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P. W. SHIMER, Easton, Pa. (written discussion*).-When lump calcium cyanamid is immersed in the melt of mixed chlorides of the alkalies and alkaline earths in the manner described in the paper, the amount of sodium cyanide formed in the melt, as shown by numerous analyses, is but a small fraction of that formed by the reaction referred to by Mr. Johnson. The case-hardening effects in my process are, however, at least as good as when the common cyanide baths are used. Moreover, when compared with the cyanide baths, the gases evolved in the new process are harmless, consisting of nitrogen, carbon monoxide (which burns to carbon dioxide on the surface of the melt), and occasionally a little carbon dioxide. These gases are not irritating or poisonous, whereas the vapors arising from cyanide baths are both irritating and poisonous. The complex chemical reactions that take place in and on the surface of the melt are being investigated by the writer, who hopes, in due time, to communicate the results of his work.

Jan 7, 1919

By Vernon Read

Among the technical problems in AEC's Project Plowshare is the necessity of determining the precise effects of nuclear blasts in all kinds of ground formations. This calls for extensive in-situ sampling with full core recovery. In the exploration drilling that often precedes a new test detonation, the AEC and its contractors have applied both novel and established sampling techniques in many new ways, giving improved core recovery and reduced costs in all subsurface sampling and testing. Unique among these new techniques is one that achieved full recovery and virtually undisturbed samples from near-surface layers of unconsolidated boulder-strewn alluvium. This approach involves a combination of oilfield and mining core drilling equipment. Oilfield heavy drill collars, rotary stabilizers and thick, vibration-reducing oil emulsion drilling mud were used in combination with the precise hydraulic feed control, fast (over 300 rpm) bit rotation, light drilling weight, hard rock core barrels and multi-step diamond bits that are common in mining industry diamond drilling.

Jan 8, 1963

In high-volume mining operations, preventive maintenance programs that include standardized replacement wear parts can boost equipment availability and lower unit costs. Meeting the daily production targets depends heavily on keeping equipment working as close to full time as possible. This is the case at one medium-sized western surface coal operation producing approximately 2.7 million t/y (3 million stpy). The mine, located in western Wyoming, removes in excess of 8 million m3 (10.5 million cu yd) of highly abrasive overburden each year. According to the mine superintendent, "Abrasion at this mine is some of the worst I've ever seen. Shovel points can wear out in little more than one shift. Dozer blades some- times last two weeks, but can wear out sooner. And ripper points really take a beating. If we can replace this fast-wearing iron with small pieces that go on quickly, we think that's the way to go."

Jan 3, 1978

By W. A. Hustrulid, N. A. Ross

An analysis of the design of medium to hard rock tunneling machines is presented. The developed equations are used to compare performances and machine requirements using kerf and fixed pick cutters to bore a given rock. With the use of pick cutters, required thrusts can be greatly reduced and still achieve the same boring rate as with present day tooth or kerf cutters. It appears that the cutting coefficient, which for most boring machines is of the order of 0.1, should be increased to one or larger to facilitate rock removal by cutting rather than grinding. The depth of cut and the indexing distance should be greatly increased to make use of inherent rock weakness.

Jan 1, 1971

By T. D. Tiemann

The chemical and mineralogical composition of Caribbean bauxite ores are described. Extraction of alumina by several processes from both Haiti and Jamaica bauxites is discussed and data presented. IMMENSE deposits of bauxite occur in the Caribbean islands of Hispaniola and Jamaica in the high plateau lands and have been excellently described by 0. C. Schmedeman.' The bauxite occurs as deposits in catchments or etched depressions in Tertiary limestone believed to have been deposited in the Eocene and Oligocene periods.' In appearance both the Haiti and Jamaica bauxites resemble a relatively high iron clay and have indeed been mistaken for such.' They are very soft and friable and disperse readily on vigorous agitation in water. The color range in general is light brown to red. Chemically, the outstanding characteristic of the bauxites is the low silica and high ferric oxide content. The extremely low silica makes them particularly valuable for the production of alumina in the Bayer plant since silica is responsible for the loss of both alumina and soda chemically combined as XNa,OYSiO2,ZAl2O2. The ferric oxide, only traces of ferrous iron are present, offers no interference in the production of high grade alumina. Typical oxide analyses of three types of ore are given in Table I2 and a list of the elements occurring in spectrographic quantities in Table 11." The size of the individual particles in the ore makes successful petrographic examination extremely difficult. The ores contain some relatively coarse grains of heavy minerals such as ilmenite, magnetite, and rutile, but other than occasional crystals of a few microns, the greater portion of the minerals are submicroscopic in size and approach colloidal dimensions. The mineralogic composition of the ores has been investigated by X-ray and differential thermal analysis.' These investigations indicate that the predominant mineral phases present are gibbsite (A1203.3H2O), boehmite (Al2O3.H2O), hematite (Fe2O3), and goethite (Fe2O3-H2O). There is no evidence of the occurrence of diaspore (Al2O3.H2O) in either the Haiti or Jamaica ores, but some type of "amorphous" alumina may be present in some of the bauxites of Jamaica." The temperature stability regions in the alumina-water system have been investigated and are given in recent literature. In the temperature range where the hydrated forms are stable, as determined by hydrothermal bomb methods," ibbsite is the stable phase to 155°C (311°F), boehmite from 155°C (311°F) to 280°C (536oF), and diaspore from 280°C (536°F) to 450°C (842°F). Although quite similar in many characteristics, the Haiti and Jamaica ore show a divergence in mineralogic composition that is reflected in the extractability of the alumina described in later paragraphs. Two principal differences occur in mineralogic composition. The iron-bearing mineral in the Haiti ores is predominantly hematite, while in the Jamaica ores goethite is predominant.4 Directly related to the extraction of alumina are the two minerals, gibbsite and boehmite. Boehmite is relatively high in the Haiti ores and in some of the less soluble Jamaica ores, while gibbsite predominates in the ores in Jamaica amenable to the American Bayer process of extraction. Pedersen and Related Processes In general, all processes for the extraction of alumina involving sintering or fusion of bauxite ores with limestone, soda ash, or a combination of limestone and soda ash followed by leaching, are based on the formation of alumina compounds that. yield alumina soluble in the subsequent leach. The principal idealized reactions in respect to alumina and silica for the three types of processes are as follows: Soda Ash Sinter: A12O3 + Na2CO3 = Na2O-Al2O, + CO2 SiO2 + Na2CO3 = Na2O . SiO2 + CO2 A12O2 + SiO2 + Na2CO3 = Na2O.Al2O8. SiO2 + CO2 Leach (with excess water): H2O + Na2O-A12O3 = 2 NaOH + A12O3 (insolution) H2O + Na2O-SiO2 = 2 NaOH + SiO2 (in solution) Soda Ash— Limestone Sinter: Na2CO2 + A12O3 = Na2O.A1203 + CO2 2CaCO3 + SiO2 = 2CaO . SiO2 + 2CO2 Leach (with excess water): Na2O' A1208 + H2O = 2NaOH + A13O3 (in solution) These latter reactions are the basis of the sinter process currently used for the recovery of soda and

Jan 1, 1952

By B. I. Routh

A STUDY of the effects of temperature on the gel strength of drilling muds is a natural outgrowth of the present era of deep drilling. The control of the gel solids' is now considered important because it affects the wall-building qualities; the suspension of weighting material; the removal and release of sand, cuttings, and gas; and the control of cav-ing formations. With regard to the effect of temperature on gel strengths Herrick2 states: "Temperature variation within ordinary limits does not have much effect on yield points." Lewis, Squires and Thompson3 investi-gated one clay and found no marked change with temperature in either yield point or mobility. Reed4 found that potassium bentonite showed a great increase of gelation with increase in temperature and qualitatively there occurred a marked increase in viscosity upon heating. The apparatus used in these experiments consisted of a Stormer viscosimeter, Marsh funnel viscosimeter, rectangular and cylindrical shearometers, Mudwate hydrometer, and other minor laboratory equip-ment. The various methods of measuring viscosity and gel strength have been extensively described by Evans and Reid.5

Jan 1, 1938

By G. J. Heuer, J. N. Dew, G. C. Clark

The effect on well behavior of partial permeability barriers, changes in producing rates and well spacings have been calculated through use of a radial, unsteady-state, two-phase-flow mathematical model. This model allows for variations in permeabilities and porosities with distance from the wellbore. The numerical methods necessary to solve the problem require use of a highspeed digital computer, in this case an IBM 704. In each instance, pressure and saturation gradients, gas-oil ratios and recoveries around a well producing by solution-gas drive have been calculated as a function of time and distance from the wellbore. Comparisons are made to show the effect of changes in producing rate and of varying permeability near the wellbore and out in the formation on the production and pressure history of the well. The effect of different well spacings on producing rate and ultimate recovery is considered. Although the mathematical description of the reservoir is simplified in comparison to an actual reservoir, the results do give some insight into the difficult problem of spacing and proration in a heterogeneous solution-gas-drive reservoir. Results show that for the cases considered spacing has little effect on ultimate recovery and that permeability barriers removed from the well decrease producing rate for a period of time but have only a small effect on ultimate production. INTRODUCTION The effect of spacing and producing rate on the production characteristics and ultimate recovery of a well producing by the solution-gas-drive mechanism have been topics of interest to the oil industry for many years and the subject of many hearings before state regulatory bodies. The problem is very complicated because of the difficulty of simulating in the laboratory a reservoir producing by the solution-gas-drive mechanism under anything like normal field conditions. This paper gives the initial results of a study aimed at determining the effect of these factors on production from reservoirs simulated by a mathematical model. Two-phase, unsteady-state equations are used to calculate pressures, saturations, and rates of oil and gas flow as a function of time and distance from the wellbore. The model is radial, and reservoir properties may be varied with distance from the wellbore. A decrease in permeability at a given distance results in a low-permeability ring concentric with the wellbore through which all the fluids from more distant portions of the reservoir must flow. The current mathematical model allows for variation of permeability, porosity and saturations as a function of distance from the well. Any desired drainage radius for the well may be selected. Drainage radii of 745 and 1,053 ft, which correspond to 40- and 80-acre spacing, were chosen for the calculations which follow. A large amount of the input data has been held constant. No investigation was made into the effect of changes in fluid properties and relative permeability characteristics on oil and gas production behavior. Fluid properties and relative permeabilities are essentially those of the White Mesa portion of the Greater Aneth area in southeastern Utah. A recently concluded hearing before the Utah Oil and Gas Conservation Commission to determine spacing for the field aroused interest in the possible effect of permeability constrictions located some distance from the well on production and recovery. This interest stimulated the present study. In this paper, no attempt has been made to simulate any field production characteristics exactly. Only the solution-gas-drive mechanism has been investigated, and production by liquid expansion has not been considered. This investigation is exploratory in nature but does give some insight into the problems of spacing and proration in a solution-gas-drive field having permeability variations. THE MATHEMATICAL MODEL The mathematical model is similar to that proposed by West, Garvin and Sheldon.' Approximately the same techniques have been used in arriving at a solution. The equations are nonlinear, partial differential equations which have been known for some time. The particular equations used for this study neglect the effects of capillary pressure and gravitational forces. The advent of modern digital computing equipment has made their solution practical. Basically, the method solves for pressure, saturations, and oil and gas flow rates as a function of distance and time. In our model, distance to the

By F. W. Jessen

The Mechanism of solution of salt and mixed halites of sodium and potassium is reviewed. The variation in the rate of salt removal under both laminar and turbulent flow conditions is discussed. Many changes are possible in the development of solution cavities whether used for production of salts or for storage of hydrocarbons. The parameters influencing the type and shape of cavity formed with single well or multiple well systems are examined and information presented regarding field application of techniques developed and the means of controlling overall configuration of solution cavities.

Jan 1, 1972

By E. H. Fahmy, L. C. Uren

During recent years, oil producers have observed with interest the practical success which has attended the application of water as a medium for displacement of oil from its reservoir sands in the Bradford field of northern Pennsylvania and southern New York. Here, according to various authorities, additional recoveries of frorn 2,000 to 12,000 bhl. of oil per acre have heen secured by this method, after ordinary flowing and pumping. rnethods of production had practically reached the lower limit of economic operation. Notwithstanding the success which has attended the practical use of the flooding process in the Bradford field, oil producers in other regions are skeptical of its value when applied under physical conditions differing markedly from those which characterizc the Bradford field. Its usc would probably he construed as illegal in most of the oil-producing states. This general relnctance on the part of oil producers in other regions to accept the flooding process is due in large part to lack of infor-n~ation regarding the factors that influence its operation and efficiency. With the purpose of clarifying to some extent the issues involved, and of determining when the flooding proccess may or may not beeffee-tivcly ernployed, the writers have conducted a serics of laboratory exper-imentments under carefully controlled conditions, designed to indicate, the influence of various physical, chemical arid lithologic factors. These experments have not been conducted under conditions identical with those which exist at depths far below the earth's surface, so that direct quantitative comparisons with field results are not justified, hut it is believed that the experimental results at least warrant qualitative inter-pretations that may he applied to field conditions. The methods employed in the conduct of these experiments are briefly explained, and the results, together with the conclusions based thereon, arc presented. FactoRs Influencing Displacement of Oil froM SaNdS by WAteR- flooding Before presenting the experimental data, it, will he desirable to con-sider the manner in which the residual oil is retained within the oil sand

Jan 1, 1928

By H. S. McQueen

The insoluble-residue method for the examination and correlation of limestones and dolomites, or other sedimentary rocks containing calcium and magnesium carbonates, originated and was developed in the laboratory of the Missouri Geological Survey. The numerous and ever-increasing problems in the field of applied geology, and the need for a tool or aid in the solution of them, led to experimental work with samples collected from deep wells, in the early part of 1924. The success attained, almost at the outset, with this method was so great that the method has now been developed from the state of the experimental to the realm of large-scale, every-day routine. In a previous paper the writer1 described the procedure in detail and the characteristics of the residues obtained from certain Paleozoic formations in Missouri. The purpose of the present paper is to discuss the economic application of the insoluble-residue method. Developmental History Within the Ozark region of southern Missouri the geologic column consists of Lower Ordovician (Canadian of Ulrich) and Upper Cambrian formations, which are composed mainly of dolomite with subordinate amounts of sandstone, shale and limestone. Chert is found to some extent in all except one of the dolomite formations. The stratigraphy of the region is complex because the dolomites have lithologic similarities, fossils are few and often poorly preserved, and identifiable horizons within the comparatively thick formations are not common. Although considerable stratigraphic work of an areal nature had been done for a period of many years by the Missouri Geological Survey, the detailed geologic succession had not, until a few years ago, been systematically worked out. The problems of subsurface stratigraphy were even more complex. This region constitutes the main ground-water province of the State of Missouri and within it wells of varying depths are drilled in order to obtain supplies of ground water. In the work of the State Geological Survey in connection with the drilling of water wells for public supplies * Published with the permission of the Director, Missouri Geological Survey and Water Resources. Manuscript received at the office of the Institute Feb. 20, 1936. Assistant State Geologist of Missouri; Missouri Geological Survey, Rolla, Mo. References are at the end of the paper.

Jan 1, 1937

The Institute conducts jointly with the American Society of Civil Engineers, American Society of Mechanical Engineers and American Institute of Electrical Engineers, certain activities as listed below, and is joint owner with them of certain properties. United Engineering Trustees, Inc. When Mr. Carnegie made his gift which made possible a home for the engineering societies, a separate corporation was organized to act as a holding company and to manage the common property. This was long known as the United Engineering Society, but the name has now been changed. to one which more nearly reflects the real function of the corporation. It holds title to the Engineering Societies Building and to various funds placed in its charge and is managed by a Board of Trustees, of which three are chosen by each of the four societies, American Institute of Mining and Metallurgical Engineers, American Society of Mechanical Engineers, American Institute of Electrical Engineers and American Society of Civil Engineers, which have equal and undivided interests in the property. The land and building cost two million dollars. During the gear 1934, the constitution and By-laws of The United Engineering Trustees, Inc., were thoroughly revised and a better organization of its functions was affected: The Engineering Foundation and the Engineering Societies Library were made "departments? of the United

Jan 1, 1936

By John A. E. M. Church

THE prospector's pan was the first implement used for saving gold, and its action is so effective that it has never been equalled for thorough work. Copper plates, blankets, sluices, and amalgamators of several patented designs have thrust it aside, but in spite of all the advances made there is no dispute among experienced men as to the comparative thoroughness of the work done by it and its rivals. When its rivals are doing their best, the pan can take their discarded refuse and prove their inefficiency by producing from it not only gold, but even the mercury which has been lost from the machines themselves. The trouble with the pan has always been that it was only a tool. Man was the machine that moved it. His work was high-priced, the quantity treated small, and it was impossible to use the pan for any but the richest sands. As a consequence the best gold-saving appliance known has been discarded for years and replaced by machines of inferior excellence, but which could more than make up for their limited ability in saving gold by their capacity for treating great quantities of ore. Mr. Peck is one of the old-time amalgamators of the Comstock district, and the first idea of the new machine came to him as he used to pan below the tailrace of his mill. No matter how fine the work of the mill was, the pan invariably proved that better could be done. The tailings always contained gold, silver, and mercury. This state of things is just as true to-day, after all the improvements that have been made, as it was then, and the much-vaunted method of the " Washoe process" consists in extracting 72 per cent. of the gold and silver by one operation, and then repeating this operation half a dozen times to get out about one-third of the remainder. With all the advances of twenty years in milling, there is nothing more crude in metallurgy than the treatment of tailings in many of the large mills of the West.

Jan 1, 1880

By C. A. Heiland

Measurements of gravity with gravimeters have come into increased use in this country and abroad in the past five years. Probably 100 to 125 gravimeter parties are working in the United States alone. In oil exploration, gravimeter methods have relegated the gravity pendulum definitely to second place, if not third, and now closely rival and possibly surpass the torsion balance in many applications. Gravimeters have lately been applied in mining, although it is doubtful whether they will ever replace electrical or magnetic methods in this work. Notwithstanding the widespread application of gravimeters, there has been no article covering the entire field in the domestic or foreign literature. The purpose of this paper is to meet the demand for comprehensive engineering information on the subject. The working principles of a number of gravimeters will be illustrated and treated in relation to the action of corresponding seismometers and astatization methods. The mathematical discussion of theory has been confined to the most necessary fundamentals and been given in as elementary form as possible. A description of calibration methods constitutes the last part of the paper. The symbols shown at the top of page 197 will be used in equations throughout the paper. Dynamic and Static Gravity Methods Methods of measuring gravity fall into two groups: dynamic and static methods. The first group involves the measurement of time. Examples are: determinations of the period of oscillation of a pendulum, measurements involving the free fall of a body, and comparisons of gravity with the centrifugal force of a rotating body. Measurements in the second group of gravity methods are concerned with deflections of certain indicators when the force of gravity is in equilibrium with another comparison force.

Jan 1, 1940

By C. A. Heiland

Measurements of gravity with gravimeters have come into increased use in this country and abroad in the past five years. Probably 100 to 125 gravimeter parties are working in the United States alone. In oil exploration, gravimeter methods have relegated the gravity pendulum definitely to second place, if not third, and now closely rival and possibly surpass the torsion balance in many applications. Gravimeters have lately been applied in mining, although it is doubtful whether they will ever replace electrical or magnetic methods in this work. Notwithstanding the widespread application of gravimeters, there has been no article covering the entire field in the domestic or foreign literature. The purpose of this paper is to meet the demand for comprehensive engineering information on the subject. The working principles of a number of gravimeters will be illustrated and treated in relation to the action of corresponding seismometers and astatization methods. The mathematical discussion of theory has been confined to the most necessary fundamentals and been given in as elementary form as possible. A description of calibration methods constitutes the last part of the paper. The symbols shown at the top of page 197 will be used in equations throughout the paper. Dynamic and Static Gravity Methods Methods of measuring gravity fall into two groups: dynamic and static methods. The first group involves the measurement of time. Examples are: determinations of the period of oscillation of a pendulum, measurements involving the free fall of a body, and comparisons of gravity with the centrifugal force of a rotating body. Measurements in the second group of gravity methods are concerned with deflections of certain indicators when the force of gravity is in equilibrium with another comparison force.

Jan 1, 1940

By S. P. Burke

THE presence of gas in coal mines necessitates the use of costly ventila-tion arrangements and the use of expensive mining methods. On the other hand, the gas itself in many instances is of considerable intrinsic value, and its separate recovery might conceivably be a profitable under-taking. This paper is concerned with a study of the movement of gas in coal strata with the object of determining the laws governing gas move-ment and thus making at least a preliminary step toward the solution of the more practical problem of its control or recovery. Naturally, so important a subject has received much attention from scientists and engineers. In most cases, however, the studies have been concerned with the origin1?, the amount2, the composition3 and the method of retention4 of the gas in coal; or, from the more practical side, have been concerned with the phenomena and conditions associated with outbursts5 or explosions and their control. Numerous studies also have been made of the permeability of coal to gas6, of gas pressures measured in coal seams, etc. The authors are unaware, however, of any attempt to present a consistent or complete picture of the laws governing the movement of gas through the coal.

Jan 1, 1935

By B. Silliman

THESE ores occur in the Laurentian rocks in the town of Clifton, St. Lawrence County, New York. The Clifton Mining Company have opened these magnetites upon their estate of 23,000 acres, on the waters of the Grasse River, an affluent of the St. Lawrence, which flows for about nine miles across the estate, exposing a section of the formation, and affording ample water-power at numerous points. In approaching this district from De Kalb Junction, upon the Watertown and Ogdensburg Railway, the observer passes from the zone of the specular ores, which abound to a great extent in Jefferson County, across a belt of non-metal-liferous limestones, continuing for some miles intermingled with metamorphic rocks, and gradually giving place to heavy beds of granitic and porphyritic gneiss, the weathered surfaces of which present a gray and rough appearance, from the washing out of the feldspar; leaving the quartz very prominent, and completely disguising the real character of the rock, which, when freshly broken, has a lively reddish appearance from the predominance of flesh-colored and red feldspar. Beds of fine-grained quartzite appear also intercalated in the granitic gneiss. These are the dominating rocks of the magnetite region, but the magnetite is always found, so far as the speaker's observation extended, associated with beds of calcite, carrying hornblende, black and green, biotite, and brown garnet interspersed with yellow and magnetic pyrites. The strike of these rocks is about northeast, and their dip about 40° to 45° southeast.

Jan 1, 1873

By Sidney Cornell

THE technical- advantages of adding oxygen to air and producer gas, or using it as a reactive agent, producing 400 B.t.u. gas instead of. the present 150 B.t.u., with higher flame temperatures and a reducing flame possible, with a smaller volume of gases passing through a furnace, will result in quicker melting, sharp working, and the production of a higher quality steel. Probably electric-furnace quality steel can be produced in an open-hearth furnace using oxygen. A modern, standard, 100-ton open-hearth furnace, with all equipment, costs from $350,000 to $500,000; there are about 1000 open-hearth furnaces in this country. When considering the use of oxygen in the open-hearth furnace, it is necessary to study: (1) The use of oxygen in the present furnaces, such that modification of existing furnaces and equipment cost the minimum, although the full advantages of oxygen are not thus obtainable. (2) The use of oxygen in a furnace designed for its use, producing quality and quantity steel at the lowest possible cost. This entails the junking of approximately one-half the value in existing equipment-writing off $250,000,000. The basis of such an estimate is the present cost of manufacturing open-hearth steel. Objection may be taken to some of the unit prices here given, but while some companies obtain their ores for much less, the prices quoted are -market price. They are used to show the maximum economy obtained by oxygen at that point.

Jan 11, 1924

By Warren Smith

IT has been 5 years since the writer left the Philippine Islands and while in that country his chief work did not lie in this field, though he has visited all but one of the localities mentioned in this article. The principal field studies relating to oil were made by his colleague, Mr. Wallace E. Pratt. The writer's investigations dealt with the general stratigraphy and paleontology of the Philippines. With the exception of the investigations made by Mr. Pratt and the writer very little information on this subject is available. A number of geologists in the employ of large oil companies have visited the Islands from time to time but, following the general rule, the public has scarcely ever been permitted to learn anything of the results. The writer is indebted to the Bureau of Insular Affairs, Washington, for late information regarding recent legislation in the Islands relating to petroleum. All the known oil seeps, petroleum residues, such as ozocerite, and natural-gas emanations are associated with Tertiary sediments. The chief seeps and most promising prospects are located as follows: 1. Bondoc Peninsula (lower end), Tayabas Province, Southeast Luzon. 2. The west coast of the island of Cebú from Alegria north to, and perhaps beyond, Toledo. 3. Central Mindanao not far from Lake Lanao. 4. The ozocerite veins on the Island of Leyte in the northwestern part in the vicinity of the town of Villaba. 5. Natural gas from some deep wells in Tertiary shale formations on the eastern flank of the Cordillera and extending out under the plain on the island of Panay.

Jan 2, 1920

By M. J. Duggin

Structural similarities between the E, X, and iron carbides are illustrated. Experimental evidence regarding phase transformations occurring during ternpering reactions in finely divided carbides, thin-film carbides, and carbides which occur in steels is considered and possible mechanisms for the E — x and x — 9 transformations proposed. HOFER1 has shown that within the appropriate temperature ranges carbon monoxide will react with finely divided a iron to form either iron carbide or x iron carbide. He has shown that at an elevated temperature the E iron carbide will transform to the x iron carbide (Hagg carbide) which, upon further elevation of temperature, will transform to 9 iron carbide (cementite). Jack,2,3 using X-ray diffraction methods, has observed that during the tempering reactions occurring in steel the E iron carbide formed in the first stage of tempering passes into two-dimensional platelets of 0 iron carbide during the second stage of tempering. The three-dimensional form of the 0 carbide is formed during the third stage of tempering. Jack suggested2 that the two-dimensional platelets of 0 carbide could be related to the faulted x iron carbide. Okada and Arata4 investigated a Swedish steel containing 1.05 wt pct C and approximately 1.0 wt pct Mn using permeability measurements at low field strength. A Curie point of 360°C was observed in the quenched steel, which indicated the presence of E iron carbide. On tempering at 400°C the specimen developed a Curie point at 230°C, indicating the presence of x iron carbide, and on tempering at 700°C the specimen developed a Curie point at 190°C which was assigned to 0 iron carbide. The carbides were extracted electro-lytically and the use of X-ray diffraction techniques4r5 indicated the carbide with a Curie point of 230°C to be x iron carbide. The Curie points of the carbides are 10 to 22°C lower than the accepted values which is probably due to the presence of manganese in the carbides, since it has often been observed (e.g., Ref, 6) that a partial substitution of manganese for iron in cementite will lower the Curie point of this carbide. Hofer' summarizes additional evidence of the tempering reactions in steel in which E iron carbide, formed during the first stage of tempering, transforms to x iron carbide during the second stage of tempering. During the third stage of tempering, the x carbide disappears as the 0 carbide is formed. By carburizing thin iron films in a CO gas stream, ~a~akura' has been able to produce the E, X, and 0 iron carbides. He found that below 250°C the E iron carbide was formed; between 250" and 350°C the x iron carbide was formed and above 350°C the 0 iron carbide was formed. He has shown that the E iron carbide transforms to form x iron carbide at 380" to 400°C and that the x ir°n carbide transforms to form the 0 iron carbide at approximately 550" C; both of these phase transformations are irreversible. Hofer' presents a review of evidence to show that the sequence of reactions occurring during tempering processes subsequent to the formation of E iron carbide formed by the direct carburization of finely divided a iron is the same as the sequence of reactions which occur during the tempering processes subsequent to the formation of E iron carbide in steel during the first stage of tempering. It is evident from Nagakura's work that identical tempering reactions are found in thin films of iron which have been carburized to form iron carbide. The purpose of this paper is to discuss the structural similarities between the E, X, and 0 carbides and to suggest a possible mechanism by which regions of the E carbide, formed during the first stage of tempering, may transform to the x carbide during the second stage of tempering. For the finely divided or thin film carbides a mechanism will be proposed for the transformation of the x carbide to the 0 carbide during the third stage of tempering, although it will be suggested that there is evidence that such a transformation may not occur in steels. STRUCTURAL DATA OF THE E, X, AND 0 IRON CARBIDES € Iron Carbide. It is evident from X-ray diffractions and electron diffraction', investigations that the metal atoms in the E iron carbide form an hcp structure with lattice constants ah = 2.752A, ch = 4.3534, using electron diffraction, reports the lattice paramet$rs of the superlattice cell to be a = 4.767A, c = 4.354, c/a = 0.9134. He finds that the carbon atoms occupy the octahedral voids in the metal atom structure so as to form a hexagonal stacking sequence with its basal plane parallel to that of the metal atoms. Considerable long-range disorder occurs in the positioning of the carbon atoms, however, which is in agreement with the possible range of composition Fe2C-Fe3C discussed by Hofer.' Barton and ale" have made X-ray diffraction measurements on a sample of E iron carbide extracted from a catalyst in an organic process. Although there were few reflections recorded on the obtained X-ray powder diffraction pattern, they have proposed that the structure could belong to one of the three possible space groups p3m1, P63/mmc, or Pbcn if one assumed the composition to be Fe2C. Nagakura, using electron diffraction data, suggests a space group of P 6322 for a specimen of c iron carbide of apparent composition Fez.&. x Iron Carbide. The x iron carbide has been studied by Duggin and Hofer" and by Jack and wild,' who

Jan 1, 1969

Jan 1, 1882