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By I. R. Kramer

[The final paper in the diffusion symposium was given by I. R. Kramer. The author called attention to the diffusion characteristics of chromium deposited on the surface of steel by treatment with chromium chloride and alloyed with the surface layer of the steel by thermal treatment. As the data cited were previously published in the paper " Chromizing of Steel," by I. R. Kramer and Robert H. Hafner (Metals Technology, October 1942, and in the Transactions, volume 154, 1943, pages 415-420), it is unnecessary to reproduce these data here. The following paragraphs are taken from the author's presentation.— Editor.] Aside from the well-known practical application of the diffusion phenomena to carburizing and calorizing, -diffusion also finds application in adding alloying elements to the surfaces of steel parts. The chromizing of steels is a process by which the surface of a low-alloy steel may be enriched with chromium to form a highly corrosion-resistant case; This chromized case differs from an electroplated coat in that it is a diffused layer integral with the base metal and has all of the properties of a high-chromium steel. Recently a method of chromizing has been developed in Germany by Daeves, Becker and Steinberg in which gaseous chromium chloride and hydrogen are passed over the steel at temperatures of 1650° to 1800°F. The chromium chloride reacts with the iron to give chromium and iron chloride. The chromium atoms are deposited on the surface and diffuse in as the iron atoms diffuse out, forming a layer rich in chromium. The principal role of hydrogen is to remove the carbon from. the surface of the steel. Of the two mechanisms, chemical reaction and diffusion, the one operating at the slower rate will determine the rate of formation of the layer. In this case, diffusion is slower and therefore any factors influencing its rate will affect the process. The rate of diffusion is influenced by the temperature and crystal structure of the parent metal. Depth-concentration studies show that the concentration falls off gradually for a considerable distance and then drops sharply at about 13 per cent chromium, the point coincident with the boundary of the gamma loop. The influence of the composition of the base metal upon diffusion is quite important. The depth of penetration of the chromium decreases as the carbon content increases and, of more importance, the chromized layer becomes brittle and is likely to spa11 if the carbon content is too high. It appears that in order to chromize successfully the carbon must be fixed by strong carbide-forming elements such as chromium or molybdenum, which decrease the diffusion of carbon. If this is not done, the carbon will diffuse from the interior faster than the chromium can diffuse inward, thus forming a carbide barrier. The corrosion resistance of the chromized layer is high, and these steels offer some unique advantages over other corrosion-resisting coating or alloys. While chromizing is not meant to replace stainless steels, it may serve in the saving of alloying elements. The chromizing process uses soft or low alloyed steels that can be easily hot or cold formed and since the chromized layer is soft and firmly adherent, chromized parts can be subjected to cold deformation without spalling or chipping and without loss of corrosion resistance.

Jan 1, 1944

By I. R. Kramer

[The final paper in the diffusion symposium was given by I. R. Kramer. The author called attention to the diffusion characteristics of chromium deposited on the surface of steel by treatment with chromium chloride and alloyed with the surface layer of the steel by thermal treatment. As the data cited were previously published in the paper " Chromizing of Steel," by I. R. Kramer and Robert H. Hafner (Metals Technology, October 1942, and in the Transactions, volume 154, 1943, pages 415-420), it is unnecessary to reproduce these data here. The following paragraphs are taken from the author's presentation.— Editor.] Aside from the well-known practical application of the diffusion phenomena to carburizing and calorizing, -diffusion also finds application in adding alloying elements to the surfaces of steel parts. The chromizing of steels is a process by which the surface of a low-alloy steel may be enriched with chromium to form a highly corrosion-resistant case; This chromized case differs from an electroplated coat in that it is a diffused layer integral with the base metal and has all of the properties of a high-chromium steel. Recently a method of chromizing has been developed in Germany by Daeves, Becker and Steinberg in which gaseous chromium chloride and hydrogen are passed over the steel at temperatures of 1650° to 1800°F. The chromium chloride reacts with the iron to give chromium and iron chloride. The chromium atoms are deposited on the surface and diffuse in as the iron atoms diffuse out, forming a layer rich in chromium. The principal role of hydrogen is to remove the carbon from. the surface of the steel. Of the two mechanisms, chemical reaction and diffusion, the one operating at the slower rate will determine the rate of formation of the layer. In this case, diffusion is slower and therefore any factors influencing its rate will affect the process. The rate of diffusion is influenced by the temperature and crystal structure of the parent metal. Depth-concentration studies show that the concentration falls off gradually for a considerable distance and then drops sharply at about 13 per cent chromium, the point coincident with the boundary of the gamma loop. The influence of the composition of the base metal upon diffusion is quite important. The depth of penetration of the chromium decreases as the carbon content increases and, of more importance, the chromized layer becomes brittle and is likely to spa11 if the carbon content is too high. It appears that in order to chromize successfully the carbon must be fixed by strong carbide-forming elements such as chromium or molybdenum, which decrease the diffusion of carbon. If this is not done, the carbon will diffuse from the interior faster than the chromium can diffuse inward, thus forming a carbide barrier. The corrosion resistance of the chromized layer is high, and these steels offer some unique advantages over other corrosion-resisting coating or alloys. While chromizing is not meant to replace stainless steels, it may serve in the saving of alloying elements. The chromizing process uses soft or low alloyed steels that can be easily hot or cold formed and since the chromized layer is soft and firmly adherent, chromized parts can be subjected to cold deformation without spalling or chipping and without loss of corrosion resistance.

Jan 1, 1944

By C. B. Alcock, M. G. Hocking

The kinetics of the growth of sulfate layers on blocks of Cu20 has been studied between 688" and 800°C. At 788c the over-all weight increases followed the parabolic rate law, with k = 216 30 sq mg per cm4 min, using a 1:1 entering gas mixture of SO2:02. At 757 after an initial linear period the parabolic rate law was followed, with k = 57.8 10 sq mg per cm4 min. The gas mixture required a platinum catalyst to produce the maximum SOs pressure. The sulfation rate at 757' and 788c was high until all the CUZO had changed into a core of CuO, when it became very much lower. At 757°C marker experiments showed that the sulfates (CuO. CuS04 and CuSO4) grow outwards from the oxide surface, but CuO. CuS04 mixed with CuO was found beneath the markers. At 688 markers were found at the CuO. CuS04/CuS04 interface. Visual observations at 757 showed a liquid eutectic moving beneath the sulfate surface. causing very rapid sulfation and extruding to solidify as thick 'needles" up to 8 mm long. Marker experiments have shown conclusi.cely that CuO grows on Cu20 in air by the outward migration of copper. ThermODYNAMIC measurements on the sulfate and basic sulfate of copper, reported recently,' are followed here by measurements of the rates of formation of these sulfates on cuprous oxide, in order to provide a background for the understanding of roasting processes. peretti2 and McCabe and Morgan3 have shown that the phase Cu20 lies next to Cu2S when the sulfide is roasted under conditions where sulfates will be formed. Since this would present too complex a system for kinetic study, the present work4 has been based on the kinetics of sulfation of the oxide phase. The results of a study of the kinetics and mechanism of the sulfation of cobaltous oxide have recently been reported.4,5 Results on the sulfation of cuprous oxide have also appeared,6 but are at variance with those to be reported here. This seems to be because the previous workers6 did not obtain constant SO3 pressures from the SO2/O2 sulfating gas mixtures used, as will be discussed later. Wadsworth, Leiter, Porter, and Lewis found that the sulfates produced when SO2/O2 mixtures are passed over Cu20 at red heats are CuS04 and the basic sulfate CuO.CuSO4. When the decomposition of CuS04 was followed' by differential thermal analysis, a stage corresponding to CuO .CuS04 was reached before decomposition into the oxide occurred. APPARATUS The vertical furnace used for quantitative studies was a conventional resistance-heated and propor- tionately controlled furnace with an even zone (1 deg) which was 4 cm long. The gas mixtures of SO2 and 02 were made by mixing measured flows from capillary flowmeters and drying over phosphorous pentoxide before passing them into the Pyrex top-piece of the furnace assembly. A mullite tube of bore 2% cm was used as reaction vessel and at the bottom of this tube was a trap for SO3, which condensed as a colorless liquid. The residual gas was led into a fume cupboard for ventilation to the atmosphere. The furnace used for visual observations of needle growth and other phenomena consisted of a transparent silica reaction tube of bore 3 cm, having an optically flat silica window sealed into its wall. The reaction tube was clamped vertically, inside a mullite tube of bore 4 cm and length 42 cm which was heated by Kanthal windings. The window in the silica reaction tube was arranged opposite a hole 3 cm wide and 2 cm tall which had been cut in the wall of the mullite winding tube 19 cm from its top end. A binocular microscope was used to look through the window, illumination being provided by a focusing microscope-lamp offset sideways and downwards. The oxide block to be sulfated was suspended from the removable Pyrex top-piece to the reaction tube, by means of which it was inserted at the start of the experiment, and through which entered the S02/02 gas mixture. The variation of the temperature inside the reaction tube with horizontal and vertical displacement from the window was investigated, and, while it can be said that the temperature was constant 1 deg, its value at a given position was known only to 12 deg. In both furnaces, the oxide block to be sulfated was suspended from a small silica hook immediately downstream from a platinum thimble used as catalyst, which was held on a long silica rod from a Pyrex spring attached to the removable Pyrex top-piece of the furnace. The spring was only included in the quantitative sulfating furnace; its sensitivity was 1.4 cm per g and it was found to be free from creep in a 16-hr test when carrying the working load. The extensions were followed by a cathetometer which could be read to 0.001 cm, corresponding to i0.7 mg. Extensions of the spring were measured on adding weights between 5 and 500 mg to the working load (thimble + oxide block), and Hooke's law was closely obeyed. SAMPLES Cuprous oxide blocks were prepared by oxidizing Johnson Matthey "Specpure" copper sheet of 1 mm thickness (impurities: iron at 3 ppm, silver at 2 ppm, lead, nickel, sodium, and silicon each at 1 ppm, calcium, chromium, magnesium, and manganese each at less than 1 ppm) for 6 days in air at 1000°C in a re-crystallized alumina boat. It has been reported7 that when Cu20 is prepared by heating copper sheet for 1 day the central plane of the blocks produced consists

Jan 1, 1967

By RAY LYMAN WILBUR

SINCE boyhood I have had a keen interest in mining engineering. To see the prospector with his pack outfit and his pan, followed by the assayer and the trained engineer, has always had -something of the lure of romance for me. It is appropriate that the American Institute of Mining and Metallurgical Engineers should hold a general meeting in California, since this State has long been a home of mining engineering. Here, after the early open methods of mining, it has been necessary for the universities to train men in geology and mining, so that the earth could be penetrated and the rich ledges opened. In the eighty years in which the mines of California have been offering experience to the miners of the world, we have seen mining engineering evolve from a comparatively simple art, covered largely by rule of thumb, into a complex group of specialties, each utilizing the very latest discoveries in the various fields of physical sciences. Mining, too, has become a great business requiring large financial support and the most careful handling. Those mining engineers who have applied new processes in special fields have thus been able to give a wide-flung range to their activities in all parts of the world. The hand of nature in distributing minerals over the surface of the earth has compelled the mining engineer to become a modern pioneer, facing the heat of the tropics as well as the frozen regions of the north. There has been a marked cosmopolitan aspect to mining engineering, since the engineer had to go wherever the prospector discovered favorable leads. This has meant dealing with the harshest of conditions, the handling of labor of all sorts, the control of sanitary conditions, and relations to all forms of transportation. Naturally this has called on some of the very best minds in all countries to unlock the stores of hidden wealth. To make them available for civilization has been the job of the mining engineer.

Jan 1, 1929

By C. S. Harloff, Frank R. Corwin

THE Nichols Copper Co., associated with the Phelps Dodge Corp. and the Calumet & Arizona Mining Co., has constructed at El Paso, Tex., and is now operating a copper refinery with a yearly capacity of 100,000 tons of anodes. Transportation facilities were perhaps the most important of the considerations that led to the selection of this site. The rapid industrial development of the Middle and Far West has increased the consumption of copper there. The advantage of local refining as against shipping the copper to the Atlantic sea- board is apparent. Copper refined in the Southwest is equally competitive for export shipment, either from the Gulf or the Pacific Coast ports. The tonnage of copper produced in the Southwest not only justifies the construction of this plant, but may warrant considerable expansion in years to come.

Jan 1, 1930

By L. L. McDaniel

Copper smelters of various kinds have operated in the Morenci district since 1872, but all have been abandoned with the exception of the present Morenci Smelter of Phelps Dodge Corporation, which was completed in 1942. During the five-year period starting in 1937, the Morenci ore body was prepared for open pit mining, pilot mill test work was carried out, and a complete reduction works, of which the Smelter is a part, was designed and erected. Actual construction work on the Morenci Smelter was started in the fall of 1940, and warming up of the units began on April 1, 1942. Charging of the reverberatory furnaces commenced on April 18, 1942, and the first anode copper was produced on April 26, 1942. The smelter was originally designed to handle the production of the Morenci Concentrator on a 25,000 ton per day program, but by the time the smelter was in operation, plans were already underway to increase the smelter capacity to handle the production of the concentrator which was being enlarged to 45,000 tons a day capacity as a war-time necessity. This extension to the smelter was completed and the new units were put in operation toward the beginning of 1944. The original smelter consisted of a smelter crushing plant, bedding plant, two direct-smelting reverberatory furnaces with two waste-heat boilers on each furnace, three converters, an anode department, a stack, and all of the usual accessory smelting equipment. The extension consisted of increasing the bedding plant from three to five beds, the reverberatory department from two to four furnaces, and from four to eight waste-heat boilers, and the converter department from three to six converters. A third converter aisle crane was added and additions were made to the flue systems and conveyor systems throughout the smelter; but no change was made in the smelter crushing plant or the anode department, and the same stack was used for all additional Smelter units. A blister casting machine was installed at that time in the south end of the converter aisle to handle excess and emergency production above the capacity of the anode department and in 1947 a converter aisle skull breaker and a lime burning plant were added as the final units for a complete plant. The choice of direct smelting over calcine smelting for the Morenci Smelter was made after careful study by members of the Western organization of Phelps Dodge Corporation and after test runs on direct smelting of Morenci concentrate had been made at the Douglas Smelter of Phelps Dodge Corporation. The Morenci furnace charge is made up of comparatively high grade concentrate with no ores of smelting grade available and with only flux, a small amount of copper precipitate and the usual amount of smelter secondaries to be smelted with the concentrate. The simplicity of direct smelting for this charge and the large amount of waste-heat steam available from direct smelting operations were factors influencing the decision to adopt direct smelting for Morenci. The design of the Morenci Smelter and the type of units selected followed best experience at the Douglas Smelter of Phelps Dodge Corporation. A description of the original smelter before operations started was given in an article in the May 1942 issue of Mining and Metallurgy. The purpose of the present article is to describe the enlarged Morenci Smelter, with a discussion of metallurgy and operating practice and to show tabulations of operating and metallurgical results obtained. Because of beginning operations during the early years of World War 11, many problems caused by labor shortage were encountered, but no major difficulties developed in starting the new plant. However, because of labor shortage, full scale Smelter production was not reached until the fall of 1946. Fig 1 shows a general plan of the Morenci Reduction Works. The arrangement of the smelter equipment is shown in Fig 2, a sectional view of the smelter is shown in Fig 3, and the smelter flow sheet is shown in Fig 4. Metallurgy The metallurgy of direct smelting, being more or less fixed by the character of the charge, is not subject to the control available in calcine smelting. Slags may be modified by the addition of suitable fluxes, but the grade of the matte is determined almost entirely by the iron:copper ratio of the concentrate. The direct smelting operation involves distributing the wet concentrate along the sidewalls and in the bath of a reverberatory furnace by means of some suitable feeding device and raising the temperature of the charge so that first the moisture is driven off, then the first-atom sulphur is eliminated, and finally the sulphide portion of the charge melts and runs into the bath, carrying with it the non-sulphide portion which has been partially fluxed to form a suitable slag. The fusion of the non-sulphide portion is completed by contact with the irony converter slag which is regularly being poured into the reverberatory furnace. The smelting rate of the charge is influenced by the mineralogi-cal composition of the sulphide portion of the concentrate and by the composition and amount of the non-sulphide portion including the fluxes added. The copper in Morenci concentrate is chiefly in the form of chalcocite, intimately associated with pyrite, and non-sulphide content is very low so that

Jan 1, 1950

By R. J. Grace

Primarily, this report presents the results of direct efficiency tests which were conducted on the 200-hp Coal-Pak, hot water generator, No. 3 unit, at the Otterbein College heating plant in Westerville, Ohio. Also included is a comparison of fuel consumption of the old plant with that of the new plant, a comparison of efficiencies obtained by the indirect method on a 300-hp Coal-Pak, and the cost of gas vs coal to show the savings effected by the latter. Tests were conducted with ten different bituminous coals selected by Mr. S. A. Frye, business manager at Otterbein College. The coals, of ten different suppliers, from four different states and eight different seams, represented competitive products economically available to the heating plant. The tests were conducted by the usual plant personnel which consisted of the plant superintendent and two assistants. No outside supervision of any kind was given during the tests. The tests were made from Dec. 13, 1960, through Mar. 4, 1961. During this period, 300.03 tons of coal were burned in the No. 3 unit. This tonnage represented 25.5 pct of the total coal requirements for the 1960-61 season. Operation during the period was typical for the comfort heat load which the plant supplies. Of the 78.12 operating days, the boiler was on bank or holdfire 14.31 days, or 18.32 pct of the time. The length of individual bank periods varied from 2 hr to three days. Run periods varied from about 2 hr to 7.26 days. DESCRIPTION OF PLANT AND HEATING EQUIPMENT The new Otterbein College heating plant, completed in the summer of 1957, is located in a 50x50 ft boiler room on the lower level of a combination maintenance building and heating plant. The building is situated away from the main college complex on a hillside, which allows for on-grade delivery of coal to the three bunkers. The bunkers are located directly above and connected with the individual stoker hoppers. Fig. 1 shows an in-plant view of the Coal-Pak installations. The No. 3, hot water, unit is at the extreme right. The heating plant consists of three 200-hp Coal-Paks. Unit No. 1 is operated at 4 psi and carries the steam heating load of 14,000 sq ft EDR (steam) installed in two buildings. Provision has been made to convert these buildings to hot water heating at some future date. Since the unit under maximum load conditions operates only at about 50 pct steaming capacity, a heat exchanger was installed to convert steam to hot water. Thus, during light loads in mild weather the unit can be employed more efficiently to supply both steam and hot water and eliminate the need for operating either of the two hot water units. Units No. 2 and No. 3 serve a hot water heating circuit for a large group of 21 buildings of the College. These boilers deliver hot water at temperatures up to 200°F to the various buildings through distribution lines in tunnels. The present calculated maximum heat loss for the College is 15.195 million Btu per hr. The Coal-Paks have individual design capacities of 6.700 million Btu per hr. Table I lists the design date for the Coal-Paks. The No. 3 unit was chosen as the test unit, primarily because of its bunker location at the far end of the delivery ramp. Because of this location any excess coal above bunker capacity could be conveniently stored and isolated from the adjoining bunkers. Each bunker has a capacity of 30 to 35 tons of coal. The No. 2 and No. 3 hot water generators are equipped with automatic controls which maintain the

Jan 1, 1962

By R. H. Jacoby, V. J. Berry

Future depletion performance and ultimate oil recovery from reservoirs producing under volumetric control are often predicted with the aid of a material balance equation. When the reservoir fluid is very volatile, however, certain assumptions implicit in the use of the conventional methods are no longer valid. This is became laboratory differential vaporization test procedures do not adequately represent the reservoir depletion process and the performance of surface separation facilities. In such cases recovery of stock tank oil per unit of pressure decline can be predicted only from a detailed knowledge of the separator conditions and the over-all composition of the fluid entering the wellbore at each stage of depletion. Surface recovery is not simply related to the total quantity of liquid flowing into the well under reservoir conditions. In order to improve predictions for reservoirs which produce volatile oils, a step wise method of calculation has been developed. This method uses relative permeability data and multicomponent flash calculations to predict oil and gas production as a function of reservoir pressure. Calculations are presented for a reservoir containing a volatile crude oil, and predicted tank oil recovery by primary depletion is more than twice that predicted by conventional methods which are known to be adequate for ordinary black crude oils. Calculated maximum produced gas-oil ratio is less than one-fourth of the conventional prediction. Wellstream compositions have also been used to determine variation in stock tank oil composition and liquid content of the separator gas. This information is of particular importance for crude stabilization calculations and for design of gasoline plant facilities to recover LPG and natural gasoline. INTRODUCTION The estimation of oil reserves and the prediction of future recovery performance of petroleum reservoirs is a frequent task of the petroleum engineer. If the reservoir produces under volumetric control, performance calculations for primary depletion are made by combining oil and gas material balances with the gas-oil flow characteristics of the reservoir rock. For black oil reservoirs, the Schilthuis1 type material balance is commonly employed. For gas or gas-condensate reservoirs, where only one phase is flowing under bottom-hole conditions, a more simplified material balance is used. In the period in which these material balance methods were conceived and put into practice, it was common to classify reservoirs according to the type of fluid produced as (1) black oil reservoirs, or (2) gas or gas-condensate reservoirs. Recently, however, deeper drilling and more extensive studies of reservoir fluid properties have led to the recognition of reservoir fluids with phase characteristics between those of ordinary black oils, and gases or gas-condensate fluids. These intermediate fluids contain relatively large amounts of the hydrocarbons ethane through decane and are found in deep, high temperature (250°F) reservoirs. Such fluids are often referred to as high shrinkage crudes or "volatile oils." They are usually characterized by tank oil gravities above 45° API. high solution gas/oil ratios,

Jan 1, 1958

By Shiro Ban-ya, John F. Elliott, John Chipman

The activity of carbon in Fe-C austenite at 1150°C has been determined for concentrations up to about 2.1 pct C using the equilibrium: C + COz = 2CO; equations have been derived expessing the activity as a function of carbon content on the basis of twelve mathematical models. Several of these represent the data satisfactorily. ACCURATE information on the thermodynamic properties of austenite in the binary system Fe-C is needed as a basis for studies of transformation and precipitation in steels of all sorts, alloy as well as plain carbon. The many attempts to approach this problem through statistical thermodynamics require sound and dependable experimental data in order to evaluate the several models which have been suggested. In this paper we are concerned with the experimental determination of the activity-composition relation in austenite at the temperature of its widest range of stability, approximately the eutectic temperature (1153°C). Accurate investigation of the activity of carbon in austenite may be said to have begun with the work of Dunwald and wagner.' A more detailed study was carried out by R. P. smith2 on the two equilibria: More recent work on these two equilibria has been reviewed by Chipman,3 who pointed out the experimental hazards associated with studies of Eq. [I]. Studies of this reaction involve rather small values of the ratio these are susceptible to errors due to traces of moisture in the apparatus according to the reaction: Ellis, Davidson, and Bodsworth4 evaluated K, for their experimental temperatures and used desiccants to control water vapor pressure. While they were able in this way to obtain consistent values for K1 it cannot be said that all of the uncertainties of the method have been overcome. Results by both methods reported by Schurmann, Schmidt, and wagener5 appear to be consistent except at very low carbon content. Reaction [2] was employed in the experimental work reported here. It is to be recognized, however, that it is not applicable to projected studies of certain alloy steel compositions involving stable oxide-formers.

Jan 1, 1970

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 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 L. S. Darken

IT has been known for sometime that in an ionic lattice, such as that of Ag2S or FeO, the migration velocity of the anion may differ markedly from that of the cation, the cation being usually the more mobile. It has been shown, for example, that during the formation of silver sulfide tarnish on silver, the tarnish layer grows principally by the motion of silver cations through an essentially stationary silver sulfide lattice. Similarly, the growth of wüstite scale on iron proceeds principally by motion of iron ions, this being accomplished with the aid of vacant iron lattice sites into which the iron may readily move. Likewise investigations of solid solutions of various salts show that there is usually considerable difference in the mobility of the different cations. Measurements of the mobility of various metals in liquid mercury indicate that the various metals move at different rates relative to the mercury. In view of the foregoing it seems reasonable to suppose that when any single phase solution is acted upon by a field, the atoms of different elements respond in different ways; in particular, that the force arising from a particular concentration gradient in a binary alloy would cause the atoms of one component to move with a drift velocity which is in general different from that of the atoms of the other component. The recent experiments of Smigelskas and Kirkendall1 support this viewpoint, since they found, in essence, that during diffusion in alpha brass zinc moves appreciably faster than copper. This was evidenced by the relative motion of inert molybdenum wires. Such a phenomenon is incompatible with the place interchange theory of diffusion proposed by several authors, most recently by Birchenall and Mehl.2 This theory has, however, also been questioned3.4 for other reasons, principally because of the high energy required for direct atomic interchange. The rather large difference between self-diffusivity, as determined by tracer technique, and mutual diffusivity, as determined with the aid of another element at low concentration, might also be interpreted as favoring the above idea; however, Birchenall and Mehl have pointed out that there is another possible interpretation of this difference; this is discussed later. A rather interesting and pertinent observation was made by Schwartz,5 who noticed that tungsten lamp filaments, heated by direct current, commonly fail by necking down in the region at the temperature gradient near the positive end, with a concomitant swelling at the corresponding position near the negative end. He introduces considerable auxiliary evidence to show that this phenomenon is occasioned by the motion of tungsten cations which migrate in the high temperature region from the positive end toward the negative end. The mechanism of this migration is not clearly understood. If, however, this experimental evidence be accepted, we are forced to conclude that alloying elements in the tungsten may migrate by the same or a similar mechanism, whatever it may be, at a greater or lesser rate, thus giving rise

Jan 1, 1948

By R. E. McNulty, R. D. Heidenreich, C. H. Gerould

TIIE electron microscope techniques and their application to magnesium alloys that are to be discussed in this paper are the result of research at The Dow Chemical Co. over the past three years. The view- point underlying the work is not wholly metallurgical, but has evolved through a variety of problems related to the physics and chemistry of surfaces. It can be said that the interest and stimulus were closely associated with a desire to employ effectively the electron microscope in research concerning the properties of solids as related to their physical structure. Only a portion of this work will be described here, and, consequently, many points of interest and debate are of necessity either only briefly recognized or are completely omitted. As has been pointed out by Desch,1 a great deal of the knowledge of the structure of metals has been obtained through microscopic studies of the surfaces of metallic specimens prepared in a particular manner. This information, when added to that obtained by means of thermal, electrical, X-ray, dilatometric and other methods, has been of great value both from a theoretical and a practical view- point. With the introduction of new instruments such as the electron diffraction camera and the electron microscope, it would be expected that still more information could be obtained. These two instruments have in many instances been very effective when directed toward the investigation of metallic surfaces, provided the proper methods of surface preparation were employed. Experience shows that the problems of surface preparation greatly limit the general application of these instruments to metallographic studies. It was found necessary to discard the standard metallographic procedures in applying the electron microscope to magnesium alloys and to work out new methods, which were required to satisfy certain conditions. These methods are unique to magnesium only in the specific chemical reactions occurring during etching. The presentation of the methods and results will be ordered as follows: I. Electron Microscopy of Surfaces. 2. Surface Preparation of Magnesium Alloys. 3. Discussion of Microstructures. a. Pure Magnesium and Single-crystal Studies. b. Types of Precipitation. c. Some Common Structures. d. Special Micrographs and Techniques. e. Structure of Mg-A1 Solid Solutions. 4. Correlation of "Fine Structure" with Corrosion Behavior of Magnesium Alloys.

Jan 1, 1946

By M. G. Corson

THE theory of hardening by interference with slip which has been so clearly developed by Jeffries and his co-workers requires that an alloy to be amenable to age or heat hardening should contain among its components some that will stay in solid solution at high temperatures and precipitate as a secondary phase on cooling. This secondary phase may be either a more or less pure individual element (chromium in the case of copper, anti-mony in the case of lead), or some intermetallic com-pound. Those cases of hardening which depend on the precipitation of a compound are not only the most frequent, but are also far superior in the efficiency of hardening obtained. However, the slip interference theory as stated in its most general form is not sufficient to foretell new cases of this type of hardening and also will not explain some phenomena of a more intricate nature. It is not sufficient that a secondary phase might be absorbed by the main one at high temperatures and precipitated at the lower ones. The kinetics of this precipitation and the accompanying. physical phenomena of dimensional changes play independent and highly important parts. These kinetics, while not yet sufficiently studied to he formulated in the shape of physicochemical equations, might find their expression-in a qualitative systema-tization of the phenomena of precipitation according to two different viewpoints. To begin with, we encounter the question as to the velocities of the precipitation and of the growth of the phase precipitated. To harden a metal in an efficient manner we must be able to control the precipitation on one hand and also to bring the total of the secondary phase to such a number and size of the particles pre-cipitated as, will produce a desirable hardening effect under commercially feasible conditions of. age or heat hardening. From this viewpoint six different cases may be dis-cerned.

Jan 7, 1928

By B. Ladanyi

The problem of rock behavior under concentrated loadings has been the subject of a number of studies in the past and has been receiving increasing attention by rock mechanics investigators in recent years. Its application covers various fields, but main interest in its solution has arisen in connection with the problems of drilling, bearing capacity, and rock testing. These widely different purposes and fields of interest probably have been one of the reasons why, in spite of the large amount of published experimental data and several theoretical studies, there are still many points which need further clarification. Another reason for this situation undoubtedly is due to the fact that the rock behavior in indentation is complicated by a great number of influencing factors. Experimental evidence shows that, depending on the rock type (mechanical properties, porosity), environment (ambient effective pressure, pore fluid, temperature), and the type of loading (indenter shape, initial embedment, load level, loading rate), the rock response to indentation may vary within very large limits. The widely different rock behavior has made it impossible up to now to treat the problem with a consistent single mathematical theory, but has required instead a series of simplified models covering only certain most important events in the failure sequence. As far as the theory of rock indentation is concerned, this chapter does not add much new information. Its main purpose is, however, to state the indentation problem in a general manner and to indicate which points need to be studied in more detail before its definite solution is attempted. Also, since excellent reviews of the state-of-art of rock indentation in drilling have recently been given,1-4 this will not be repeated here, and only references pertinent to the points of the problem under study will be quoted. The theoretical part of this study attempts to give a quantitative evalu-

Jan 1, 1972

By Nathaniel Herz

PARTING of bullion before shipment to the mint had been considered by the Homestake Mining Co. at various times, but had never been attempted before 1933, be- cause the margin of profit appeared to be too small to warrant the complications in refining. When the gold standard was abandoned by the United States in the spring of 1933, however, parting of the bullion was decided upon. The method selected was the Miller or chlorine process, which consists of the passing of gaseous chlorine into a bath of molten bullion, converting all metals other than gold into chlorides, and remov-

Jan 1, 1935

By Robert W. Hunt

THE memorable features of American history have been making fast during the last century, and notably so since 1860; and they are by no means confined to political or to any one branch of scientific development. Of all the industrial arts, none show a greater change or a mightier progress than the Bessemer manufacture. And this year, while we are celebrating the first centennial of our national life, we can also celebrate the first decennial of American Bessemer practice. While not forgetting or undervaluing what has been done in other countries, I have thought that a brief history of the introduction and development of the Pneumatic or Bessemer process in America would be of interest. In 1863 the Kelly Pneumatic Process Company was formed and an arrangement entered into with William Kelly, who had taken out letters-patent of the United States, Nos. 16,444 ; 17,628, re¬issued as 505; 18,910, dated January 10th, 1857 ; June 23d, 1857; November 3d, 1857; and December 22d, 1857, respectively. This association was composed of the Cambria Iron Company, E. B. Ward, Park Brothers & Co., Lyon, Shorb & Co., Z. S. Durfee, and, later, Chouteau, Harrison & Valle joined the combination. Not satisfied with possessing the control of the Kelly patent, they sent Mr. Z. S. Durfee to England, to secure for this country Mushet's patent on recarburization, No. 17,389, dated May 26th, 1857, the same having been taken out in England on September 22d, 1856. In this Mr. Durfee was successful. Previous to the application of William Kelly for a patent, Henry Bessemer, of England, had taken out patents dated February 12th, 1856, and August 25th, 1856, in this country. Kelly claimed priority in the discovery of the principles of the process, and the Patent-office allowed his claim by granting him his patents. In the autumn of 1862 Mr. Alexander L. Holley, while in England, was impressed with the importance of Mr. Bessemer's inven¬tion, and so fully foresaw its future, that, upon his return to the United States, he induced Messrs. John A. Griswold and John F. Winslow, of Troy, New York, to join him in endeavoring to possess Bessemer's American patents. Mr. Holley returned to England in

Jan 1, 1877

By Rich Akerman

as 1866, I wish to assure both these gentlemen that I had not seen the section when I designed mine, :md even if I had, I should not have then dared to put it forth as a standard for English rail makers; tind the soundness of my opinion has a simple but conclusive proof in the statement made concerning the extra price which was at that time required for their production. I need not say that I highly approve of the original Welch section, for it is in principle similar to the design which I made ufteen yeam subsequently; and from a professional point of view I would fully concecle to Mr. Welch the credit of first designing the modern steel-rail section. From com- mercial, matter of tict, and practical point of view, he was, however, before his time by many years; or to put it in another way, rail making was ten years behind its time when the new metal steel was first introduced for rails. If his design has been incorrectly identified with my name (as the sections are similar in principle, though they differ in thickness of flange and web), I beg to say (1st) that I much regret the misun- Understanding which has arisen through no fault of niine, aud (2d) that no confusion has been intentionally created by me. It is a pity that the section designed so long ago has not been made public at an earlier date, as it would make a really goal stand- and pattern, anil even now be quite equal to present requirements. In conclusion, I wish to say that I have never desired to claim any invention or novelty by the publication of my sections; they Were put forth as being such as English railmakers could and would produce at the ordinary market. price, and as being the best and most suitable to be so obtained. Had Mr. Welch or Mr. Holley put forward theirs ten or fifteen years ago, I should have been the first to recommend theru. In fact I should have been glad to see their narnes associated with rail patterns in their own country, in the same way as mine has been. PROFESSOR RICH. AKERMAN, STOCKHOLM, SWEDEN: i AGREE with your (Mr. Sandberg's) views that it is too early yet to stipulate only one definite chemical composition in the rails. Such a stipulation, I think, might he justified, if it were not for the manganese; but this metal changes the properties of the iron aud steel in tho same direc- tion ae carbon, silicon. and phosphorus, by increasing its tensile strength, stiffness, hardness, and brittleaess. If the iron and steel does not only contain carbon and manganese but also phosphorus,

Jan 1, 1881

By G. W. Healy, W. D. Forgeng, N. R. Griffing

The liquidus surface of the C-Cr-Fe system to 1900°C has been mapped from carbon solubility and freezing point measurements, metallographic observations, and published data. In the graphite field, the surface drops precipitously to meet a slope descending from the Cr3C2-C join through the mixed carbide fields to a meandering eutectic valley; this flows from the Cr-C to the Fe-C edge. On the low-cavbon side of the valley, the surface rises to the chromium corner. 1 HE purpose of this inquiry was to gain a more complete knowledge of the C-Cr-Fe liquidus surface. This required an extensive study of carbon and chromium-rich alloys which, in the past, have received the least attention. Sanbongi el al.1 measured the solubility of carbon in liquid alloys containing up to 25 wt pct Cr at temperatures of 1460" and 1545°C and found that it increased with chromium content and temperature. Lucas and wentrup2 also made solubility experiments in graphite crucibles, but at higher chromium contents in the range of 38 to 80 pct and at temperatures of 1550" to 1700°C; however, their experiments were relatively few, and the effect of temperature was not consistent. The present investigation included compsitions ranging from 0 to 94 pct Cr and 1.4 to 11.7 pct C at temperatures up to 1800°C. Saturation experiments in graphite crucibles, thermal analyses during freezing, and metallographic and X-ray diffraction studies were employed to obtain desired information which, together with published data from other investigations about the binary edges and the ternary system at lower carbon levels, made possible the construction of a comprehensive C-Cr-Fe liquidus surface. C-CR-FE LIQUIDUS SURFACE The derived ternary liquidus surface is shown in Fig. 1 where the solid curves are liquidus isotherms. The dashed curves and the binary edges are the liquidus field boundaries of the primary crystals, the arrows along these boundaries indicating their direction with decreasing temperature. Each intersection of three internal boundaries is the composition of liquid involved in four-phase isothermal equilibrium with the three primary crystals whose liquidus fields touch there. It may be observed that a total of six four-phase equilibria occur at melt temperatures. The general topography of the liquidus surface consists of a eutectic valley sloping down from the Cr-C edge at 3.2 pct C to the Fe-C edge at 4.25 pct C. The liquidus surface rises in two directions from the valley, one hillside terminating at the Cr-Fe edge while the opposing hillside rises toward the carbon corner out beyond the top edge of Fig. 1. Both hillsides are interrupted by intersections of surfaces or joints representing the liquid colmpositions of various three-phase equilibria. Seven primary crystals occur, namely a(bcc), ?(fcc), graphite, (Fe, Cr)3C capable of dissolving as much as 15 pct Cr, and three different chromium carbides in which iron is partially soluble by substitution for chromium. The composition ranges of the primary l~hases at melt temperatures are shown

Jan 1, 1962

By Harry L. Brown, Philip E. Armstrong

Young's modulus doto ore presented for W, Mo. Ta. V, Cr. Ni, Ti, and Zr as a function of temperature up to about 0.7 of the melting points. A plot of reduced temperature us reduced modulus produces a general correlation except for titanium and zirconium. Young's modudlus data for some representatiue commercial graphites are given up to 2400°C. All results were obtained from longitudinal resonance-frequency measzrrements of 4-in. long samples, corrected for simultaneously measured thermal expansion. Comparison of poly crystalline and single-crystal tungsten behavior indicates that all the observed modulus values are frequencv -dependent at the higher temperatures. STATIC measurements of elastic properties of materials at elevated temperatures are extremely difficult to make since the elastic behavior is obscured by relatively large first-stage creep effects. Dynamic methods which avoid this difficulty by utilizing the measurement of the resonance frequency of a simple vibrational mode have been described in the 1iterature.l-3 The authors have extended the operating temperature range of this type of measurement to above 2000°C and have described the equipment elsewhere.~ The Young's modulus data presented here were obtained with this equipment, using samples about 4 in. long and 1/4 in. diam, supported horizontally at the center and excited to the fundamental longitudinal resonance frequency. Young's modulus was calculated by the formula: E = 4f2f2p where E = Young's modulus, / = frequency, 1 = length, and p = density. Dilatometric data were obtained simultaneously by optical measurements of the change of length of the sample. For the metals tested, an attempt was made to obtain modulus values that would be representative of the pure, strain-free, randomly oriented material. All of the graphites studied exhibited a high degree of elastic anisotropy, while the method assumes an isotropic homogeneous material. However , when the values for Young's modulus obtained for AUC graphite were compared with those taken from static measurements at room temperature they were found to be only about 4 pet higher. This is excellent agreement considering the low precision of modulus calculations from stress-strain curves. The difficulty in using data of apparent Young's modulus for anisotropic materials arises when the attempt is made to use these data and shear-modulus data to obtain Poisson's ratio. The results are usually meaningless and sometimes absurd.' RESULTS Table I lists the sources, impurity content, thermal history, and dilatometric constants of the metal samples that were investigated. All the metal samples were tested under a vacuum of 1 to 5 x 10-5 Torr. Where our dilatometric data agreed with previously published data, the table lists the previous values and the literature reference. Where no reference is given, the constants were determined from our dilatometric data. Table II presents the modulus data in units of millions of psi as a function of temperature in degrees centigrade. The numbers were obtained from curves fitted to the experimental data. For some types of calculations, such as those attempting to correlate creep data, the slope of the modulus curve is of interest, and this information also is reported in Table 11. It is always tempting to try to fit physical-property data into some general pattern and then use this pattern to predict the behavior of other similar materials. The general pattern for an elastic modulus of a metal seems to be a linear deoro- with increasing temperature Over the range between 0.1 and 0.4 of the melting temperature, then a progressive1y decreasing value up to the melting point. Metals appear to retain finite moduli

Jan 1, 1964