Search Documents

By S. J. Kidder, G. C. McCartney

The Helen Mine, of the Algoma Steel Corporation, in the Michipicoten district, Ontario, Canada, has produced more than 6,240,290 tons of iron ore. Prior to and during World War I, 2,823,369 gross tons of brown ore were shipped, and from 1939 to the end of the 1944 season, 3,416,921 gross tons of siderite ore were produced from open-pit operations. Brief descriptions are given of the nature of the ore, the mining methods employed and the manner of treatment of the ore. Shipment of the finished product, known as Algoma sinter, is made to blast furnaces in both Canada and the United States. The iron-ore bodies—i.e., the oxide ores of the Old Helen and the siderite of the New Helen—are a part of a tabular shaped area of iron formation that extends over a length of more than 100,000 ft. and has a maximum width of 1000 ft. The ores are considered to be a product of introduction of iron-bearing material accompanied by replacement of the rocks already present. It is shown that introduction took place subsequent to the development of the major folded structures. It is believed the iron-bearing material emanated from an igneous source. Introduction The Michipicoten mining district derives its name from the Indian word1 meaning "place of bold promontories" or "region of big places," and anyone who has visited this part of Canada will agree that the district is well named. In 1897, there was active prospecting for gold in the district and the Ontario Bureau of Mines2 opened a recording office at the Hudson's Bay post at Michipicoten River. In the summer of 1897, Ben Boyer, probably searching for gold, discovered an outcrop of brown iron ore at the east end of a small lake, less than 8 miles, in an air line, northeast of the nearest point on Michipicoten Harbour. In the following year, extensive surface exploration and diamond drilling disclosed a commercial body of nonbessemer brown ore, possibly 700 ft. long and 200 ft. wide, of about the following analysis:3 Fe (natural), 57.15 per cent; S, dried at 212°F.. 0.113; SiO2, dried at 212°F., 4.00; P, dried at 212°F., 0.125. The property (Figs. 1-3) was taken over by E. V. Clergue and ultimately was transferred to the Algoma Steel Corporation. The Algoma Central Railway shortly afterward built its line from Michipicoten Harbour to the mine, together with an ore dock at the Harbour. Thus, within three years of its discovery, the mine had adequate shipping facilities and a market for its ore. Production of Brown Ore and Pyrite The first shipment of brown ore was made in July 1930. By 1939, the mine was shipping at the rate of 170,000 long tons

Jan 1, 1949

By C. O. Rison

HIGH explosives, particularly nitroglycerin, have been used in torpedoes for the purpose of shooting oil and gas wells for more than 60 years. The early history of the oil industry in Pennsylvania is not clear as to who actually torpedoed the first well, although in 1865 the Roberts Torpedo Co. procured a patent covering the process. Gunpowder was first used, although nitroglycerin was substituted shortly afterwards. Wells are shot for the purpose of increasing the flow of oil and gas A shot-hole in the producing horizon, with its contributory fissures and fractures, increases the area of and stimulates drainage into the hole. The shot-hole also acts as a collecting basin from which the oil is pumped. As a rule, hard or close-grained sands or limes are shot, other more or less porous and soft formations usually do not require shooting. and might be injured by blasting. Shooting is also resorted to in mechanical trouble such as straightening crooked holes, sidetracking pipe or tools, and for severing frozen strings of casing or drill pipe. Explosives arc also used sometimes to extinguish oil or gas-well fires although that work, which involves unusual conditions and methods, does not properly come within the classification of oil-well shooting. Some Factors to Be Considered in Shooting Wells Although nitroglycerin has been used extensively for more than half a century in shooting oil and gas wells, there is still a great deal of uncertainty as to the proper method of shooting or the amount of explosive required to produce best results in a particular formation. The possibility of shooting unproductive or cavey formations above or below the productive horizons, shooting into lower water, destroying casing seats, and the splitting or collapsing of casing strings, are factors that require consideration. The engineering departments of a number of the larger oil companies are making a study of methods of shooting, and the amounts of liquid nitroglycerin or other explosives required in shooting various productive

Jan 1, 1929

By R. M. Brick, Arthur Phillips

The Institute of Metals Division Lecture in 1936, given by R. F. Mehl, on diffusion in solid metals1, was introduced with the statement that "the phenomena of diffusion are intimately related to many basic problems of the metallic state, but in addition to this the process of diffusion is of first importance practically." In view of the scope of that lecture, it does not seem necessary to review the importance, history or present status of diffusion problems. One aspect of the subject of diffusion that has received little attention became of some immediate importance in the course of a study on segregation. When a solid solution alloy freezes, the familiar mechanism of solidification requires that the first nuclei formed be low in solute concentration, with a resultant normal segregation or coring effect during freezing. Theoretically, musion of solute atoms during solidification should result in a homogeneous solid solution. Actually, of course, it is impossible in most binary alloys to obtain a cooling rate that will permit diffusion to eliminate coring in the freezing dendrites. For a given alloy, the extent of diffusion attained up to the point of final solidification will determine the degree of enrichment in solute atoms of the final liquid phase. The flow of this liquid into dendritic contraction channels and the solute concentration of the liquid seem to be the determining factors as to whether the final gross segregation is normal, inverse or absent. The purpose of the present study of diffusion was to determine to some extent the separate diffusion rates of copper and magnesium into pure aluminum with a view to clarifying previous results on segregation in these alloys; i.e., the fact that under similar freezing conditions aluminum-copper alloys segregate inversely and aluminum-magnesium alloys segregate normally. Of concomitant interest were the questions of the homogenization times required for segregated ingots or partially melted, i.e., "burnt," structures, and the solution heat-treatment times required for cast, hardenable aluminum-copper and aluminum-magnesium alloys, for worked and annealed structures, and so forth.

Jan 1, 1937

By H. C. Schultz

CERTAIN local conditions were known to govern in large measure the successful adaptation of liquid-oxygen explosives to the large-scale blasting at Chuquicamata. The wide variation in hardness of the rock at this mine makes necessary the use of several types of explosives. A locally manufactured, relatively cheap black powder is used in blasting the softer waste and capping material, where a thorough displacement breaks the ground sufficiently. Before the introduction of L. 0. X., an ammonia dynamite of about 65 per cent. strength was being used exclusively in the harder underlying orebody, where a strong disruptive as well as a displacement effect is required for breaking the ore. The L. 0. X., as developed for quarry work in the United States, has a practically pure carbon cartridge material, and the explosive has an extremely high rate of detonation, which should therefore cause it to usefully develop its full disruptive effect in hard ground. The individual blasts at Chuquicamata are large, black-powder shots which dislodge masses of rock averaging 250,000 tons each, and dynamite shots which dislodge masses averaging 80,000 tons each. It was desirable, therefore, to attempt to displace with L. 0. X. the faster, higher-cost ammonia dynamite used in the smaller blasts. It was not considered practical to attempt to displace the low-cost black powder with L. 0. X., as estimated costs showed no probable saving if this were accomplished. Since it was desirable to continue shooting relatively large blasts for effective operation, it was recognized that larger storage facilities than had been in use would be needed for the liquid oxygen. Because of the difficulty of transporting and discharging large storage containers of efficient design, the better plan appeared to be storage and discharge of the liquid at the place of manufacture, and transportation of the filled soaking boxes to the blast.

Jan 1, 1928

By F. H. Deily, D. S. Rowley, R. J. Howe

By Robert L. Llewellyn

Preparation of coal begins at the face in underground mines or in the pit with surface mines. Impurities in raw coal can be in the seam itself or in extraneous material taken in mining from the roof or bottom. Raw coal is prepared only to the extent that is necessary to make the product salable. Over 60% of all coal production is processed to some extent in cleaning plants. For underground mines the proportion cleaned is 72% as compared to 42% from surface and 15% from auger mines. Coal supplied for coking purposes is nearly all upgraded by washing, while for the largest market, electric power generation, a high proportion is shipped as a raw product with processing, in whole or in part, only as necessary when excess impurities are mined with the coal. This chapter will deal primarily with plants that process or wash coal to some extent and only incidently with mines shipping raw run-of-mine coal crushed to a top size of, usually, 2 to 4 in., with little, if any, other treatment. ECONOMICS OF COAL PREPARATION During the past decade, major changes have occurred affecting the market, profit, and long-rang planning of the coal industry. Mining companies have become "partners" with consumers at many new and some old mines, both for steam and metallurgical coals. Coal properties have become "assigned" tonnages at mutually agreed upon conditions and prices. Lower unit-train tariffs have been instrumental in helping coal markets to compete against oil and atomic energy. Cod prices for power plants are still on a Btu (British thermal unit) basis but with more emphasis on sulfur content. For metallurgical coal, the lower and medium volatile coals are in demand and the price rises, generally, as the volatile percentage is lower. Moisture affects the Btu value of coal almost the same as ash content, but dusty conditions during loading and unloading are no longer accept-

Jan 1, 1973

By Arthur Wade

During the year 1938, there was some drilling in Queensland, New South Wales and Victoria, as follows: Queens1and.—At Hutton Creek, lat. (approx.) 25° 45' S.; long (approx.) 149°, drilling was done by Drillers limited (subsidiary Oil Search) to a depth of 4688 ft., to the Lower Permian(?). There were small gas showings. The hole mas abandoned. At Mt. Bassett, lat (approx.) 26" 20' S.; long. (approx.) 149", Roma Blocks Oil Co. No Liability drilled to a depth of 4033 ft. The hole bottomed in granite. There were small showings of' oil and gas above bedrock in what may be Permian but is not yet determined. The company intends to run a formation tester. New South Wales.—At Kulnura, lat. (approx.) 33" S., long (approx.) 151°, the Kamilaroi Oil Company Ltd. (subsidiary of Oil Search Ltd.) drilled to a depth of 6293 ft. The Permian, probably Upper Marine Series, was reached. Drilling is to continue. Victoria.—At Romawi, lat. (approx) 37" 50' S., long. (approx.) 147" 45', a dry hole 3246 ft. deep bottomed in the Jurassic and was abandoned. It was drilled by the Governments of the Commonwealth and the State of Victoria. At Lakes Entrance, 1st. (approx.) 37" 50' S.; long. (approx) 748", a small showing of' oil (a few pints a day) was obtained from a well drilled 1275 It., to the Upper Oligocene-Glaucnnitc series, by the Austral Oil Drilling Syndicate, No Liability. Future Drilling Preparations is are being made by companies fur further test drilling in 1939, and the Governments of the Common wealth and the State of Victoria are continuing test holes for information only in the Gippsland district of Victoria. In Papua and New Guinea, no test drilling was done in 1938, but several companies are carrying on geological investigation and it is expected that, some test holes will be drilled during 1939.

Jan 1, 1939

By Arthur Wade

During the year 1938, there was some drilling in Queensland, New South Wales and Victoria, as follows: Queens1and.—At Hutton Creek, lat. (approx.) 25° 45' S.; long (approx.) 149°, drilling was done by Drillers limited (subsidiary Oil Search) to a depth of 4688 ft., to the Lower Permian(?). There were small gas showings. The hole mas abandoned. At Mt. Bassett, lat (approx.) 26" 20' S.; long. (approx.) 149", Roma Blocks Oil Co. No Liability drilled to a depth of 4033 ft. The hole bottomed in granite. There were small showings of' oil and gas above bedrock in what may be Permian but is not yet determined. The company intends to run a formation tester. New South Wales.—At Kulnura, lat. (approx.) 33" S., long (approx.) 151°, the Kamilaroi Oil Company Ltd. (subsidiary of Oil Search Ltd.) drilled to a depth of 6293 ft. The Permian, probably Upper Marine Series, was reached. Drilling is to continue. Victoria.—At Romawi, lat. (approx) 37" 50' S., long. (approx.) 147" 45', a dry hole 3246 ft. deep bottomed in the Jurassic and was abandoned. It was drilled by the Governments of the Commonwealth and the State of Victoria. At Lakes Entrance, 1st. (approx.) 37" 50' S.; long. (approx) 748", a small showing of' oil (a few pints a day) was obtained from a well drilled 1275 It., to the Upper Oligocene-Glaucnnitc series, by the Austral Oil Drilling Syndicate, No Liability. Future Drilling Preparations is are being made by companies fur further test drilling in 1939, and the Governments of the Common wealth and the State of Victoria are continuing test holes for information only in the Gippsland district of Victoria. In Papua and New Guinea, no test drilling was done in 1938, but several companies are carrying on geological investigation and it is expected that, some test holes will be drilled during 1939.

Jan 1, 1939

A-Metal Mining B-Minerals Beneficiation F-Coal H-Industrial Minerals

Jan 11, 1950

By Larry Kaufman, Morris Cohen

THE solid phase equilibria' and the martensitic transformation in the iron-nickel system have been the subject of considerable study. In addition, there have been numerous investigations on the calorimetric and thermodynamic properties of iron-nickel alloys. The purpose of the present work is to extend the existing information concerning the martensitic reaction in the iron-nickel system, and to develop a general thermodynamic treatment which will encompass the equilibrium and non-equilibrium phase

Jan 1, 1957

By V. Koump, R. H. Tien, W. J. Kim

This paper presents an approximate solution of the problem of freezing of a binary alloy. he alloy is in the form of a one-dimensional slab of finite thickness. The surface temperature of the slab is assumed to be constant and lower than the solidus (or eutectic) temperature. The densities of the liquid and the solid are assumed to be equal. For a given binary alloy system, initial concentration of solute and surface temperature, the solution yields a) the temperature distribution in the solid skin, b) the temperature, concentration, and solid fraction distribution within the solid-liquid region, and c) the positions of the liquidus and the solidus (or eutectic) fronts as a function of time. The results of calculation for Fe-C and Fe-P systems are presented. In this investigation we are considering the problem of solidification of a binary alloy. The alloy is in the form of a one-dimensional slab of finite thickness. The molten alloy is initially at liquidus temperature. At time zero the surface of the slab is reduced to a temperature T, < Te,, where Te, is the solidus (or eutectic) temperature and T, is a constant. The densities of solid and liquid alloys are assumed to be equal and independent of temperature and composition. A qualitative picture of solidification of an alloy, under these conditions, is illustrated in Fig. 1. During the initial stage of solidification, before liquidus front reaches the center of the slab, freezing proceeds by propagation of two isothermal fronts, the liquidus front and the solidus (or eutectic) front. The fraction of solid at the liquidus front is zero; the fraction of solid at the solidus front is unity, The solid fraction and the temperature distribution between the two fronts and the width of the solid-liquid region change with time. During the later stage of freezing, after the liquidus front reaches the center of the slab, the liquidus front disappears. The solid fraction and the temperature at the center of the slab, as well as throughout the solid-liquid region, are now changing with time. The solidification is completed when the fraction of solid at the center of the slab reaches unity. In solution of this problem we seek to determine a) the temperature distribution in the solid, b) temperature, concentration,

Jan 1, 1968

By Edward Jeffrey

THE use of coke in metallurgy, to any important degree, dates from the middle of the 18th century. Its utilization came most opportunely for European civilization. The forests of Europe, except in the most remote and inaccessible regions, had been largely fed, in the form of charcoal, into the smelting furnaces. For a hundred years-the middle of the 17th to the middle of the 18th century-there was a stationary condition of population corresponding to the exhaustion of European forests. This situation, which was particularly evident in Great Britain, was due to the fact that the forests had been depleted and the practical utilization of coke had not begun. The coking industry is essential for our metallurgical industries, which in turn are basal to healthy economic progress. But coke is of great importance, not only on its own account, but for its byproducts, which enter fundamentally into all the arts of peace and war. The dyestuff industry and the manufacture of explosives are intimately connected with one another, as was shown by the recent war. The subject of coking coal, therefore, is well worthy the serious attention both of practical industry and the scientific investigator. The most valuable coking coals, from the metallurgical standpoint, are derived from the coals of highest ranks. Coals, for example, that have a carbon ratio of from 70 to 80 per cent. yield the most valuable coke for the blast furnace. The difficulty of investigating these coals, however, is great, for they are rather friable and delicate and possess a high carbon content, which makes them difficult to manipulate. They present, on account of their high carbon content, a considerable degree of opacity when examined, in thin sections, under the microscope. The tenderness of structure and blackness of such high-grade coking coals as those of Connellsville and the Pocahontas region make them extremely difficult to investigate.

Jan 1, 1925

By CHARLERS R. FETTEE

A slight decrease in drilling activity occurred in the oil fields of western Pennsylvania during 1945 and a considerable decrease in the shallow-gas territory (Upper Devonian or higher). The number of deep tests (Middle Devonian or deeper) completed was two less than in 1944 and these did not open any new reserves of natural gas. Thus far, no commercial oil has been encountered in sands below the Upper Devonian in Pennsylvania. Oil production declined 8 per cent.

Jan 1, 1946

By R. G. Bowman

Discussions of processes for the manufacture of white lead generally open with the statement that white lead is the oldest chemical pigment known to man. This fact is of more than historical interest; in the light of the present extensive use of white lead, it indicates that the compound possesses characteristics that make it unique among white pigments, and superior to all in its particular field. A greater variety of processes have been proposed for manufacturing white lend than for any other one chemical compound. Only a few of these processes have come into commercial use, however, and a large part of the present production here and abroad is made by the process used in ancient times. The outstanding disadvantages of the old process are that it is slow and laborious, affords no control of the product, and yields at best an impure material lacking in uniformity. Improved processes, sometimes classed all together as "quick processes," have had as their main object the shortening of the time required. Most of them accomplish this and some have yielded a superior product as well, but only two or three are now in use commercially. For centuries the manufacture and mixing of paints have been treated as an art, and the practice has been much influenced by tradition and precedent. There is a reluctance to abandon old materials for this purpose, and as few new uses for white lead have been developed, the adoption of the quick processes has been slow. The electrolytic production of white lead is not new, a large number of processes and forms of apparatus have been proposed and patented within the past 25 years, all directed toward the production of white lead, wholly or in part, by electrolysis. One or two of these processes were tried commercially but proved unsuccessful. Process The Sperry process, used by the Anaconda Lead Products Co., is the invention of Elmer A. Sperry, and was worked out to a commercial basis at the East Chicago plant. It resembles, in a general way, earlier methods, but embodies the features that make it possible to operate

Jan 1, 1926

By J. Charles Miller

THE expansion of facilities for rapid transportation of perishables by train, truck and airplane has necessitated consideration of refrigerants of a minimum weight and volume per pound of cooling and has stimulated the use of solid carbon dioxide commercially. The gas probably has not had wide application in the past in air-cooling equipment for mines, theaters or buildings, owing to its thermodynamic properties, as will be deduced from examination of Table 2. However, consumption of the liquid in carbonating beverages remains a dominant factor. In addition to these uses, carbon dioxide is employed to a limited degree as an explo-sive in the liquid form, as a freezing agent in plumbing, in laboratories for low-temperature work, and in the manufacture of golf balls.

Jan 1, 1936

By William Waters Van Ness

The Pierrefitte mines, situated in the South of France, in the district of the Hautes-Pyrenees, owe their name to the fact that the first mining operations of any extent, and of comparatively reccnt date, were carried out in the neighborhood of the village of Pierrefitte, which is a branch terminus of the Midi railway. The Pierrefitte mines, however, embrace a wide extent of country and several different concessions, on most of which comparatively little exploration-work has been done. The portion of the property presently to be described is a zone running roughly E—W., over a distance of about 5 miles from the valley of Cauterets to the valley of Estaing, the ridge dividing these valleys being a spur of the main chain of the Pyrenees, and running more or less at right angles to it. According to local tradition, which various indications tend to confirm, these mines are of ancient date, the first workings being attributed to the Romans, who are supposcd to have sought not only the lead but also the silver which is contained in the ore. Old slags have been found in the neighborhood which might well have been produced from the cupellation of lead-ores. These old workings, while of considerable extent at times, do not seem to have extended beyond a depth of 100 ft., even this depth being somewhat exceptional. The old notarial records of the district show that mines were known to exist, and that they were even worked, in the sixteenth century, but since the mines were abandoned (by the Romans or others) considerably prior to this period, very little

Jan 1, 1909

By R. D. Pehlke, J. V. Gluck

A study was made of the effect of small additions of metallic solutes on the thermodynamic activity of zinc in dilute solution with molten bismuth in the range 450o to 650°C. The experimental measurements were made in a multielectrode galvanic cell using. a fused LiCl-KCl electrolyte. The activity of zinc in binary solution exhibited a strong positive deviation from Raoult&apos;s law and obeyed Henry &apos;s law to at least 0.050 mole fraction. The ternary addition of lead, gallium, or indium increased the activity of zinc. Cadmium or tin additions slightly decreased the zinc activity. Copper, mercury, silver, or antimony caused moderate decreases, while gold strongly decreased the zinc activity. The results are expressed in terms of Wagner&apos;s interaction parameter ejZn and a second-order cross-interaction parameter. The interactions for copper, gold, silver, and antimony showed a linear dependence with reciprocal absolute temperature, while the other interactions were essentially independent of temperature over the experimental range. Since tin and antimony decreased the zinc activity, the hypothesis of a purely periodic variation with atomic number was rejected. A semiquantitative explanation was possible with a free-electron model when relative electronegativities were used to express changes in the electron/atom ratio caused by the solute addition. Random solution and quasi-chemical models correctly predicted the majority of the interactions for which binary data were available to apply them. A knowledge of the thermodynamic interactions in liquid (and solid) metallic solutions is of considerable theoretical and experimental interest in the formulation of quantitative thermodynamic relations for metallurgical processes. The approaches to defining the interactions may be either phenomenological (i.e., "What mathematical function adequately describes observed behavior and permits extrapolation to new situations?") or theoretical, such as a specific model

Jan 1, 1968

No phase of the steel industry is more typical of its remark- able progress than is the evolution and development of the modern American blast furnace. The founding of the Institute in 1871 also marked the beginning of a new era in the pig-iron industry. The rapidly expanding westward development of the country, with its seemingly unlimited markets, gave rise to unprecedented demands for blast-furnace products. The manner in which the iron industry responded provides a fascinating chapter in the history of industrial development. Prior to this period, the iron industry of the United States, largely concentrated in the East, was based upon the consumption of local iron ores and local fuels, the latter predominately charcoal and anthracite. Small, isolated furnaces were located near scattered ore and fuel sources, and the completely integrated ironworks and steelworks were yet to be developed. In about 1860 exploitation of the newly discovered rich ore deposits in Michigan and the successful adaptation of blast furnaces to coke produced from coal of the great Pittsburgh seam in western Pennsylvania proved to be major factors in firmly establishing the general westward shift of the industry. But these were largely economic in character, and it was not until about 1870 that the aggressive, individualistic nature of the ironmaster asserted itself in no uncertain manner. No longer limited by relatively inadequate equipment and inferior raw materials, and spurred as well as encouraged by those who supplied capital for these new enterprises, furnacemen began to establish unheard of records in iron production. It is not surprising that Pittsburgh was the center of this new activity. Its tenor is best indicated by the following account :l

Jan 1, 1948

By W. A. Backofen, B. C. Wonsiewicz

The Plasticity transition in magnesium was studied by plane-strain compression of single crystals and polycrystalline material at temperatures from about 20" to 307°C. Reduction of single crystals along the c axis was accommodated by twinning on {1011) and retwinning on (10 12}, followed by basal shear in the doubly twinned volume. Deformation in that mode can result in sufficient independent shears for arbitrary shape change. Fracture in c axis compression, below about 100°C, has been related to excessive shear caused by unloading from the stress for {1011} twinning (-50 ksi at 20°C) to that for slip within the twin (-3 ksi); ductility follows from heating because the stress difference is lowered and the twin volume, in which elastic strain energy is dissipated on unloading, is increased. The stress for (1011) twinning is strongly temperature-dependent but not given by a critical resolved shear stress law. The latter is attributed to the influence of stress concentration from prior intersecting shear on nonbasal planes, the former to the temperature dependence of the preliminary slip. THE basic symmetry of hcp crystals has the effect of limiting the number of independent slip systems and making twinning an important deformation mechanism. The general result in wrought polycrystalline aggregates is a more or less sharply developed texture (or preferred orientation) which underlies a strong anisotropy in mechanical behavior. Knowing how the one influences the other is essential background for the use of such materials. Magnesium was of interest in this work because of the unexplained plasticity transition that it undergoes somewhere in the neighborhood of 200°c.&apos;&apos;~ At lower temperatures plastic deformation before fracture in polycrystalline material is limited, while at higher temperatures extensive deformation is possible. The transition temperature commonly determines the lower limit of the range in which magnesium is worked. The limited ductility can be traced to a lack of independent crystallographic shears. A minimum of five are required for arbitrary shape change.&apos; Around room temperature, however, slip on all known systems provides only four.&apos; In each case, the slip direction is in the (0001) basal plane so that slip does not allow strain along the c axis. With increasing temperature, more slip occurs on the ( 1011) pyramidal plane and the ( 1010) prism plane but without change in direction.&apos;?&apos; Thus, that development alone cannot explain the transition temperature.

Jan 1, 1968

By W. S. Owen, T. Bell

The variation ox the M, temperature with nitrogen concentration has been determined experinzentally. The free-energy difference between martensite and the parent y Phase at the M, temperature,is computed for Fe-C and Fe-N alloys using recent solubility data fm the Fe-N system and new data for the variatim of the activity of the interstitial solute in the y phase with concentration. The "geometric model" is considered also, and the importance of Zener ordering is noted. It is shown that, although at any chosen concentration the M, temperature and the activity are significantly different in the two alloy systems, the free-energy duference is the same within the limits of experimental error, thus Providing further evidence of the very close similarity between the martensite transformations in Fe-C and Fe-N alloys. TO estimate the free-energy change accompanying the martensite transformation in binary interstitial alloys it is necessary to know the variation of the Ms temperature with interstitial solute concentration and some thermodynamic data. To date, only the Fe-C system has been discussed because this was the only system for which relevant experimental measurements had been made, but even in this case the data available are insufficient to permit the free-energy change to be calculated without the assumption of a thermodynamic model for the y and a solid solutions. The last comprehensive discussion of the topic was by Kaufman, Radcliffe, and Cohen in 1.960.&apos; Since that time Ellis, Davidson, and Bodsworth2 have redeter mined the activity of carbon in y iron as a function of carbon content and Atkinson3 has measured the activity of nitrogen in Fe-N austenite. The M, temperature of Fe-N is reported in the present paper. Thus, it is now possible to assess the free-energy change accompanying the martensite transformation in Fe-N alloys on the same basis as that used to assess the change in Fe-C alloys. This comparison is of interest because it has been shown recently4 that the structure of the martensite formed in Fe-N alloys changes with nitrogen content in a manner exactly parallel to the changes in structure in the Fe-C series and that the strain associated with the distortion of the iron lattice in either the y or the a phase by a nitrogen atom is the same as that produced by a carbon atom. The work to be described tests whether or not this close similarity between the two systems extends to the thermodynamics of the martensitic transformations. THE Ms TEMPERATURES FOR Fe-N MARTENSITE Bose and Hawkes5 found the M, temperature of a eutectoid Fe-N alloy (2.35 wt pct N) to be 35°C. This single determination appears to be the only reported measurement of the M, temperature of an Fe-N alloy. In the present work a series of more than fifteen different specimens containing between 0 and 2.7 wt pct N were prepared by controlled nitriding of pure iron wire 0.010 in. diam. The iron was supplied by B.I.S.R.A. and was designated ACN2. The nitriding procedure, all aspects of which are critical, has been described in detail elsewhere.&apos; Each specimen was quenched from the austenitizing temperature into brine at 20°C without removing the specimen from the ammonia-hydrogen atmosphere in which it was ni-trided. Alloys containing up to 0.7 wt pct N were fully martensitic. More concentrated alloys contained progressively more retained austenite. At 2.34 wt pct N the specimen was completely austenitic after quenching to 20°C. The M, temperature of specimens with M, temperature above 20°C (those containing less than 2.35 wt pct N) was determined by a thermal arrest technique. For the more concentrated alloys (2.35 to 2.70 wt pct N) the variation of electrical resistance with temperature down to -196°C was used. Unlike Fe-C alloys, Fe-N alloys cannot be reaus-tenitized in vacuum or in an inert atmosphere because excessive loss of nitrogen occurs, even in short times, at high temperatures. Consequently, the alloys were reaustenitized in the ammonia-hydrogen mixture corresponding to nitrogen equilibrium at the temperatures used. The specimens were quenched in a blast of cold hydrogen gas and the temperature, measured by a thermocouple welded to the 2.5-in.-long specimen, was recorded on a high-speed recorder. In the first experiments 0.002-in.-diam chromel-alumel wire thermocouples were used but it was found that these gave erroneous readings due to contamination by nitrogen pickup. Pt-Pt 13 pct Rh wires of 0.002 in. diam were found to be satisfactory. Further details of the experiments are available in the original thesis.7 The cooling rate was controlled between 400° and 4000°C per sec by adjusting the hydrogen pressure. At least three cooling curves were obtained for each composition. Each specimen was analyzed for nitrogen after quenching. To aid in the accurate location of the martensite arrest points a series of cooling curves of 0.010-in.-diam platinum wire were recorded and these, which did not contain an arrest, were used as comparison standards. Four specimens, each in the form of a 3-in. loop, were prepared from each of the four alloys containing more than 2.35 wt pct N. One specimen was used for nitrogen analysis, one for X-ray diffraction, and two for resistance measurements below 20°C. The latter specimens were quenched from 20°C into constant-temperature baths at selected lower temperatures.

Jan 1, 1968