polished electrolytically in 60 pct H2SO4 and etched in 35 pct H3PO4 solution at 0.2 to 0.4 v for 30 sec to 3 min. The best method for setting the proper voltage for etching is to increase the voltage until gas bubbles are evolved vigorously from the specimen and then cut it back by 10 pct. It is necessary to heat the specimen above 500°C after deformation in order that etch pits will be formed. This "decoration" treatment permits carbon to segregate to the dislocation rendering them sensitive to etching. It was demonstrated that carbon was the decorating impurity by decarburizing some specimens in wet H2 at 1200°C. The susceptibility to etch pitting was lost following this treatment but could be restored by carburizing in contact with graphite. Some rearrangement of the dislocations in the as-deformed structure occurs on heating at 500oC and above so that the technique can not be used to study the nature of dislocation patterns in deformed specimens. Extended etching does not change the number of pits although the background becomes rough and the pits quite large. The polycrystalline specimens with various strains were examined after annealing at different temperatures. Typical patterns are shown in Figs. 1 and 2. In the unstrained specimen, Fig. 1, the density of pits is 2.5 X 10' per sq cm. All grains show pits regardless of their orientation although there is a

Jan 1, 1961