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By J. W. Hickman, E. A. Gulbransen

One of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film. A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film. A comprehensive program has been undertaken to study these phenomena. This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C. Before the introduction of the electron diffraction technique, it was necessary to use either direct chemical analyses or X-rav diffraction analyses to determine the nature of the oxide film formed on the metal or alloy. Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry. In special cases the information obtained may be identical, but in general both viewpoints are necessary. Much of the early work was carried out on the oxidation of bulk samples where thick films were obtained. The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses. Although much useful information has been obtained in this manner. little could be learned about the character of the protective oxides during the period when the films were actually protective. Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique. In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective. Literature The oxidation of iron has been extensively investigated by X-ray and electron diffraction. Jackson and Quarrelll found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature. The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe³O4; between 515° and 900°C. the stable film was FeO. Above the upper change point of iron the oxide was found to be Fe³O4. From 400' to 515°C., FeO, Fe³O4 or a mixture of the two oxides was found. Recrystallization of the air-formed film below 400' and above 900°C. led to the formation of Fe3O4. In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described.

Jan 1, 1947

By J. L. Lamont, W. Crafts

Studies of the effect of composition of steel on hardenability by Grossmann,' and as-quenched hardness by Field2 and by the authors, have made it possible to predict the results of quenching when the composition and cooling rate are known In order to extend the application of the hardenability calculation to the quenched and tempered condition in which steel is finally used, a survey has been made of the hardness changes caused by tempering. From this study a method has been developed for the prediction of hardness and tensile strength of steel in the tempered condition. The method of calculation was developed from Rockwell C hardness tests on quenched and tempered Jominy specimens and is expressed in Rockwell C hardness units. It is of an additive type in which the degree of softening from as-quenched hardness is estimated. Tem-pred properties may be calculated within about plus or minus 5 Rockwell C hardness or plus or minus 15,000 lb. per sq, in. tensile strength. This degree of accuracy is less than that necessary for the control of heat-treatment, but is adequate for the comparative evaluation and selection of alloy steels. The formula indicates that tempered hardness is primarily dependent on as-quenched hardness and, as in the hardening reaction, the progress of tempering is controlled mainly by the carbon content. Alloys tend to retard softening by a secondary hardening mechanism in which the alloy appears to migrate from ferrite to the carbide phase. The factors for the effects of alloys in tempering vary so much from the effects of alloys in hardening that different steels of equivalent hardenability may, after like heat-treatment, differ considerably in tensile strength. Procedure In developing the method for calculating tempered Rockwell C hardness, simple and complex steels were tested over a range from 0.08 to 0'65 per cent carbon and up to 2.68 per cent manganese, 2.18 silicon, 3.50 chromium, 4.94 nickel, and 1.06 molybdenum. The steels were made as small induction-furnace heats at the Union Carbide and Carbon Research Laboratories, Inc' The accuracy of the method was finally checked on a variety of carbon, low-alloy and high-alloy types of heat-treating steels produced under commercial conditions. The method was based on a study of tempered Jominy bars, and its validity was tested by correlation with the center hardness and tensile strength of oil-quenched and tempered bars from 1/2 to 4 in. in diameter. The method of calculation was derived from the differences in Rockwell C hardness between as-quenched and quenched and tempered Jominy specimens. Prenormalized Jominy hardenability speci-menS quenched from a normal temperature for austenitizatios were used to obtain a range of as-quenched Rockwell C

Jan 1, 1948

By Robert E. Palmer

The Hawkesworth detachable drill steel shank and bit were invented by A. L. Hawkesworth, while he was a mechanical foreman for the Anaconda Copper Mining Co., at Butte, Mont. Mr. Hawkesworth died on June 16, 1925, at the time that his invention was practically a proved success. The first application for patents was made by him in November, 1918, and the bit is now being manufactured under patents issued in 1922 and 1923. The credit for its development in the early stages belongs to A. L. Hawkesworth, Roy S. Alley, Harry A. Gallwey, E. J. Bowman and various officials of the Anaconda Copper Mining Co. Later improvements, manufacturing problems and the direct usage in the mines were originated and perfected by the mechanical department under C. D. Woodward, E. R. Borcherdt, head of the Rock Drill Equipment Department, Robert E. Kelly of the Mechanical Department, and various operating department heads of the Anaconda Copper Mining Co. The author wishes to acknowledge the assistance of these officials in the preparation of this paper. Comparison of Costs Using Regular Drill Steel and Detachable Drill Steel In 1922 production was satisfactory and sufficient enough to warrant a complete installation in an operating mine. The study and tests were made at the Badger State mine, the production of which averaged 1200 tons of ore per day. E. R. Borcherdt, head of the rock drill equipment department, was in direct charge of the trials, installation, operating problems and records during the entire .period, arid still continues in that position. This mine is a typical Butte mine, operated through a standard four-compartment shaft, served by a double drum hoist and an auxiliary hoist. The texture of the ground and ore has all the variations from soft to very hard granite and sulfide ore with production from levels between the

Jan 1, 1930

By R. Ingerson

Bore surfaces of used guns commonly show a pattern of cracks in various degrees of development. It has been suggested that these cracks may aid erosion by providing channelways for the gases, eventually leading to the tearing out of blocks of metal. Under the general studies of gun erosion conducted at the Geophysical Laboratory it appeared desirable to consider this factor, and to determine the resistance to surface cracking offered by gun steel and by various other materials that might be used in the bores of guns. Method and Apparatus In order to make such a determination it is necessary to have (I) an arrangement in which the surface to be studied can be subjected to conditions similar to those in a gun with respect to temperature, pressure (developed by explosion gases), composition of the gases and length of time the surface is exposed to the gases; and (2) a specimen that can be examined readily after any number of shots, and then fired again, if necessary. The first of these conditions can be met by using an explosion vessel designed by H. S. Roberts of the Geophysical Laboratory. Fig I shows a cross-section of the apparatus. The "gun" G from which the charge is fired is made from the receiver of a caliber 0.30 army rifle, M1903, and the charges are prepared in caliber 0.30 cartridge cases. The test specimen S is held in place by a cone-shaped plug P and by a steel bridge B which is bolted to the outside of the explosion vessel on either side of the section shown. The plug, in turn, is held in place by a screw collar C. Maximum pressure is controlled by a brass rupture disk R. Part of the explosion gases flow past the two flat areas on S. Temperature and composition of gases, and the time before the rupture disk breaks, can be controlled by amount and kind of powder used, and pressure can be controlled by using rupture disks of different thickness. While the explosion vessel used was not designed so that temperature and pressure could be measured, in other vessels of closely similar size and shape containing proportionate charges of the same kind of powder as that used for standard testing procedure, values of 2700°K and 50,000 psi were obtained. Since the orifices past the flat areas on the plug are small compared to the rupture disk hole (I:I6), most of the gas goes out through the rupture disk when it breaks. The amount that goes by the plug depends on (I) the pressure attained before the rupture disk breaks and (2) the time it takes for this pressure to be built UP. The second condition (examination at will after any firing) is met by using for specimens short rods that have flat areas ground on opposite sides. These flat

Jan 1, 1949

By Joshua I. Tracey, Mackenzie Gordon

THE bauxite deposits in central Arkansas were formed by weather¬ing, in early Eocene time, of fresh or kaolinized nepheline syenite above the water table in a subtropical climate of fairly continuous moisture. Four types are recognized: (1) residual bauxite deposits on kaolinized nepheline syenite, (2) residual deposits on kaolin and bauxite detritus, (3) alluvial deposits of sorted pebbles and pisolites of early Wilcox age, and (4) rubble deposits of later Wilcox age. All were invaded by kaolin and siderite during subsequent burial by Eocene sediments. PART I-FIELD RELATIONS OF THE DEPOSITS The Arkansas bauxite region for years has produced about 95 pct of the domestic supply of bauxite of the United States and it contains today reserves of more than 40 million tons-nine tenths of the known domestic reserves. During World War II, the Arkansas bauxite deposits were explored jointly by the U. S. Geological Survey and the U. S. Bureau of Mines. Some 6000 holes were drilled by rotary rigs under contract to the Federal Govern¬ment, which resulted in the discovery and delimiting of approximately 20 million tons of ore in place. Detailed study of the many sections cored through the bauxite, of data from a much greater number of drill holes made available by all the operating companies, and of the extensive mine faces exposed in the strip pits, has yielded valuable geologic information about the origin of the deposits. It is now possible to piece together a paleotopographic picture of the deposits and the now-buried land surface on which they formed. The bauxite region in the center of Arkansas (Fig 1) contains two producing districts: one in Pulaski County, just south of Little Rock, and the other in Saline County, about 15 miles to the southwest. The deposits in both districts are associated with hills of nepheline syenite, bosses of a large batho¬lith that was intruded into Paleozoic rocks and later buried beneath coastal plain sediments deposited during Cenozoic time. The folded Paleozoic rocks are exposed in the northwest half of the state and are covered in the southeast half by the nearly flat-lying coastal plain sediments. The older rocks were intruded by nepheline syenite, probably in Late Cretaceous time, and sub¬sequently were eroded so as to expose the top of the batholith. In Paleocene time, marine limestone and laminated black silty clay of the Midway group were deposited in an advancing sea, and covered all but the most elevated parts of the batholith. Erosion of the islands of nepheline

Jan 1, 1952

By James D. McClung, H. J. Gluskoter, M. R. Geer

INTRODUCTION The purpose of coal preparation is to improve the quality of coal to make it suitable for a specific purpose by (1 ) cleaning to remove inorganic impurities; (2) sizing-crushing or screening, or both; or (3) special treatment, such as dedusting. The properties and quantities of impurities in coal are of major importance in the design and operation of steam generating equipment. Al- though boilers are often designed and equipped to use a wide range of coals, no boiler will perform equally well with all types of coals. All coals have certain properties that place limitations on their most advantageous use. These limitations are especially stringent for many of the older installations. Because of a general lowering of quality of raw coal in recent years, the need for coal cleaning has significantly increased. Among the factors contributing to the need for increased coal preparation are (1) increased demand for quality brought on by market and environmental requirements; (2) increased extraneous dilution caused by mine, health, and safety laws; and (3) depletion of the higher-quality coal seams.

Jan 1, 1979

By W. Crafts, J. L. Lamont

Studies of the effect of composition of steel on hardenability by Grossmann,' and as-quenched hardness by Field2 and by the authors, have made it possible to predict the results of quenching when the composition and cooling rate are known In order to extend the application of the hardenability calculation to the quenched and tempered condition in which steel is finally used, a survey has been made of the hardness changes caused by tempering. From this study a method has been developed for the prediction of hardness and tensile strength of steel in the tempered condition. The method of calculation was developed from Rockwell C hardness tests on quenched and tempered Jominy specimens and is expressed in Rockwell C hardness units. It is of an additive type in which the degree of softening from as-quenched hardness is estimated. Tem-pred properties may be calculated within about plus or minus 5 Rockwell C hardness or plus or minus 15,000 lb. per sq, in. tensile strength. This degree of accuracy is less than that necessary for the control of heat-treatment, but is adequate for the comparative evaluation and selection of alloy steels. The formula indicates that tempered hardness is primarily dependent on as-quenched hardness and, as in the hardening reaction, the progress of tempering is controlled mainly by the carbon content. Alloys tend to retard softening by a secondary hardening mechanism in which the alloy appears to migrate from ferrite to the carbide phase. The factors for the effects of alloys in tempering vary so much from the effects of alloys in hardening that different steels of equivalent hardenability may, after like heat-treatment, differ considerably in tensile strength. Procedure In developing the method for calculating tempered Rockwell C hardness, simple and complex steels were tested over a range from 0.08 to 0'65 per cent carbon and up to 2.68 per cent manganese, 2.18 silicon, 3.50 chromium, 4.94 nickel, and 1.06 molybdenum. The steels were made as small induction-furnace heats at the Union Carbide and Carbon Research Laboratories, Inc' The accuracy of the method was finally checked on a variety of carbon, low-alloy and high-alloy types of heat-treating steels produced under commercial conditions. The method was based on a study of tempered Jominy bars, and its validity was tested by correlation with the center hardness and tensile strength of oil-quenched and tempered bars from 1/2 to 4 in. in diameter. The method of calculation was derived from the differences in Rockwell C hardness between as-quenched and quenched and tempered Jominy specimens. Prenormalized Jominy hardenability speci-menS quenched from a normal temperature for austenitizatios were used to obtain a range of as-quenched Rockwell C

Jan 1, 1948

By Walter R. Hibbard

THE increased strength of a polycrystal-line metallic aggregate compared with that of its individual crystals generally has been associated with complex stress distributions at the grain boundaries resulting from atomic irregularity between grains. This disregistry, together with the necessity for adjacent crystals to deform 'compatibly regardless of the single crystal crystallographic strain mechanism, complicates this mechanism so as to increase the metal's resistance to deformation. Although Taylor1 has shown from purely mechanical considerations the requirement for at least five active slip systems to absorb the complexities during the homogeneous deformation of polycrystalline face-centered cubic metals, experimental studies by Barrett and Levenson2 indicate that this is feasible only in a qualitative sense because of deviations from homogeneous deformation. Seitz and Read in their review3 state: "Unfortunately . . . present knowledge of the grain boundary influence is not sufficient to complement the work in single crystals and provide us with a good foundation for treating polycrystals." The purpose of this investigation was to attempt to clarify the gap between single crystals and crystalline aggregates by an analysis of the effects of deformational stresses. Some of the results were described by C. H. Mathewson in his 1943 Campbell Memorial Lecture.21 PREVIOUS INVESTIGATIONS Since the performance of single crystals deformed under pure stresses has been relatively thoroughly investigated, the most significant researches are concerned primarily with deviations from single crystal behavior of large grained specimens. Qualitative grain boundary effects involving the observed amount of slip were reported by Carpenter and Elam5 in 1921. Individual crystals in a two or three grained aluminum specimen deformed by tension acted in the normal manner described by Taylor and Elam4 except for marked modifications at the grain boundaries. There the power to withstand deformation was considerably increased, leaving a ridge on the specimen where decreased slip occurred, often noticeable 34 in: from the boundary. Adcock,6 Yamaguchi,7 Seumel,8 Hirst9 and others have also reported this phenomenon as a qualitative trend. Yet attempts by O'Neill10 and Ljunggren11 to measure a difference in hardness at grain boundaries in undeformed specimens were unsuccessful. Miller12 measured quantitatively the reduction in slip near the boundary between the single crystal and polycrystalline areas of zinc specimens. These effects consisted of two parts: I. Next to the polycrystalline interface the distribution of stresses was so altered

Jan 1, 1948

By Roy D. McLellan

Electrolytic production of cadmium at the Great Falls plant started in the first part of the year 1925. Prior to that time, an experimental unit had been in operation for a few months during the year 1922. At present the plant is the largest producer of cadmium, not only in the United States but in the world. Electrolytic cadmium is characterized by its very low content of impurities. The main impurities, which are lead, copper, zinc and iron, do not aggregate more than 0.05 per cent., leaving a cadmium content better than 99.95 per cent. The consumption of cadmium has increased rapidly since the war, with the growing use in the plating industry. Cadmium plating has come into prominence because of its connection with the automobile and radio industries. As a protective coating, a deposit of cadmium is superior to zinc. Cadmium is also used extensively in alloys. Important among these is the alloy with copper used in telephone and trolley wire. In proportion of 0.5 to 1.2 per cent., cadmium adds materially to the strength and wearing qualities. Practically all commercial zinc concentrates contain a small amount of cadmium. In the electrolytic zinc process, the cadmium that is dissolved in the regular leaching operation is removed from solution with metallic zinc, generally added in the form of zinc dust. This precipitate also contains the copper taken into solution and the excess of zinc dust, which is required in order to insure a complete removal of all impurities. The precipitate is treated by a separate process to recover the copper, cadmium and excess zinc. In order to make the metals more soluble and to render insoluble such impurities as iron, arsenic and antimony, the precipitate is roasted. The roasting is carried out in gas-fired McDougall furnaces, with a roasting temperature of about 700' C. The roasted residue is leached with dilute sulfuric acid, spent electrolyte from the zinc electrolyzing, containing 10 to 12 per cent. free H2S04. The leaching is done in cylindrical tanks of 30 tons capacity, agitated

Jan 1, 1930

By Michael Perch, Charles C. Russell

Nearly 75 per cent of the total coke production in the United States in 1940 was consumed in blast furnaces. In 1939 the percentage was 69.9, and in 1938 it was 61.3. To produce a net ton of pig iron 1757 lb. of coke was required in 1940 and 1760 lb. in 1939. These figures indicate how dependent the production of pig iron is upon the production of coke. The rate of iron production is in some measure influenced by the physical and chemical characteristics of the coke. Blast-furnace operators believe that the physical properties of coke profoundly influence the operation of the furnace. Although it is true that coke of a wide variety of physical properties is used in American blast furnaces, the periodic fluctuation of these properties is one of the causes of irregularity of blast-furnace operation. The purpose of this paper is to present a broad picture of the physical properties of by-product coke that are generally considered to be important by coke-oven and blast-furnace operators. Effects of the kind of coal used, the preparation of the coal, the rate of coking, and other factors will be considered. Of all these variables, the kind of coal used is by far the most important. In this discussion use will be made of the method of coal classification by rank' standardized by the American Society for Testing Materials. Although this method of classification has been an American stand¬ard for several years, it has not been given the attention it deserves, especially in connection with the selection of coal for production of coke. Despite the fact that many producers of blast-furnace coke are limited to some particular source or sources of coal, a good understanding of the principles involved in setting up the standard method of classification may lead to a better appreciation of the causes of changes in coke characteristics. Furthermore, where it is necessary to select new coals as a substitute for the original supply, this method of classification can be of great assistance. The data presented have been gathered from many sources, but no attempt has been made to cover the vast literature. Instead, some of the more important data have been selected to show how coals and their carbonization affect some of the physical properties of coke. It must be emphasized that generalizations concerning the behavior of coking coals are presented and that individual coals may vary widely from the specific behavior depicted. Nevertheless, it is believed that the data illustrate certain typical behaviors. Neither was it possible to cover completely all the factors involved; for example, the macroscopic constituents of coal are believed to have important effects on the physical properties of coke, but since there is little information available for such study, and since vitrain, clarain, and durain are neither

Jan 1, 1944

By T. E. Leontis

The specific effect of various rare-earth metals on the room- and elevated-temperature properties of magnesium has been evaluated. Alloys containing didymium exhibit the highest tensile and compressive strengths at room and elevated temperatures. All the rare-earth metals increase the creep resistance of extruded magnesium at temperatures in the range of 400° to 600°F, but the degree of enhancement depends on the temperature and on the concentration of the added metal. THE effects of rare-earth metals on the properties of sand-cast magnesium were discussed in some detail in earlier paper by the author.' The present paper deals with the effect of the same alloying elements on the properties of extruded magnesium. This investigation also had as its aim the development of a wrought alloy having a better combination of room-temperature strength and ductility and elevated-temperature strength and creep resistance than is found in magnesium-Mischmetal-manganese alloys, which have been reported earlier.2-5 The only known attempt to study wrought magnesium alloys containing pure cerium instead of Mischmetal was made by Mellor and Ridley.6 They found that in the form of rolled bars there is a definite, optimum cerium content for creep resistance at 200 °C and that the creep resistance of these alloys at 200 °C is significantly Improved by heat treatment at 550" to 580"C. In the present investigation the compositional variation in mechanical properties of the following alloy systems is presented: I—magnesium-Misch-metal. 2—magnesium-cerium-free Mischmetal. 3— magnesium-didymium. 4—magnesium-cerium. 5— magnesium-lanthanum. Alloys containing predominately praseodymium are not included in this series because of the lack of this material. Experimental Procedures The alloying ingredients used in preparing the alloys described herein are the same as those reported in the earlier paper.' Cerium-free Mischmetal is the rare-earth mixture remaining when the cerium is removed from Mischmetal, which contains all the rare-earth metals as they occur naturally in mon-azite sand, the ore from which Mischmetal is produced. Removal of both cerium and lanthanum from Mischmetal leaves what is commonly called "didym-ium," consisting predominantly of neodymium and praseodymium. Although the composition of the particular batch of each metal used may differ somewhat from the analysis presented previously, these differences are not great enough to warrant repeat- ing the specific composition of each material. The electrolytic magnesium used as the starting material in these alloys has the same typical analysis as that given in the earlier paper.' The alloys were prepared in small laboratory melts applying all the necessary precautions for alloying rare-earth metals with magnesium described by Marande.' Most melts were large enough to cast one 3 in. diam billet 10 in. long. In a few cases, particularly the didymium-containing alloys, the lack of sufficient amounts of the rare-earth metal limited the size of the billet to 6 to 8 in. All billets were scalped to a diameter of 2 15/16 in. and faced to a length of 9 ¼ in. as limited by the size of the extrusion container. The alloys were extruded into ½ in. diam rod on a 500-ton direct-extrusion press using a 3 in. container. The details of the extrusion step are: billet preheat, 925°F (2 hr); container temperature, 900°F; die temperature, 900°F; extrusion speed, 10 ft per min; reduction ratio, 36:1; and percent reduction, 97.3. The lower melting point of alloys containing didymium' necessitated reduction of the extrusion speed to 5 ft per min in order to prevent hot shorting during extrusion. Adequate lengths were cropped from both ends of each extruded rod to assure that all the material used for tests was extruded under uniform conditions. Tensile and compressive properties at room temperature are reported in the several conditions of heat treatment. The ASTM designations are used to distinguish these conditions as follows: T5—Direct age at 400°F (16 hr) T4—Heat treat at 950°F (4 hr) for alloys containing didymium T4—Heat treat at 1050°F (4 hr) for all other alloys T6—T4 + age at 400 °F (16 hr) The lower heat-treating temperature for alloys containing didymium is necessitated by the lower melting point of these alloys. All heat treatments were conducted in electrically heated, circulating-air furnaces. A protective atmosphere containing 0.5 to 1.0 pct sulphur dioxide was used for the high temperature heat treatments. Tension and creep specimens 6 Yz in. long and compression specimens 1½ in. long were cut from the extruded rod. A reduced section of ? in. diam was machined on the tension specimens, whereas on the creep specimens a reduced section of 0.450 in. diam

Jan 1, 1952

By P. W. George

This paper presents geological data regarding deposits of over 7,500,000 tons of fine-grained sulphide ore in barite gangue. A series of pyroclastics and arkoses was intruded by sills of quartz porphyry in connection with batholithic intrusions of granite 3 miles from Buchans. Gentle folding, with fracturing acid shearing of tuff beds and intruded quartz porphyry, accompanied and followed the intrusion of granite and porphyry. The sulphide-barite mineralization is localized primarily in fractured and sheared tuff beds, but also in the sheared quartz porphyry. Two structures have proved particularly favorable for mineralization-one, the center of an anticline; the other, a series of weak, incompetent tuff beds intruded by thin sills of quartz porphyry and located between strong beds of arkose. During the folding the weak tuff with intruded quartz porphyry was intensely sheared and contorted and subse-quently mineralized by sulphides and barite.

Jan 1, 1937

By G. Ansel, J. P. Doan

The important literature concerning zirconium in magnesium-base alloys is predominantly contained in patent references. Sauerwald, Eisenreich, and Holubl-4 discovered the profound grain-refining influence of small amounts of zirconium on cast magnesium and the attendant increases in strength and ductility. They extended their work to reveal that limited amounts of certain other elements, including zinc, could be added for further improvement in strength and hardness. British Patent 5111375 relates to the parent discoveries of Sauerwald, Eisenreich, and Holub. All of these references deal primarily with casting characteristics and properties in the cast state. Minor mention is made of desirable tensile strength, ductility, and toughness of wrought Mg-Zr alloys* modified by one or more additional elements. No extensive reference in the literature5. has been found to the particular characteristics of wrought blg-Zn-Zr alloys, with which the present paper is concerned. The work to be discussed represents essentially an extrusion study of the blg-Zn-Zr alloys and indicates that this system is highly interesting in the wrought state both academically and commercially. Accordingly, an important aim of this paper is to describe the hot-workability, tension and compression properties, metallography, and toughness of these alloys. Compositional variations are limited to the ranges 0 to 7 per cent Zn and 0 to I per cent Zr. Experimental Procedure Alloying and Casting Alloying ingredients were cell magnesium, commercial zinc (intermediate grade), and a chloride salt containing approximately 50 per cent ZrCl² and 50 per cent alkali chlorides. This salt is produced by Titanium Alloy Manufacturing Company. Melting, alloying, and pouring procedure essentially followed the crucible process as described by Nelson.6 The magnesium was melted using Dow No. 310 flux, and the temperature raised to 1350° to 1400°F for the alloying operations. After alloying of the zinc, the zirconium containing salt was added in small portions with vigorous stirring. This is an adaptation of the method described in British Patent 533264.7 The alloying efficiency of zirconium was approximately 30 per cent. During the alloying of zirconium, fluorspar was added in amount required as a flux-inspissating agent. Next the melt was refined with Dow No. 310 flux and held quietly for 15 min. Finally billets were cast in a book-type permanent mold

Jan 1, 1947

By K. E. Brown, F. W. Jessen

By utilizing an 8,000-ft experimental field well equipped with 10 gas-lift valves and 10 Maihak pressure recorders, gas-lift tests were conducted with port sizes ranging from 5/16 through I in. The well was equipped to provide accurate means of measuring surface pressures, temperatures, quantity of injection gas and fluid production. The tests were conducted in 2%-in. OD tubing, and the well was making 95 per cent water. A complete evaluation of gas-lift-valve port sizes shows the relationship of per cent recovery, gas-liquid ratios, minimum pressure created at the operating valve and horsepower requirements for each port. The length of time necessary for the fluid in the tubing to reach equilib.rium conditions after each cycle was recorded. Fallback of fluid at depths of 477, 969, 1,685, 2,493 and 4,290 ft was noted. For each port size, pressure loads of 2.50, 300, 350, 400 and 450 psi were lifted with a valve operating at approximately 550 psi at 6,000 ft. Gas-liquid ratios for each load were varied from excess gas to a gas volume per cycle whereby the load failed to reach the surface. Numerous curves are presented in evaluating the accumulated dara. The results show a 1-in. port to be the most efficient under all conditions. The production of intermittent liquid slugs against different-sized surface chokes was evaluated. These tests were conducted from a 7/16-in. ported valve at 4,072 ft. Tests indicate that, when possible, a %-in. in diameter choke or larger should be used at the surface. In the past few years most of the advancement in gas-lift operations has been made in continuous-flow operations. Yet, it is estimated that at least 70 per cent of the wells on gas lift in the United States are of the intermittent type. Since the term "slug flow" is sometimes used in both intermittent- and continuous-flow operations, it would be well to distinguish between the two types of flow. Continuous-flow gas lift is defined as a method whereby the fluids are produced at a continuous rate at the surface. This generally requires a continuous injection of gas through a surface choke; however, various other control devices sometimes are installed to eliminate freezing, to shut-off gas during natural flow periods, etc. The actual flow of fluids in the tubing may be of the slug type (one of many flow patterns known to exist in continuous flow). Intermittent flow is defined as a method of gas lift whereby the liquid is produced in separate piston-type slugs. Perhaps this type of flow could best be thought of as a ballistic-type flow where the liquid leaves bottom as a piston, propelled by a slug of expanding gas. Gas generally is injected through some type of control at the surface at predetermined intervals. However, the valve may have characteristics whereby gas can be injected through a small choke and still result in a ballistic-type flow. The purpose of the experimental work was to evaluate the most efficient port size to be used on the operating valve for the ballistic type of lift and, in addition, to establish the importance of utilizing a surface choke large enough to allow slugs to be produced without detrimental effects. This work is part of a compre- hensive study of both intermittent-and continuous-flow gas lift, representing a joint project conducted by the Ohio Oil Co., the Sun Oil Co., Otis Engineering Corp, and The U. of Texas. The problem of evaluating port sizes has been given little previous attention. Some work undoubtedly has been done which has not been published to date. Some tests were conducted when the wireline, mechanically-opened valve (Nixon) first came on the market. This valve was capable of utilizing full tubing area as its port size. It is known that this was a very efficient valve, but to the authors' knowledge the results of tests have never been published. EXPERIMENTAL EQUIPMENT These tests were conducted on an actual field well, the Ohio-Sun Unit Well No. 2-E, in the North Markham-North Bay City field, Matagorda County, Tex. The well incorporated 23/8-in. OD tubing and produced 95 per cent water. Since the running of equipment was to be quite elaborate and expensive, a well was selected in which both intermittent- and continuous-flow tests could be conducted. This particular well was capable of producing in excess of 1,000 B/D of liquid (95 per cent salt water), yet with a 3/64-in. in diameter bottom-hole choke, production was controlled to 82 B/D. Most of the intermittent tests were conducted at this low rate. Figs. 1 and 2 show all the surface and down-hole equipment. As can be seen, every attempt was made to insure that ample equipment was available for reliable testing procedures. Fig. 1 shows the surface testing equipment. The input gas was controlled first by a regulator, then

By J. P. Nielsen, H. Margolin, E. Ence

The Ti-Ni phase diagram has been investigated up to 68 pct Ni with iodide titanium base alloys by metallographic, X-ray, and melting point methods, and from 68 to 90 pct Ni by examination of as-cast structures of sponge titanium base alloys. NVESTIGATION of the nickel-rich portion of the I Ti-Ni phase diagram was first reported by Vogel and Wallbaum in 1938.' This work was subsequently extended to lower nickel contents by Wallbaum' who indicated the possibility of a eutectic reaction for nickel contents below 38 pct. Long et al.3 studied the titanium-rich portion of the phase diagram and found eutectic and eutectoid reactions below 38 pct Ni. However, the temperature of the eutectic indicated by Long et al. was considerably lower than that suggested by Wallbaum. Long and his coworkers synthesized their alloys by powder metallurgical techniques and encountered oxygen and/or nitrogen contamination. Thus the diagram which was obtained did not represent binary alloying conditions. However from these results the features of the binary diagram were predicted. At Battelle Memorial Institute4 the Ti-Ni diagram was investigated up to approximately 11.5 pct Ni with sponge titanium alloys. The range of temperatures used was not sufficient to define the eutectoid temperature or composition. The data of Wallbaum2 and Long et al.8 were of particular interest for the present study, and although the work was originally concerned with the region below 40 pct Ni, the investigation was extended to higher nickel contents in an attempt to resolve the differences between these workers. Experimental Procedure Preliminary work on the Ti-Ni system was carried out with duPont Process A sponge titanium alloys to reduce the amount of subsequent work to be done with iodide titanium base alloys. The sponge titanium used contained 99.71 to 99.77 pct Ti, 0.1 pct Fe and 0.005 to 0.009 pct Ni. The iodide titanium obtained from the New Jersey Zinc Co. contained 99.9 to 99.95 pct Ti. Nickel used with sponge titanium was 98.9 pct pure. The high-purity nickel alloyed with iodide titanium was cobalt-free with approximately 0.05 pct C and was obtained through the courtesy of the International Nickel Co. The 15 g sponge titanium charges for melting were prepared by compacting in a die or by placing the weighed portions of nickel and titanium directly into the furnace. Iodide titanium charges were made by drilling holes in the as-received rod and inserting the nickel or by wrapping the nickel in sheet. Sponge titanium alloys containing from 0.2 to 90 pct Ni and iodide titanium alloys containing 0.2 to 68 pct Ni were prepared by these methods. In addition to these alloys several 1/2 1b sponge titanium alloys were supplied by the Allegheny Ludlum Co. The charges were melted in an arc furnace under an argon atmosphere. The procedures used were similar to those reported in the literature5,' and the furnace has been described.' Except for iodide titanium alloys with 40 to 68 pct Ni (see section on copper contamination), each alloy was melted for 1 min, then either turned over or broken before re-melting for an additional minute. Currents of 200 to 400 amp were used depending on the melting point of the alloy. Prior to heat treatment, alloys containing less than 14.5 pct Ni were hot-forged at 750°C. With the exception of alloys in the homogeneity range of the compound TiNi, alloys of higher nickel contents could not be hot-forged. Heat treatment of iodide titanium base alloys was carried out in argon-filled quartz capsules which were broken under water at the conclusion of heat treatment to quench the specimens. Temperatures were controlled to ±5oC and annealing times up to 48 hr were used. For melting point determination, specimens were placed in carbon crucibles which were in turn en-capsuled in argon-filled quartz capsules. The start of melting was determined by rounding of corners and by metallographic examination. Complete melting was considered to have occurred at that temperature at which the specimen assumed the shape of the crucible. Specimens were prepared for metallographic examination by mechanical polishing or by an electrolytic procedure." For alloys containing up to 80 pct Ni Remington A etch7 50 pct glycerine, 25 pct HNO,, 25 8 HF) was used. For higher nickel alloys aqua regia and Carapella's etch (5 g FeCl,, 2 ml HNO,, and 99 ml methyl alcohol) were employed. Specimens to be exposed for powder patterns were prepared by filing, by breaking specimens in a

Jan 1, 1954

By G. Krauss, W. Pitsch

The fine structure of the bcc martensite formed in an Fe-33 wt pct ATi single crystal of arrstenite is sho~on by transmission electron microscoPy to consist of combinations of transformation twins, stacking faults, deformation twins, and regular arrays of parallel screw dislocations. These structures constitute evidence for the multiple lattice-invariant deformations which operating during the formation of martensite could produce the real habit-plane scatter measured by a two-surface analysis of the plates formed in the single crystal of this investigation and reported in the literature for other Fe-Ni rnartensites. CRYSTALLOGRAPHIC theories1,2 of martensitic transformation show that the habit plane of martensite in a parent lattice is dependent in part upon an inhomogeneous distortion or lattice-invariant deformation which takes place on a fine scale within a martensite plate during its formation. Several recent theoretical papers3,4 have addressed themselves to an analysis of a wide variety of conceivable lat-tice-invarient deformations and the habit planes which they produce, while experimental investigation have been concerned with either the measurement of habit planes or the description and identification of the martensitic fine structure which reflects the nature of the lattice-invariant deformation operating during transformation. In Fe-Ni alloys with subzero Ms temperatures, the group of alloys with which this paper concerns itself, habit planes have often been found to scatter an amount greater than might be expected from possible experimental errors,5-7 and fine twinning has been identified as a major constituent of the fine structure of martensite.8-11 It has been suggested3,4 that more than one type of invariant shear occurs during martensitic transformation. This possibility has been experimentally supported12,13 by the observation of both dislocation configurations and twinning in a single martensite plate. The purpose of this paper is to report additional evidence for multiple lattice-invariant deformations in martensite and so to account for the real scatter in the habit planes of the martensite plates formed in Fe-Ni alloys. EXPERIMENTAL PROCEDURE The Fe-Ni single crystal was produced by pulling a high-purity iron and nickel charge through a single-crystal vacuum furnace in an alumina crucible. The crystal was double-melted to promote homogeneity and to increase its size by further additions on the second pass. In its final form the crystal was 4 cm in diam and 5 cm long. The nickel and carbon contents were analyzed at 32.9 and 0.006 wt pct, respectively. The austenite of this alloy first transformed to martensite by bursts at about -120°C, and, to preserve as much of the austenite as possible, all transformation was performed just below -120°C. Some observations were made on transformed samples which had been heated for 2 min at 340°C. It is assumed that the features of the martensite of these samples, Figs. 1 and 4, are the same as those of the as-quenched martensite. Orientation of the crystal by X-ray diffraction established 10.735 0.609 0.3161? as the axis of the crystal, an orientation that was checked within 2 deg by neutron diffraction. Further checks by electron diffraction of samples cut normal to the axis confirmed this orientation within the larger limits of error inherent in electron diffraction of thin foils. The X-ray orientation was the one used for the two-surface analysis of the martensite habit planes. A two-surface analysis was performed on the quadrant of the single crystal which had been oriented by both X-ray and neutron-diffraction techniques. Photomicrographs at X50 were made on two surfaces along an edge 2 cm long. Fiducial marks and the fact that many of the plates were almost completely surrounded by retained austenite made good matching of individual plates on two surfaces possible. The habit-plane trace on a surface was taken as the best line parallel to the long axis of a plate. A measure of the accuracy afforded by this criterion was provided by a family of very large plates which appeared at intervals along the entire 2 cm length of the edge. The plates all had habit-plane traces within 2 deg of one another. Many of the plates did not show midribs and, therefore, the use of midribs7 to represent habit-plane traces was not feasible in this investigation. The over-all experimental accuracy is estimated to be better than ±2 deg. Samples for transmission examination in a Siemens Elmiskop I at 100 kv were prepared by cutting 2-mm-thick discs from the single crystal, removing about 0.5 mm by chemical polishing,14 trans-

Jan 1, 1965

By J. L. Rodda, R. L. Wilcox, E. C. Truesdale

In recent years various problems in connection with research work on the preparation and properties of zinc-base alloys have required reliable information concerning the constitution of the zinc-rich portion of the iron-zinc equilibrium diagram. On numerous occasions rather positive indications were obtained that, for example, the solubility of iron in zinc was incorrectly represented on the current equilibrium diagrams. A careful study of all the available literature relating to the iron-zinc system led to the conclusion that much of the early work was unsatisfactory as measured by present standards of experimental accuracy, and as a result it was decided to redetermine the location of the liquidus curve and of adjacent portions of the diagram. Part I of this paper comprises a description of the experimental methods and a summary of the results by means of which the zinc-rich end of- the iron-zinc diagram has been revised in the following ways: 1. Measurements of the solubility of iron in liquid zinc by several different sampling methods, leading to a relocation of the liquidus curve. 2. Microscopic, conductivity, and X-ray studies of the solid solubility of iron in zinc, which, together with thermal analyses, have resulted in new values for the solid solubility and the eutectic temperature and composition. 3. Heating and cooling curves, obtained by a refined differential method, leading to new locations for the two peritectic horizontals. In Part I1 of the paper the attempt is made to review all of the published work having a bearing on the constitution of the iron-zinc system, and to correlate the present results, and some recently published data involving the use of X-ray technique, with the earlier work, much of which was done from 25 to 30 years ago.

Jan 1, 1936

By E. H. Roberts, L. G. Swenson, F. C. Nix, R. A. Morgen

THE binary system lead-antimony has been the subject of comprehensive investigations in these laboratories by Dean' and his associates. The effect of a third constituent on this system, particularly on the lead-rich alloys in which dispersion hardening was found, has a commercial value as well as an academic interest. This paper covers the effect of the addition of copper, bismuth and tin, all of which are likely to be found in commercial lead-antimony alloys, and is divided into three parts, as follows: I. The System Lead-Antimony-Copper II. The System Lead-Antimony-Bismuth III. The Lead Corner of the System Lead-Antimony-Tin These three systems are of three different types, and hence may be considered as covering three general kinds of additions. Bismuth forms no compounds with either lead or antimony and forms solid solutions with both. Copper forms several compounds with antimony as well as solid solutions but with lead it forms a two liquid layer system and no appreciable solid solution. Tin is soluble in both lead and antimony in the solid state and also forms a compound with antimony. The effect of small amounts of bismuth on the lead-antimony alloys is small, having no appreciable effect on the solubility of antimony. The temperature of the solidus floor is lowered appreciably by the presence of bismuth, cutting down the range of heat treatment. Copper, on the other hand, due to compound formation, increases the apparent solubility of antimony. The excess antimony is tied up with the copper finally and so is not available for dispersion hardening. The net result of addition of small amounts of copper is to shift the dispersion hardening peak of the

Jan 1, 1928

By E. A. Gulbransen, J. W. Hickman

One of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film. A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film. A comprehensive program has been undertaken to study these phenomena. This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C. Before the introduction of the electron diffraction technique, it was necessary to use either direct chemical analyses or X-rav diffraction analyses to determine the nature of the oxide film formed on the metal or alloy. Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry. In special cases the information obtained may be identical, but in general both viewpoints are necessary. Much of the early work was carried out on the oxidation of bulk samples where thick films were obtained. The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses. Although much useful information has been obtained in this manner. little could be learned about the character of the protective oxides during the period when the films were actually protective. Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique. In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective. Literature The oxidation of iron has been extensively investigated by X-ray and electron diffraction. Jackson and Quarrelll found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature. The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe³O4; between 515° and 900°C. the stable film was FeO. Above the upper change point of iron the oxide was found to be Fe³O4. From 400' to 515°C., FeO, Fe³O4 or a mixture of the two oxides was found. Recrystallization of the air-formed film below 400' and above 900°C. led to the formation of Fe3O4. In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described.

Jan 1, 1947

By G. L. Oldright, T. B. Brighton, C. M. Dice

The base bullion from the lead blast furnace contains varying amounts of the impurities left in the smelter feed by the concentrator, regardless of the method of smelter operation. These impurities may be held in part in mechanical suspension rather than being present as true alloys. However, usually there is little free space in the crucible in which to separate these drosses before the bullion is taken from the lead well. When such a dross is melted in a laboratory crucible and allowed to cool, the products obtained are lead bullion, speiss, and matte in well separated layers. Typical analyses of layers are: Analyses. Per Cent Element Bullion Speiss Matte Pb.............................................. 92.0 41.2 38.3 Cu.............................................. 2.4 36.3 40.6 As............................................... 4.0 16.5 4.3 Sb............................................... 0.7 0.2 0.4 S................................................ 0.6 1.9 13.1 Fe............................................... 0.0 0.0 0.0 Totals......................................... 99.7 96.1 96.7 The absence of iron in these products drossed from the blast-furnace bullion proves that the impurities for the greater part are not simply finely divided blast-furnace speiss or matte that has been dissolved or dispersed in the lead, but are held in solution by the liquid metal and rise to its surface as infusible compounds when the temperature of the bath is lowered. In general, the drosses made locally are metal sulphides and arsenides and not oxidized compounds. The large content of metallic lead also does not seem to be retained because of oxidized compounds

Jan 1, 1937