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By T&apos Kê, ing-sui

INTRODUCTION ACCORDING to the classical theory of elasticity, the elastic portion of the stress-strain curve is represented by a straight line. Such a representation implies that there is a linear relationship between strain and stress and also that strain is a single-valued function of stress and vice versa. Actually, such a one-to-one correspondence between strain and stress does not exist in real metals. A well-known example is the elastic after-effect on unloading. Another familiar example is damping or internal friction, that is, the dissipation of energy attending vibration. In an extensive review of such phenomena, Zener1,2 has proposed the term "anelasticity" to denote that property of a solid in virtue of which strain is not a unique function of stress in the non-plastic region. The phenomena arising from anelasticity are called anelastic effects. The measurements on inelastic effects are, important in many fields of metals technology. Thus, in precise instruments such as watch springs, difficulties often arise from the slight dimensional changes after fabrication. The internal friction or damping capacity of metals is often an important factor in deciding whether they are appropriate for instruments in which there are accompanying vibrations.' However, for metal scientists, the study of anelastic effects furnishes a powerful tool for understanding many properties of metals in terms of their microstructures or atomic interactions. In order to utilize the anelastic measurements to their fullest extent for acquiring such information, the experimental studies of anelasticity must be interpreted by appropriate mathematical analysis. For a great many problems, however, the necessary information often can be obtained by general qualitative arguments. From the definition of anelasticity, any physical changes occurring in a specimen as a result of the applied stress will cause anelastic effects if such physical changes are accompanied by a delayed change of elastic strain. Under these circumstances, we have the condition that strain lags behind the stress. We may mention the stress-induced transportation phenomena as examples. These include the stress-induced thermal diffusion," the stress-induced diffusion of particles,8-12. and the stress-induced viscous slip along the microelements in metals.12-15 The differential equations describing the microscopic mechanism in these phenomena lead to relations in which stress is linear with respect to strain (and/or their derivatives). Thus if we can - demonstrate that the superposition principle is valid under the circumstances in which the anelastic effects are observed, we would expect in. the macroscopic relation a linear relationship between stress and strain and their derivatives. This report is to describe a number of anelastic effects observed in alpha-iron, and an attempt is made to derive valuable information from a critical study of these

Jan 1, 1948

By B. Egeberg, H. B. Smith

Britannia metal is a white alloy consisting primarily of tin and antimony, the tin greatly predominating. The alloy usually contains a small amount of copper and occasionally very small amounts of one or two other metals, such as bismuth, zinc, and lead. It is capable of being cold-rolled, it takes a high polish, and it is fairly noncorrosive; properties which make it a popular metal for many household and traveling utensils. Britannia metal is similar in many respects to pewter and has largely replaced pewter in the arts, but it should not be confused with that alloy, because pewter is essentially a tin-lead alloy, while Britannia is a tin-antimony alloy. In view of the fact that so little has been published concerning Britannia metal, the authors feel justified in presenting the results of their investigation, particularly since the behavior of this alloy under cold rolling and heat treatment differs so greatly from that of other metals and alloys. The old craftsman, engaged in the making of ornaments or tableware, heated the cold-rolled sheet metal or his finished product to a straw color corresponding to about 375" I?., claiming to produce thereby a harder and more rigid article. The fact that possibly led him to this heating was that a reheated article or sheet made from Britannia metal has a distinct metallic ring when struck a sharp blow, whereas an unheated article or sheet has a leady, dead note. No doubt he has associated the metallic ring with a greater rigidity and strength, and justly so, as will be seen later. The approximate analysis of the metal we investigated was 91 Sn, 7 Sb, 2 Cu, and the molten metal was bottom-poured into an iron mold yielding an ingot 7 3/4 in. wide by 11 in. long and % in. thick, the casting temperature being 800" F. The ingot was cold-rolled to a sheet 0.032 in. thick, sufficiently large samples for experimental purposes being cut from the sheet at intermediate stages. The samples were all tested for hardness with scleroscope and Brine11 machine, then heated to 212" F. for 30 min., and again tested after cooling to room temperature. The same samples were heated successively at 300°, 400°, and 440" F., followed

Jan 1, 1929

By H. B. Smith, B. Egeberg

Britannia metal is a white alloy consisting primarily of tin and antimony, the tin greatly predominating. The alloy usually contains a small amount of copper and occasionally very small amounts of one or two other metals, such as bismuth, zinc, and lead. It is capable of being cold-rolled, it takes a high polish, and it is fairly noncorrosive; properties which make it a popular metal for many household and traveling utensils. Britannia metal is similar in many respects to pewter and has largely replaced pewter in the arts, but it should not be confused with that alloy, because pewter is essentially a tin-lead alloy, while Britannia is a tin-antimony alloy. In view of the fact that so little has been published concerning Britannia metal, the authors feel justified in presenting the results of their investigation, particularly since the behavior of this alloy under cold rolling and heat treatment differs so greatly from that of other metals and alloys. The old craftsman, engaged in the making of ornaments or tableware, heated the cold-rolled sheet metal or his finished product to a straw color corresponding to about 375" I?., claiming to produce thereby a harder and more rigid article. The fact that possibly led him to this heating was that a reheated article or sheet made from Britannia metal has a distinct metallic ring when struck a sharp blow, whereas an unheated article or sheet has a leady, dead note. No doubt he has associated the metallic ring with a greater rigidity and strength, and justly so, as will be seen later. The approximate analysis of the metal we investigated was 91 Sn, 7 Sb, 2 Cu, and the molten metal was bottom-poured into an iron mold yielding an ingot 7 3/4 in. wide by 11 in. long and % in. thick, the casting temperature being 800" F. The ingot was cold-rolled to a sheet 0.032 in. thick, sufficiently large samples for experimental purposes being cut from the sheet at intermediate stages. The samples were all tested for hardness with scleroscope and Brine11 machine, then heated to 212" F. for 30 min., and again tested after cooling to room temperature. The same samples were heated successively at 300°, 400°, and 440" F., followed

Jan 1, 1929

By N. A. Stockett

SOUTHEAST Missouri is the largest and oldest lead-producing district in the United States. For the year 1941, the statistical picture of pig-lead production, stated in short tons (partly estimated by the Engineering and Mining Journal) is as follows. [Tons World production 2,000,000 United States production 460.000 Southeast Missouri production 242,000] The consumption of primary lead in the United States in 1941 was approximately 900,000 tons, or almost double the country's production. The largest previous year's consumption in the United States was 718,000 tons, in 1926. The largest quantities of lead are used for cable sheathing, storage batteries and white lead. During 1941 tetraethyl lead for auto and aviation gasoline consumed 50,000 tons of lead. The entire lead production of Southeast Missouri is now mined by the St. Joseph Lead Co., whose dominant position as the largest producer in the United States of lead directly from ores is best shown by the fact that in 1941 it produced approximately 31 per cent of the lead production of the United States from its mines in southeast Missouri, where 22,000 tons of ore, averag¬ing over 3.00 per cent lead, is mined per working day. It is known that lead was mined at Mine La Motte, Madison County, Missouri, by Renault in 1723. Other white men and Indians probably did some mining prior to that time. Since 1865, the recorded production to Jan. 1, 1942, shows that the St. Joseph Lead Co. and the various other companies that have operated in St. Francois County mined lead ore, which, after milling and smelting losses produced 5,00,000 short tons of pig lead. About 95 per cent of the present lead production of Southeast Missouri is mined in St. Francois County. The northern part of this area is 60 miles south of St. Louis. The remainder of the lead is obtained at Mine La Motte, about 25 miles southeast from the center of the producing area in St. Francois County. PROSPECTING In this district, most of the ore is discovered by surface and underground diamond drills and by prospect drilling underground with rock drills. Each 2-ft. length of the cuttings from these Jackhamer prospect holes is assayed for lead. These holes are marked and the records are entered on maps. It has been found that close drilling--100-ft. centers of holes, and sometimes less-is necessary in order to locate most of the smaller commercial ore bodies, many of which previously had been missed by drilling the areas with holes spaced 200-ft. centers or more.

Jan 1, 1943

Jan 1, 1880

By F. R. Morral

HOT-DIPPED heat-treated zinc coatings on sheet steel were examined with X-rays. The phases identified were compared with those listed in the modern literature of the zinc-iron system. The zeta (FeZn13) phase is shown to correspond to the phase found by Schueler (1925) in heat-treated zinc coatings. An investigation was undertaken to determine the phases present in hot-dipped FIG. I.-SYSTEM IRON-ZINC ACCORDING TO J. SCHRAMM.11 heat-treated zinc coatings on steel sheets and wire. This kind of coating on wire was studied some years ago by Schueler1 by microscopic and chemical methods. He reported a new phase, FeZn10. Later, Clark and Stillwell,2 using X-ray crystal analysis, identified a new phase in ordinary galva-nized wire, which was assumed to be the FeZn10 phase.

Jan 1, 1940

By E. V. Crane

A tremendous volume of the metal rolled annually into sheets strips and coil stock finds its way to a host of stamping and manufacturing plants which are the quantity production units of the country. Considerable in volume, too, are the rolled and extruded rods which go into forging and manufacturing plants for conversion into the same general line: those widely sold metallic necessities and luxuries of the household, the office, transportation, farming and building construction. Yet, in spite of its age and its importance, the stamping trade has been doing its "engineering" largely by trial and error. Its distinctive method is shearing out and plastically working metal to finished shape in a few quick strokes with high loads and expensive tools which are warranted only by large quantities to be produced. The principal operations have many features In common with rolling and wire-drawing methods. Combinations of stresses are diffcrent, however, and details of operations are infinite in variety. An engineering study of the subject begins with stress analysis, but must go back to metallurgy for its foundation. A grouping of pressed-metal working operations according to whether the metal is (1) sheared, (2) bent, (3) drawn or (4) squeezed has proved useful. All of these groups include instances of both hot and cold operations. For discussions of metal working properties, the division between hot and cold working is taken as the recrystallization range of temperature. This, of course, brings tin, lead and often zinc into the hot-work range at or near room temperature. The outstanding hot-working press field is in forging: particularly of brass; all of which is included in the squeezing group. Shearing Operations The shearing group of operations, including blanking, piercing, trimming, shaving, slitting, shearing, notching, parting and numerous variations and combinations of these enters once or more into the production schedule of practically every stamped or forged article. The transverse stress, set up in shearing, as shown in Fig. 1A, is a combination of an angular compressive thrust and a tensile stress which is also at an

Jan 1, 1931

By J. C. Marquardt L., J. A. Bratt, J. P. Hunt

The Quebrada Blanca copper/molybdenum prospect lies on a dissected plateau in the high Andes of Northern Chile. The Superior Oil-Falconbridge Group began exploration of the Property in 1977 under a joint venture foreign investment agreement with the Chilean government. Quebrada Blanca is a relatively high grade secondarily enriched porphry copper deposit. Primary mineralization occurred 38 million years ago and accompanied quartz monzonite intrusive. Early disseminated Primary mineralization was followed by hydrothermal mineralization, mineralized breccia, and post-mineral faulting. After supergene enrichment Quebrada Blanca was buried under late Tertiary gravels and then partially re-exposed in Quaternary time. During the past five years, a successful exploration program has developed an open-pit mining reserve, provided samples for bulk metallurgical testing, and located more than adequate supplies of water for future operations. The main orebody is amenable to conventional metallurgical treatment and contains more than 400 Mt (441 million st) of recoverable open-pit ore at about a 1:1 overall stripping ratio. The average millhead grade during the first six years of operations will exceed 1.5% Cu, plus recoverable molybdenum values. Several hundred million tons of additional reserves are available in the surrounding districts

Jan 1, 1984

By William Hilliard

IN any manufacturing business, it is of vital importance that the management should know the exact cost of the units of production. Without such knowledge, a company can sell blindly in the open market, obtaining the best prices it can in competition with other firms, and manage perhaps to continue in business for a time; but at any moment, and especially in a period of falling prices, such a firm is at a loss to know exactly at what point it can sell at a profit and exactly how much it is losing per unit if it sells below that point. Furthermore, it is necessary not simply to know the exact total cost per unit, but to know definitely all the different-factors which enter into that cost. A firm manufacturing pocket knives had been doing a profitable business for many years when it began to earn smaller and smaller profits, until there was scarcely any profit at all being realized. Being unable to determine exactly what its future policy should be, it called in experts who studied the past records carefully and followed out for a period a better cost, system. Investigation then showed that on several different kinds of knives in common use, a small profit per unit was being made. On a number of special kinds of knives, of which the firm was very proud, it had been forced to cut prices under the pressure of outside competition and had believed that a small profit per unit was still being made on that product, while a detailed cost analysis showed that a loss was being incurred on each knife of that kind produced. It then became clear that the company must either give up the special line and concentrate wholly on the cheaper knives and extend their sales to territory not yet developed; or expand its plant and produce more of the higher grade knives and thus lower the cost per unit enough to make money on the higher grade knives also, if conditions warranted such expansion. Investigation revealed that the market for large quantities of the high-grade -knives was decidedly uncertain and that the most promising move would be to manufacture only the less expensive knives on a larger scale. That plan was carried out and the concern began again to make a better profit.

Jan 1, 1932

By David R. Mitchell, Byron M. Bird

THE revision of this chapter has presented a problem in that heavy-medium jigging has come into the picture since the chapter was originally written (seven years ago), a practice in which an artificial medium is built up and maintained in the jig circuit. As this development makes the jig a "true" heavy-medium process, the method belongs in the chapter dealing with such processes. Although putting this development in its proper position in the book involves some repetition, this seems to be the best procedure, and it has been followed. As the chapter on jigs in its original form was intended to be more or less a handbook on jigging for the use of the practical man, and the great bulk of the material therein is still generally applicable, the text has been re-used in large measure. Two major changes should be noted: (1) the portion of the text relating to the refuse-withdrawing mechanism of the McNally-Pittsburg jig has been entirely rewritten, and (2) a description of the hutch valves on the Jeffrey jigs has been added. Jigging is the stratification of a mass of solid particles in upward and downward pulsations. The stratification usually is effected in a rectangular open-top container having a perforated bottom through which the pulsations of water are applied to the materials to be separated; in separating coal, to a mass of coal and refuse. Jigging usually is a continuous process involving three steps: (1) the reception of the raw coal, (2) the stratification of the coal and refuse so that the refuse settles to the screen plate, and (3) the overflow of the cleaned coal and the withdrawal of the refuse collected on the screen. The jig is the most universal washer ever devised. It is handling in practice a wide range of closely sized coals and ores, mixed sizes of coal from 8-in. to 0 through 3/4-in. to 0, and mixed sizes of ores down to 7/32-in. to 0and even smaller. It is treating materials ranging in specific gravity from that of gold at 19 to that of coal at 1.30. It is handling feeds in which the proportions of high-gravity materials range from 90 per cent or higher, as for some iron ores, to 10 per cent or less for some coals. It is handling feeds containing all shapes of particles-round, rectangular, and flat. It is handling simple separation problems and difficult separation problems.

Jan 1, 1950

By A. A. Scheil, S. I. Hoyt

In technological studies on steel considerable emphasis has been placed on the identification of the foreign inclusions, testimony of which is adequately given in the metallographic literature covering methods for their identification. The outstanding accomplishment in this field is the scheme devised by Campbell, Comstock and Wohrman for identifying various oxides, sulfides, silicates and other constituents by systematic etching tests and microscopic examination.' The time involved in carrying out this procedure has led to attempts to secure quicker methods, or at least to shorten the time required to secure essential information. An example of this is the use of dark field illuminatin,2 but when this was tried out by the authors it was found that cavities and pits on the polished surface appeared bright on a dark field and could not be distinguished from small glassy inclusions. Still another means is the Leitz Ultropak, an instrument equipped with optical units for the illumination of the specimen by reflected light to secure an effect similar to dark field illumination. The structures are made visible in exceedingly sharp details by utilizing the inherent properties of the samples, such as refractive index, absorption coefficients and reflection powers. We have had no experience with the Ultropak, but a recent paper by Benedicks and Löfquist3 describes methods for determining the refractive index of (Fe, Mn) O and MnS by the use of this equipment. Presumably this method would be subject to about the same limitations as dark field illumination, though the, feature added by Benedicks and Löfquist appears to offer great promise in inclusion identification.

Jan 1, 1935

By A. A. Scheil, S. I. Hoyt

In technological studies on steel considerable emphasis has been placed on the identification of the foreign inclusions, testimony of which is adequately given in the metallographic literature covering methods for their identification. The outstanding accomplishment in this field is the scheme devised by Campbell, Comstock and Wohrman for identifying various oxides, sulfides, silicates and other constituents by systematic etching tests and microscopic examination.' The time involved in carrying out this procedure has led to attempts to secure quicker methods, or at least to shorten the time required to secure essential information. An example of this is the use of dark field illuminatin,2 but when this was tried out by the authors it was found that cavities and pits on the polished surface appeared bright on a dark field and could not be distinguished from small glassy inclusions. Still another means is the Leitz Ultropak, an instrument equipped with optical units for the illumination of the specimen by reflected light to secure an effect similar to dark field illumination. The structures are made visible in exceedingly sharp details by utilizing the inherent properties of the samples, such as refractive index, absorption coefficients and reflection powers. We have had no experience with the Ultropak, but a recent paper by Benedicks and Löfquist3 describes methods for determining the refractive index of (Fe, Mn) O and MnS by the use of this equipment. Presumably this method would be subject to about the same limitations as dark field illumination, though the, feature added by Benedicks and Löfquist appears to offer great promise in inclusion identification.

Jan 1, 1935

ROBERT VAN ARSDALE NORRIS, who died at his home at Wilkes-Barre, Pa., on April 20, 1928, was born at Newark, N. J., on May 2, 1864, of parents who were direct descendants of such sterling New Eng-landers as Governor William Bradford, John Alden and Timothy Dwight. He went to the Collegiate School in New York and then to the Colum-bia School of Mines where he graduated with the class of 1885, having among class-mates A. S. Dwight, E. N. En-gelhardt, H. L. Hollis, G. B. Lee, Richard Moldenke, Wil-bur Sanders, Joseph Struth-ers, E. A. Wiltsee, and I. H. Woolson. His marked ability even among so many men of unusual ability caused him to be chosen as assistant to Pro- fessor Munroe in the summer school of mining and survey-ing immediately after gradua-tion, and he shortly after was also inspector of dredging operations on the Maurice River improvement work, Millville, N. J. The follow- ing year he worked in the chemical laboratory of Herman Behr in Brooklyn, and toward the end of 1886 he joined the staff of the Pennsylvania R. R. Coal Co. and the Susquehanna Coal Co. as assistant engineer. Six years later he was made principal assistant en- gineer and in 1900 he was made chief engineer of these companies. In 1904, he withdrew from them and estab- lished an office as a consulting engineer at Wilkes- Barre, later taking his son, Robert V., Jr., into partner- ship with him. They acted as consulting engineers for the coal department of the Delaware, Lackawanna & Western R. R. Co., the Lehigh Valley Coal Co., Coke Bros. & Go., Inc., the coal department of the Pennsyl- vania R. R. Co., the Wilkes-Barre & Hazelton R. R. Co., the Sterling Salt Co., and others, specializing in ex- amination and appraisal of coal properties, and also matters of Federal taxation.

Jan 5, 1928

By Henry Lloyd Smyth

In 1891-92 1 was entrusted with the geological survey of part of the large area lying between the Marquette and Menominee iron-ranges in the Upper Peninsula of Michigan, and extending from the Republic trough on the north, through portions of the valleys of the Michigamme and Fence rivers, to and including the intermediate Felch mountain range on the south. Until a few years back the larger part of this area has been very difficult of access, and much of it is difficult still. The rock-surface is for the most part covered with swamp, forest and glacial deposits of various kinds, and therefore has not invited geological study. For these reasons the district, as a whole, with the exception of the Felch mountain range, remained almost unknown from a geological standpoint until our work in 1892. Our main object was to map the pre-Cambrian rocks, particularly the iron-bearing formations of Algonkian or Huronian age, and to obtain as much information as possible with reference to their sequence and structure, In carrying out this purpose, the use of simple magnetic instruments was found to be of the greatest assistance, and indeed indispensable. In this paper the results of our experience in tracing magnetic rocks by means of the disturbances produced in these instruments, have been brought together in systematic form, with such references to the particular area as are necessary in order to illustrate general principles, with the hope that they will prove useful to other workers in the same region, or in other regions where similar conditions may be encountered. The writer was efficiently aided in the field-work by Messrs. Samuel Sanford and Charlea N. Fairchild for nearly the whole period, and E. B. Mathews and H. F. Phillips for part of it,

Jan 1, 1897

By Herbert R. Hanley

THE One Hundred and Twenty-sixth meeting-of the Institute, held in San Francisco, Sept. 25 to 29, 1922, was a success in every way. Character-istically, San Francisco presented climate suited, to the occasion, while the Committees on Arrangements left nothing undone that would contribute to the interest and entertainment of the members and their wives. There was a registration of over 230, and all sections, save three, were represented. In the technical meetings, under the leadership of Albert Burch in the mining session and C. W. Merrill in the milling session, the greatest interest was manifested in ore-hunting geology and modern ore-dressing methods. The general geologic phase developed numerous discussions and had for its aim the study and correlation of known data and the application-of these to the finding of commercial orebodies. The geologic features of the Comstock and their significance to the development of the present orebodies were discussed. This brought out matters of much technical interest as well as those of romantic nature in the history of the early life of that camp. The profitable application of modern milling methods to ores, non-commercial a short time ago, was discussed with much interest. The recent work on the Comstock ores occupied a conspicuous part in these discussions. Basic principles delineated by mathematical study of mechanical devices for the milling of ore came in for a prominent part in the program as well as the physical-chemical side of the processes devised for the winning of precious metals as a profit.

Jan 11, 1922

By J. A. Snyder, W. L. Finlay

SEVERAL notable studies of the effects of sub- stitutional solutes have been reported. Outstanding among these for its elucidation of general principles, is the summarized work of Hume-Rothery and coworkers.1 For a systematic study of the effects of substitutional solutes on the mechanical properties of the solvent lattice, the work of Brick, Martin, and Angier² on copper; of Frye and coworkers³,4,5 on copper and silver; and of Lacy and Gensamer6 and of Austin7 on iron may be mentioned. Titanium is one of the few elements offering the possibility of a similar study of interstitial solutes since, unlike most metallic elements, it exhibits extended solid solubility for most of the interstitial solutes—hydrogen, boron, nitrogen, oxygen, and carbon. This paper reports a survey of the effects of dilute solutions of nitrogen, oxygen, and carbon on the mechanical properties of high-purity alpha titanium. Previous Work: Van Arkel and De Boer showed" that high purity titanium was quite ductile and De Boer, Burgers and Fast established".' that not only were oxygen and nitrogen very soluble in solid titanium but that, long before the limit of solid solubility of either had been reached, these interstitial solutes rendered the metal brittle. Their electrical resistance data as a function of

Jan 1, 1951

By P. D. Merica

MY remarks are addressed to the question whether a program of international mineral control can effectively serve as a means of maintaining world peace in the kind of world envisaged by the Atlantic Charter. They do not touch the quite different questions whether such control could be appropriately used for postwar punishment of Germany and Japan, or for other purposes. I assume also that the question relates, not to the transition period immediately following the war, but to the more normal years which we hope will succeed this. Finally, they deal primarily with metals and metallic minerals rather than with. oil or coal or other minerals, although they may be applicable also to these other nonmetallic materials.

Jan 1, 1944

By William F. Butler, Mo-Hung Che

DEVELOPMENT OF MONEY AND MONEY STANDARDS This chapter is concerned with the rise, and then the decline and fall, of gold and silver as monetary metals. As a first step in tracing the history of this process, it is necessary to consider the nature of money, and the manner in which different forms of money have developed over the centuries. The origins of money go back into deepest antiquity. Once men ceased to be pure nomads and entered into even a rudimentary form of society such as clans or tribes, money had to be invented The first step was barter as farmers or hunters swapped their surplus products for things produced by artisans such as shoes, clothing, and simple tools. But such barter trading is inconvenient even in primative societies It is difficult to match up buyer and seller at any point in time There are problems in arriving at viable and acceptable terms of exchange. The accumulation of savings-wealth-is complicated. No one can be sure that a pile of furs, or wheat, or certainly fish or game can be used in the future to trade for other goods or services. So even prehistoric man saw the need for money. There was a need first for something to serve as a medium of exchange This was an essential first step in the process of specialization-or the division of labor. A farmer, a hunter, or a shoemaker could only devote his full efforts to his trade if he could be sure that he could exchange his surplus production for the other things he needed for existence. This required a medium of exchange-a form of money which would be broadly acceptable. Money was needed for two other reasons Some system of market prices was essential to facilitate the exchange of goods and services. This required some form of common denominator-some standard of value-to govern the exchange process. And there was also need for something to serve as a store of value, a place to put any excess production (savings) with the assurance that it can be used in the future to acquire a general range of goods and services. As a result, money, in one form or another, developed at a very early state in civilization. Yet the centuries have been marked by a search for a form of money which will possess in full measure all of the attributes in money-a reliable and universally acceptable medium of exchange, standard of value, and store of value. -A wide variety of things have been used as money at one time or another: shells, beads, stones, feather, metals, and even the teeth of sharks and dogs. Some of these things were obviously of little or no practical value. They were used because people had confidence in their continued acceptance as a medium of exchange. As the world evolved and as trading ex-

Jan 1, 1976

By Charles L. Mantell, Kurt Straler

The hydrogen reduction of Cr2O3 to chromium metal was found to be feasible at very low water-vapor concentrations, corresponding to dew points of -38° to -24°C, over a temperature range of 1130" to 1490°C. Hydrogen reduction under these conditions was predicted by the calculated equilibrium curves which also indicated that CrzOs is reduced directly to chromium without forming the intermediate oxide, CrO. This reduction path was confirmed by X-ray diffraction analysis. The percent reduction of Cr2O3 at each reaction temperature was constant with time, suggesting an inhibiting effect of water vapor. A small increase in the residual water-vapor concentration of a single temperature, 1490°C, strongly retarded the rate of reduction This effect was expressed by an empim'cal equation which indicated a direct relationship between "distance from equilibrium" and the rate of reduction. me effect of temperature over the range of 1130" to 1490°C was expressed in an Arvhenius plot of log rate vs reciprocal absolute temperature. From this curve the apparent enthalpy of activation was found to be 29,600 cal. Based on the hypothesis that the rate of reductiun is contvolled at the oxide-metal interface, an over-all rate equation consistent with the experimental data and the thery of absolute reaction rates was formulated. A simplification of this expression to an Arrhenius equation was justified by the overriding effect of temperature on the rate of reaction for the minimum water-vapor concentration range. MOST of the metals in Subgroup V1 of the periodic table can be prepared commercially by direct reduction of their oxides by hydrogen or carbon monoxide, at temperatures considerably below the melting points of both the metals and their oxides. Chromium is an exception, being generally reduced from its ore, Cr2O3 . FeO, by silicon in an electric arc furnace which operates above the melting point of the Fe-Cr alloy or above the melting point of chro- mium if a chromium oxide be the starting material. In reduction of chromium oxide by hydrogen, either reduction does not occur at all or the rate of reduction is extremely slow. Theoretical considerations based on the high, exothermic, free energy of formation of Cr2O3 compared to the oxides of the other Subgroup VI metals, molybdenum, tungsten, and uranium, would also suggest a slow rate of reaction and a high activation energy. Interest in the direct gaseous reduction of fine-powdered ores in fluidized beds was considered justification for examination of this reaction. In order to develop a basis for a continuing study of the commercial feasibility of the direct gaseous reduction of chromite, a study of the kinetics of the reduction of Cr2O3 with hydrogen was undertaken. To the authors' knowledge no accurate kinetic data for this reaction have been obtained. Neither has an activation energy been determined nor has an attempt been made to establish a mechanism of reaction. LITERATURE Maier10 compared the data of I. Y. Granaat,6 H. von Wartenburg and S. Aoyama, and G. Grube and M. Flad7 with that derived from calorimetric and ther-modynamic properties for the equilibria for the reduction of Cr2O3 with hydrogen. These results, plotted as the log of the equilibrium constant vs absolute temperature for the reduction of Cr2O3 and the intermediate oxide, CrO, to chromium, show agreement between the differently derived data. In both cases the equilibrium constants were extremely low. Maier showed that, over a temperature range of 1000° to 2000°K, Cr2O3 is more readily reducible than CrO. Granat assumed that CrO was preferentially formed from Cr2o3 above 1100°C. Grube and Flad's analysis of their reaction products in the 895" to 1000°C range indicated the coexistence of only Cr2O3 and chromium. The hydrogen reduction of the other Subgroup VI metals, molybdenum, tungsten, and uranium, shows that reduction of the higher oxide proceeds through all of the intermediate oxides before being reduced to the metal. Since evidence pointed to an anomaly in the reduction behavior of Cr2O3, the authors investigated the reduction path of Cr2Os.to chromium. This was done theoretically with more recently available free-energy data and experimentally by X-ray diffraction analysis. This work reinforces Maier's conclusion.

Jan 1, 1964

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