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By B. S. Lement

No appreciable stabilization of the austenite-martensite reaction occurs in a 15 pct Cr-0.7 pct C steel unless some martensite is initially present. Stabilization is induced by interrupting the subcool below M,; however, disappearance of the stabilization effect as manifest by burst formation of martensite may occur on continued holding at the final subzero reaction temperature. The higher the temperature of intermediate cycling after the initial subcool, the more permanent is the stabilization effect at the final reaction temperature. Appreciable conditioning of retained austenite occurs on reheating to about 500°C. These phenomena are explainable on the basis of the reaction-path theory. A RECENT investigation' carried out by the authors has shown that isothermal transformation of austenite to martensite definitely takes place in a 15 pct Cr-0.7 pct C steel and that appreciable amounts of martensite can form in this fashion. Investigations2-" arried out on other steels and iron alloys make it seem probable that isothermal formation of martensite is a phenomenon of fairly general occurrence. The reaction-path theory of Cohen, Machlin, and Paranjpe5,7 explains isothermal transformation on the basis of thermal activation of strain embryos which generate martensite plates with a velocity approaching that of sound. On the other hand, the nucleation and growth theory of Fisher, Hollo-mon, and Turnbull8 egards isothermal transformation as due to growth of athermally formed martensite nuclei. The experimental evidence obtained thus far favors the reaction-path theory in that the martensite reaction seems to be nu-cleation-controlled rather than growth-controlled. Stabilization is another phenomenon of importance with respect to the austenite-martensite reaction. According to the reaction-path theory, stabilization is a result of relaxation of strain embryos. It is postulated that strain embryos are present at the austenitizing temperature in the form of dislocations or lattice imperfections in the austenite which vary in the extent to which the lattice is displaced along the strain reaction path leading to martensite. On quenching from the austenitizing temperature, athermal martensite starts to form as soon as the M. is reached, because the activation energy of the transformation which decreases with decreasing temperature is lowered to below the level of the highest energy strain embryos. Martensite plates are generated during the cooling below M, from embryos possessing energies above the activation energy corresponding to the temperature at which the cooling is stopped. The distribution of lower energy embryos is changed because of the elastic and plastic strains produced in the remaining austenite as a result of the transformation. This effectively increases the number of strain embryos at all levels of energy below the activation energy and tends to stimulate further martensite formation either iso-thermally or on subsequent cooling. However, if the temperature at which the cooling is stopped is high enough for relaxation of strain embryos to occur, some degree of stabilization against further transformation may be induced. Whether stabilization will be observed on subsequent cooling will depend on the extent of decrease of activation energy with temperature. If the activation energy decreases sharply with temperature, it is possible that transformation will appear to continue with decrease in temperature in spite of the loss of embryos by relaxation. However, with a more gradual decrease in activation energy, stabilization will be manifest by no further transformation on cooling over a measurable temperature range until the

Jan 1, 1954

By Whitman E. Brown, Louis J. Erck

L. A. ROE*—This paper is one of great value to the iron ore industry. The Humphreys spiral is a relatively new tool and gives promise of being quite useful in solving certain problems of iron ore beneficiation. Spirals have been tested on a martite ore at the Benson mine of Jones and Laughlin Steel Corp. in northern New York State. Our New York ore is considerably different, physically and mineralogically, than the one mentioned in this paper, and contains only 25 pct iron. This ore can be processed on spirals to give a concentrate containing 62 pct iron with an 85 pct recovery. On our particular ore we found operating difficulties when the spiral feed was coarser than 14 mesh. These were chiefly due to excessive "build-up" of locked middlings in the spiral circuit. In extreme cases these middling particles would accumulate to such an extent that the plant had to be shut down and the spiral surge tanks cleaned out. It is interesting to note that there exists a close relationship between the results of tabling a given iron ore and concentration of this same ore on Humphreys spirals. The size range of the ore must, of course, be within those limits acceptable to spiral concentration. Comparative tests on several of our mar-tite ores showed tabling results to be the same as spiral results. The authors make no mention of the use of a tailing stream splitter (now available from the spiral manufacturer) which is a useful tool in studying iron losses in the tailings stream. 011 our particular martite ore we found a considerable accumulation of fine-sized iron ore particles in the outside portion of the tailings stream. This fraction may be amenable to further treatment. E. H. ROSE*—The authors have concluded an interesting piece of work and this paper is an excellent factual account of a rapid and somewhat unusual transi-;ion in practice in the plant described. Perhaps it was modesty on their part which caused them so casually to limit to one sentence the fact that "several other methods of concentration on the fine ores representative of the Hill Trumbull group . . . failed to produce consistently an acceptable grade and recovery of finished product." The fact is that they were confronted by a difficult mineral-dressing problem and they are to be congratulated on their courage and persistence in staying with it until a satisfactory solution was evolved. A visitor to the plant might have been mildly astonished, as I was, to see one type of concentrator handling that part of the load early in the 1947 season, its experimental replacement by another a little later, and then in 1948 to see that both types had simply disappeared and their place taken by the spirals which were operating as placidly as though they had been there all the time. In working out economic methods of beneficiating Alabama red ore, most of which development is still ahead of us, it is likely that we also will pass through a period of successive disappointments, for we too have a problem where it is next to impossible either to "guess 'end right in the first place," or, because full-scale operating cost is such an important factor, to lay the ultimate answer on the line in advance by means of laboratory experimentation. Iron ore being what it is instead of what it used to be, it is encouraging to have the example the authors have given us today that a tough nut that will not crack on the first blow or the second is apt to do so on the third or fourth.

Jan 1, 1950

By A. E. Jenkins, A. Jostsons

Isothermal sections of the Ti-0-H phase diagvam at 600°, 700°, and 800°C have been constructed from equilibrium hydrogen pressure measurements over a range of Ti-0-H alloys containing up to 34 at. pct 0. Oxygen reduces the hydrogen solubility at fixed hydrogen pressure but increases the terminal solubility in the a solid solutions at the a/(a + P) phase boundary. Metal-lographic studies of alloys annealed below the eutectoid temperature show that oxygen also increases the ter-ninal solubility of hydrogen in the a solid solution in equilibrium with the hydride phase. The effect of oxygen on hydrogen solubility is discussed in terms of the electronic and geometric structure of interstitial solid solutions. THE isothermal solubility of hydrogen in a Ti-0 alloys at 800°C has been measured by Hepworth and ~chuhmann' who subsequently used ternary Gibbs-Duhem integrations to calculate oxygen activities in binary Ti-0 alloys. The present study aims to extend Hepworth and Schuhmann's measurements to alloys richer in oxygen and to a range of temperatures. This paper presents the results of hydrogen equilibrium pressure/concentration measurements in Ti-0 alloys as well as observations on the effect of oxygen on the terminal solubility of hydrogen in a titanium. The thermodynamic properties of binary Ti-0 alloys, derived from these measurements, will be published separately.' EXPERIMENTAL METHODS Specimen Preparation. Ti-0 alloys were prepared from iodide-refined titanium and titanium dioxide obtained by hydrolysis of redistilled titanium tetrachlo- ride. Specimens containing up to 16 at. pct 0 were prepared by electromagnetic levitation3 whereas a conventional tungsten arc furnace with a water-cooled copper hearth was used to melt oxygen-rich alloys. The specimen homogeneity was indicated by the constancy of lattice parameters of samples from various parts of the ingot as well as by the sharpness of the reflections on X-ray powder patterns. Oxygen-rich specimens in the composition range (20 to 34 at. pct), where ordering has been ~bserved,~ were annealed for 300 hr at 600°C prior to use in hydrogen solubility measurements. Apparatus. The hydrogen pressure/concentration measurements were made with a modified Sieverts apparatus shown diagrammatically in Fig. 1. Specimens were placed in a clear silica tube and impurity pickup by direct reaction with silica was prevented by lining the heated end of the silica tube with thin molybdenum sheet. A double silica tube was required to eliminate loss of hydrogen by diffusion through silica at high temperatures and high hydrogen pressures, the space between the tubes being maintained at a hydrogen pressure equal to that above the specimen. Hydrogen was purified by diffusion through a Ag-Pd tube.= Hydrogen pressures were measured with a mercury McLeod gage in the range 0.001 to 4 Torr

Jan 1, 1968

By Donald D. Smythe

Tars paper describes briefly the topography and geology of the region where the mica-bearing pegmatites are found and discusses prospecting, the quality of the mica, its preparation, and evaluation of the deposits. Muscovite mica occurs in a number of widely separated localities in Brazil, but production has come largely from deposits in the southeastern and eastern part of the State of Minas Gerais (Fig. I). There the deposits form a discontinuous zone, which starts at a point 90 km. north of the city of Rio de Janeiro and extends north for some 500 km., roughly parallel to the coast. A maximum width of 180 km. is reached along the Rio Doce. To the west in Minas Gerais, and extending east into the states of Espirito Santo and Rio de Janeiro, the mica zone proper is fringed by areas in which there are scattered occurrences of mica-bearing pegmatites. A few of these outlying deposits have produced commercial mica, but most of them are unimportant. To the southwest, in the State of São Paulo, there are a number of mines, which at one time produced a very considerable amount of sheet mica, largely as a by-product of kaolin mining. These deposits, and, a few others lying between them and the main productive areas to the northeast, appear to be the southwestern continuation of the strong Minas Gerais mica zone. In the vicinity of Conquista, just north of the Minas Gerais boundary in the State of Bahia, and still farther north, near Jacobina, there are several known mica deposits. Their location indicates that they may be the northern continuation of the main mica zone. The major part of Brazilian mica production has come from four areas within the mica zone proper; from north to south, Governador Valadares, Raul Soares, Espera Feliz, and Muriaé. The first is 190 km. from north to south and reaches a maximum width of 180 km. The Raul Soares area extends 135 km. from northeast to southwest, and in places is 80 km. wide. The Espera Feliz area is 100 km. from north to south, and reaches a width of 35 km. The Muriaé area extends 150 km. from northeast to southwest and its width reaches 40 kilometers. Between the known productive areas, and in the areas directly to the southwest and to the north of them, little mica has been produced. These gaps, as well as certain irregularities in the outline of the mica zone itself, are to be ascribed either to lack of prospecting or to conditions preventing the discovery of mica, rather than to its nonexistence. Elsewhere in Brazil mica has been reported from eastern Goiaz, Ceará, Pernambuco, Rio Grande do Sul, Matto

Jan 1, 1946

By James G. Crawford

Correlation Of water with its reservoir zone or formation has been one of the applications of oil-field water analysis of greatest direct value to the petroleum engineer. The water in each producing zone tends to have diagnostic characteristics by which it can be distinguished from every other water above or below that zone in that immediate vicinity. Representative analyses of oil-field waters from producing oil and gas fields in the Rocky Mountain region are included, and the diagnostic characteristics are discussed briefly. It is concluded that the generally dilute nature of Rocky Mountain oilfield waters is a result of dilution by meteoric waters, and that there is no relationship between presence or absence of commercial oil and the character of water in a structure. Introduction The study of waters associated With oil and gas began more than 50 years ago and has been well recognized by operators, engineers, and geologists for about 30 years. It appears unnecessary at this time to recite the history of oil-field water analysis; suffice to say that it has proved its worth many times to the production engineer suddenly confronted with water problems in producing oil and gas wells. Chemists and geologists have studied the possible origin of these waters and as Yet the subject is unsolved in many important phases. There are both local and regional problems connected with the explanation of concentrations and character- istics peculiar to each field, each subsurface zone and each province. Criteria useful in postulating the Occurrence of oil Or gas in One province completely fail when applied to another, and data carefully prepared and analyzed from one field may be actually misleading when applied to another. Correlation of water with its reservoir zone or formation has been one of the applications of oil-field water analysis of greatest direct value to the engineer. The concentrations and characteristics of the waters are essential to the engineers and geologists making interpretations of electric logs in this region. The behavior of water under conditions of reservoir temperature and pressure is dependent to a great degree upon its concentration and characteristics, and thus important to the reservoir engineer. With the advent of secondary recovery methods in the Rocky Mountain region the characteristics and treatment of water will become increasingly important. Premises upon which Correlation Is Based A brief review of the geochemical history of oil-field waters will suffice to present the premises upon which correlations of the waters are based. Sedimentary rocks which are now stratified were first sediments in seas, lakes and streams. These sediments were filled interstitially with connate water. With burial the sediments were compressed arid consolidated, integrated and indurated into bed rock and much of the connate water was dispelled. Following the formation of bed rock the strata were sub-

Jan 1, 1949

By H. H. Stout

IN the early fall of 1025, the writer was conducting, in the Ledoux and Co. labora-tory, New York, experiments directed to-ward ascertaining the effect on its impurity content when cathode copper was subjected to a current of various gases at an elevated temperature below the melting point. The apparatus consisted of a vertical I-in. dia. silica tube about 12 in. long, heated on the outside. The cathodes were broken to pass 3/8-in. mesh, and a current of various differ-ent gases was passed up through a 4-in. long column of these loose cathode particles in the vertical tube furnace. Temperature was maintained to 1500° to 1600°F. and the gas treatments lasted from 3 to 6 hr. The writer observed that whenever reducing gas (H2 or CO) was used, these cathode par-ticles stuck together at points of contact with each other. The cohesion was so marked and tenacious that an examination was made of the fractured surfaces, when cathode particles were broken from the cluster. Crystal growth was always found to have taken place across the surfaces where separate particles were in contact, but only after all oxides, sulphates, etc., had been completely removed. The idea of a possible new process was then conceived and was disclosed to A. M. Smoot (V. P. Ledoux and Co.) with intent to obtain his views. The first conception as given Smoot was "to gas-clean broken cathodes, put them in an extrusion press, solidify and extrude them at around 1500°F." Smoot's reaction, after a few moments considera-tion, was, "It looks perfectly all right to me." The writer and his assistants, W. H. Osborn and H. H. Stout, Jr., after confer-ring as to ways and means, decided to go ahead with preliminary laboratory experi-ments, which, it was thought, would move the new process from the possible to the probable. This program followed a course indicated by three basic considerations: I. Since brittle cathodes were often unin-tentionally produced, it seemed probable that the laws controlling this type of deposi-tion could be ascertained. 2. We had already proved the gas-clean-ing feature. 3. There remained to prove: whether a sound, homogeneous metal billet could be produced with crystal growth established over the entire surface of each individual particle in the billet; and, if so, what would be the physical properties? Osborn arranged with Columbia Uni-versity for conducting experiments in its research laboratory to prove or disprove the third item; Columbia assigned C. A. Phillipi, Jr. to assist in the project. A press with a cylinder 2 in. high and of I-in. dia. was used. It was surrounded and heated by a resistance coil of Nichrome wire. Broken tough cathodes were used.

Jan 1, 1940

By B. M. Larsen, L. S. Darken

SOME years ago we collated all laboratory data then available to us on the distribution at equilibrium of manganese and of sulphur between metal and simple slags, and used the results in setting up an equation, which proved to be in accord with determinations of the distribution ratio of manganese and of sulphur between liquid steel and open-hearth slag, over a wide range of operating conditions. We now present an outline of our calculations and inferences on these two closely related questions, which are of especial importance because of the advisability of conserving manganese wherever possible. In general. our results show that in the open-hearth furnace equilibrium between metal and slag, with respect to both manganese and sulphur, is substantially attained during the finishing period of the heat, or in about a half hour to an hour after any additions were made. This implies that the end result will be identical whether manganese is added as alloy or metal to the liquid steel or as oxide to the slag. The proportion of total manganese retained by the steel is favored: (I) by use of the minimum amount of lime, consistent with other operating limitations, required to give a lime-silica ratio of about 2.4, which usually corresponds to a minimum practical slag volume; (2) by a high concentration in the slag of MnO relative to FeO; (3) by high operating temperature. Absorption of sulphur by the slag from the liquid metal is favored: (I) by large slag volume; (2-by a high concentration of active (or "free") lime and of manganese oxide dis) solved in the slag; (3) by low concentration of silica, iron oxide, and phosphate dissolved in the slag. DISTRIBUTION OF MANGANESE BETWEEN SLAG AND METAL AT EQUILIBRIUM On the basis that the distribution of manganese between liquid steel and slag is controlled by the reaction [FeO + Mn ;7± MnO + Fe [A] slag metal slag metal] the distribution at equilibrium, at a given temperature, is expressed by the equilibrium constant for this reaction, which is defined as [K" aFPI OFeO ? aMn] where a is the activity of the molecular species denoted by the subscript. The activity of each of the several components, although it is not known precisely, is approximately equal to the concentration of each component expressed as its mol fraction; that is, as the ratio of the number of mols of the given component to the total number of mols of all the molecular species present in the metal or slag, as the case may be. Moreover, since the activity, or concentration, of iron in the liquid metal is in fact substantially constant, the term aFe may he combined with K" to give a new constant K'. Making these changes.

Jan 1, 1942

By C.H. Lorig, M.C. Udy

Through the years much interest has been centered in attempting to develop a direct method of iron-ore reduction, to replace or supplement the present indirect blast-furnace process. It would not be difficult to produce a list of more than 500 patents dealing with the direct production of iron and steel, but the few of this type of process that have proved successful do not produce in competition with the blast furnace; they produce special products. A survey of the literature reveals that the equilibrium conditions for the reduction reactions (iron oxides with carbon monoxide and with hydrogen) have been fairly well established but that data on the rate of reaction are discordant, although the genera1 effects of the variables are known. This dissertation deals with the rate of reduction of a magnetite concentrate with hydrogen. The following variables have been studied: bed depth, gas velocity, particle size and temperature. The behavior of a single particle was also studied. Literature Two general factors should be considered in a study of reduction of iron oxide: (I) equilibrium relations, and (2) rate of reaction. The first factor, equilibrium, has received the attention of many investigators and the equilibria Fe304-FeO-H2-H2O, Fe3O4-FeO-CO-CO2, FeO-Fe-H2-H2O, FeO-Fe-CO-CO2 are fairly well established. Of the second factor, the rate of reaction, much less is known. Data are comparatively scarce and there is very little concordance. The discordance probably results from the large number of variables influencing the reactions. However, the general effect of the variables is known. Among these variables are temperature, gas velocity, particle size, porosity, gas composition (distance from equilibrium), presence of impurities, greater or less prevalence of side reactions, and even design of the apparatus itself. Wetherill and Furnasl published an excellent paper in 1934. They point out that any one or more of five processes (the chemical reaction, diffusion of the reactant through the gas film, diffusion of the reactant through the solid phase, diffusion of the reaction product through the solid phase, or diffusion of the reaction product through the gas film) may be the slow process, and thus the rate-controlling process. It is regretted that the work of these authors was limited to experiments at One temperature, and that the range of gas compositions was limited. Langmuir2 has shown that heterogeneous reactions take place at phase boundaries.

Jan 1, 1943

By M. C. Udy, C. H. Lorig

Through the years much interest has been centered in attempting to develop a direct method of iron-ore reduction, to replace or supplement the present indirect blast-furnace process. It would not be difficult to produce a list of more than 500 patents dealing with the direct production of iron and steel, but the few of this type of process that have proved successful do not produce in competition with the blast furnace; they produce special products. A survey of the literature reveals that the equilibrium conditions for the reduction reactions (iron oxides with carbon monoxide and with hydrogen) have been fairly well established but that data on the rate of reaction are discordant, although the genera1 effects of the variables are known. This dissertation deals with the rate of reduction of a magnetite concentrate with hydrogen. The following variables have been studied: bed depth, gas velocity, particle size and temperature. The behavior of a single particle was also studied. Literature Two general factors should be considered in a study of reduction of iron oxide: (I) equilibrium relations, and (2) rate of reaction. The first factor, equilibrium, has received the attention of many investigators and the equilibria Fe304-FeO-H2-H2O, Fe3O4-FeO-CO-CO2, FeO-Fe-H2-H2O, FeO-Fe-CO-CO2 are fairly well established. Of the second factor, the rate of reaction, much less is known. Data are comparatively scarce and there is very little concordance. The discordance probably results from the large number of variables influencing the reactions. However, the general effect of the variables is known. Among these variables are temperature, gas velocity, particle size, porosity, gas composition (distance from equilibrium), presence of impurities, greater or less prevalence of side reactions, and even design of the apparatus itself. Wetherill and Furnasl published an excellent paper in 1934. They point out that any one or more of five processes (the chemical reaction, diffusion of the reactant through the gas film, diffusion of the reactant through the solid phase, diffusion of the reaction product through the solid phase, or diffusion of the reaction product through the gas film) may be the slow process, and thus the rate-controlling process. It is regretted that the work of these authors was limited to experiments at One temperature, and that the range of gas compositions was limited. Langmuir2 has shown that heterogeneous reactions take place at phase boundaries.

Jan 1, 1943

By Robert M. Yonco, Irving Johnson, Martin G. Chasanov

The thermodynamics of the cadmium-rich portion of the Pu-Cd system has been studied with a high-temperature galvanic-cell method. The partial phase diagram of the Pu-Cd system was determined. The existence of the intermediate phases PuCd11 (cubic BaHg11 structure, ao= 9.282) and PuCd6 (cubic, CeCd6 structure, a, = 15.59) was established. The existence of at least one other intermediate phase richer in plutonium was indicated. PuCd11 was found to peritectically decompose into PuCd6 and liquid at 406" * 2°C. The solubility of plutonium in liquid cadmium may be represented by the equations: (355' to 399°C) log (at. pct Pu) = 6.223 -4282T-1 (399° to 632°C) log (al. pct Pu) - 5.148 - 5277T-1 > 1.156 x 106 T-2 The free energy of formation values (kcal per mole) of the two intermetallic phases are given by the equations: (PuCd11), ?Gf= -45.9 + 35.7 x 10-3 T (PuCd6), ?Gf0- -39.27 + 25.86 X 10-3T The excess free energy (kcal per mole) of plutonium in liquid cadmium may be represented by the equation: -(-16.72 * 29.54 NPu) 10-3T in which Npu and Ned are the atom fractions of plutonium and cadmium. The thermodyanamics of the U- Cd and Pu-Cd systems are compared. THERMODYNAMIC information on systems of the actinide metals with low-melting metals, such as zinc and cadmium, is useful in the design of pyro-metallurgical processes for the purification of nuclear reactor fuels. The thermodynamics of the Pu-Zn,1 Th-Zn.2,3 U-Zn,4-5 and U-Cd6 systems have been reported. The present report on the Pu-Cd system concerns the liquidus composition in the cadmium-rich region, the characterization of the two most cadmium-rich intermetallic phases, and the thermodynamic properties of these intermetallic phases and dilute liquid solutions of plutonium in cadmium. EXPERIMENTAL Phase Studies. The liquidus composition was determined by analysis of filtered samples of the liquid phase withdrawn at a series of temperatures. The apparatus and procedure were identical to that used in the previous study of the Pu-Zn system.' Briefly. a sample of the melt was withdrawn into a tantalum tube fitted with a porous tantalum filter (30-µ pore). the entire sample dissolved in hydrochloric acid (to avoid errors due to segregation

Jan 1, 1965

By Robert Henderson

SEVERAL very interesting articles have been written on the caving system of mining, but most of these papers have dealt separately with the slusher system or the chute and grizzly system. In this paper, a comparison will be made of the two methods, both of which are being used at the Climax mine. The mine is on the Continental Divide, in central Colorado, at an altitude of approximately 11,500 ft. above sea level. The long, cold winters, characteristic of the high Rockies, create a number of operating problems not usually found in other mining areas. THE ORE BODY The Climax ore body is just east of the Mosquito fault. This structural deformation has brought the granite on the east against the sedimentary rocks on the west. The ore occurs in an intensely altered granite and schist around a silicified granite core. The ore is in a highly fractured zone of moderate silicification. The principal mineral, molybdenite, is found in these fractures. Barren dikes of granite porphyry cut through the ore body and core with no apparent regularity. The grade of the ore is fairly uniform and gradually decreases toward the footwall core and also into the hanging-wall granite. The footwall and hanging wall are determined entirely by assays. The ore body is roughly dome-shaped, with the apex truncated at the surface. It is covered to varying depths with talus. A horizontal section of the ore body on the Phillipson level appears as an annular ellipse surrounding the footwall core. The ring of ore varies in width from 300 ft. to as much as 800 ft. The north-south axis of the core is about 1200 ft. and the east-west axis is about 1800 ft. In the ore zone, the rock is sufficiently strong to maintain reasonably large openings, and openings larger than haulage drifts usually have to be supported. The ore is cut by a great many fractures and shears and breaks into rather large blocks when caved, necessitating considerable secondary blasting. The waste that overlies the ore body breaks relatively fine in comparison with the size of the blocks of the caved ore and tends to run through the broken ore in the cave, causing dilution unless the draw is carefully controlled. MINING SYSTEMS For several years the ore was mined by the chute and grizzly system, a system that differs from that used in other caving mines only in the size of openings and equipment. In the chute and grizzly system, main haulage laterals were driven along the footwall core and also along the

Jan 1, 1944

By M. C. Udy, C. H. Lorig

THROUGH the years much interest has been centered in attempting to develop a direct method of iron-ore reduction, to replace or supplement the present indirect blast-furnace process. It would not be difficult to produce a list of more than 500 patents dealing with the direct production of iron and steel, but the few of this type of process that have proved successful do not produce in competition with the blast furnace; they produce special products. A survey of the literature reveals that the equilibrium conditions for the reduction reactions (iron oxides with carbon monoxide and with hydrogen) have been fairly well established but that data on the rate of reaction are discordant, although the general effects of the variables are known. This dissertation deals with the rate of reduction of a magnetite concentrate with hydrogen. The following variables have been studied: bed depth, gas velocity, particle size and temperature. The behavior of a single particle was also studied. LITERATURE Two general factors should he considered in a study of reduction of iron oxide: (1) equilibrium relations, and (2) rate of reaction. The first factor, equilibrium, has received the attention of many investigators and the equilibria Fe3O4-FeO-H2-H2O, Fe304-FeO-CO-CO2, FeO-Fe-H2-H2O, FeO-Fe-CO-CO2 are fairly well established. Of the second factor, the rate of reaction, much less is known. Data are comparatively scarce and there is very little concordance. The discordance probably results from the large number of variables influencing the reactions. However, the general effect of the variables is known. Among these variables are temperature, gas velocity, particle size, porosity, gas composition (distance from equilibrium), presence of impurities, greater or less prevalence of side reactions, and even design of the apparatus itself. Wetherill and Furnas1 published an excellent paper in 1934. They point out that any one or more of five processes (the chemical reaction, diffusion of the reactant through the gas film, diffusion of the reactant through the solid phase, diffusion of the reaction product through the solid phase, or diffusion of the reaction product through the gas film) may be the slow process, and thus the rate-controlling process. It is regretted that the work of these authors was limited to experiments at one temperature, and that the range of gas compositions was limited. Langmuir2 has shown that heterogeneous reactions take place at phase boundaries.

Jan 1, 1942

By D. W. Philips

THE problem of strata control has of necessity been prominent in mining, and accounts of individual experience and research abound in the literature of most mining countries. Organized research began in Britain by the formation of a committee, upon the recommendation of the Safety in Mines Research Board in 1923, to investigate methods of reducing accidents from falls of roof in coal mines. This committee examined current practice in supporting underground workings in the principal coal fields, and its findings have been published in the Board's publications. Toward the end of these investigations it was suggested by the Chief Inspector of Mines that committees of the several mining institutes be formed to examine the problem in their respective districts. The formation of these committees marked a new phase in research on strata control. The work, though being done in the separate coal fields, followed a scheme outlined by the Chief Mining Engineer of the Research Board, and was coordi¬nated by his office. FACTORS INVOLVED The subject is being considered in Britain from two aspects: I. To provide, by supports, means to prevent falls of fractured ground. 2. To develop methods whereby the strata can be maintained in the least broken condition and thus make falls less likely. The first aspect is the one that will most likely lead to immediate results from the accident standpoint. It depends largely upon the assimilation of already acquired knowledge regarding the proper¬ties of supports and their correct applica¬tion. The second aspect is perhaps more fundamental, and involves also the proper¬ties of the strata and their behavior under the influence of the forces induced by mining. The problem involves many natural factors that cannot be controlled, such as depth, inclination and thickness of seam and nature of the rocks. Other factors, which may be considered to a certain extent controllable, cannot be varied readily and with sufficient fre¬quency to facilitate easy investigation; some of these are: rate of advance of the working face, length of face, direction of the face with regard to cleat and inclination, system and arrangements of rock packing behind longwall faces. In any given case the very many factors present have a mutual influence upon the effects produced in the mine. For example, a study of the effects of rate of advance cannot be done without considering the effects of other factors such as nature of strata, direction of face and quality and arrangement of supports. Conversely, the length and direction of a working face

Jan 1, 1946

By Otto H. Henry, J. J. Cordiano

THOUGH powder metallurgy is one of the oldest of metallurgical processes, it is in its infancy as a branch of the modern field of metallurgy. As early as 3000 B.C., the ancients produced implements and weapons of iron by reducing iron ore in a charcoal fire and forging the resultant sponge while still hot into the desired shape. Melting and casting soon superseded the powder metallurgy practice, and it was not until the turn of the twentieth century that powder metallurgy was applied to the commercial manufacture of tungsten lamp filaments. From this beginning, the use of the powder metallurgy process spread to the manufacture of porous oil-impregnated bearings, cemented carbide tools, contact points, diamond grinding wheels, clutch facings, starter brushes, resin-bonded radio cores, magnets, metallic filters, and other parts. More recently, and particularly during the present war, there has been a definite trend toward the manufacture of machine parts by this process in competition with the more conventional fabricating methods. Notwithstanding these many developments, scientific progress has been slow. While many articles on powder metallurgy have appeared in the press and various publications, there have been too few contributions to our technical societies, with the result that there is a dearth of the type of information necessary for the full development of this science. It is of primary importance that the results of research and development be freely disseminated if powder metallurgy is to realize its fullest potentialities. PURPOSE OF INVESTIGATION Excluding the refractory metal field, all commercial powder metallurgical products made by a cold compressing and sintering operation contain voids. These voids can be substantially eliminated by subsequent severe working and heat-treatment, but such practice has not proved economical in most applications. By applying heat during the compressing operation, plastic deformation of the powder particles is substantially increased, and the resultant compact or briquette is practically free of voids. However, hot-pressing has many attendant problems, which at present preclude its use in the manufacture of precision parts. The more important of these are to devise: I. A die steel capable of withstanding high pressures at elevated temperatures. 2. A high-temperature lubricant capable of preventing excessive die wear and welding of the compact to the die walls. 3. A method of retaining a neutral or reducing atmosphere in the compacting zone of the die assembly. 4. A means of ejecting the hot-pressed specimen into a neutral atmosphere until reasonably cold.

Jan 1, 1945

By D. J. McAdam

IN a recent survey of the literature, the author has found evidence incompatible with prevalent views regarding the technical cohesive strength and yield strength of metals. Some of the evidence regarding the technical cohesive strength was presented in a previous paper,21 and views were presented that are believed to be in better accord with the evidence. In that paper, it was shown that the technical cohesion limit (contrary to prevalent views) varies with the combination of principal stresses,† and that the influence of plastic deformation on the technical cohesive strength is not in accordance with prevalent views. In this paper, consideration will be given to both the technical cohesion limit and the yield stress as affected by the combination of principal stresses. Evidence will be presented that the variations of the yield stress and the technical cohesion limit with the combination of principal stresses are not in accordance with prevalent views. Consideration will also be given to ductility and work-hardening capacity, which depend on the initial difference between the technical cohesion limit and the yield stress. By the "technical cohesion limit" is meant the mean stress at actual or potential* fracture. An example of a technical cohesion limit is the "true" breaking stress of a tension-test specimen, the breaking load divided by the sectional area at fracture. The cohesion limit thus obtained for a ductile metal, however, has been greatly altered by the plastic deformation. It is important to consider the cohesion limit of the metal prior to this deformation, and the variation of the cohesive strength with plastic deformation. The relation between the cohesion limit and the corresponding flow stress† determines the ductility of a metal and the energy that it will absorb before fracture. In this paper, as in the previous paper,21 tensile stresses will be viewed as positive and compressive stresses as negative. The algebraically greatest principal stress will be designated S1, the least principal stress will be designated S3, and the intermediate principal stress will be designated S2. In the previous paper, attention was confined to stress combinations with two of the principal stresses equal (with the intermediate principal stress S2 equal either to S3 or S1). In this paper, consideration will also be given to the effect of stress combinations with all three principal stresses unequal. In the earlier sections of the paper (pp. 1 to 14), attention will be confined to stress combinations with

Jan 1, 1942

By George Krauss, Seth R. Thomas

One complete cycle, allstenite to martensite to aus-tenite, of Martensitic transformation was induced in a commercial 18 Cr-8 Ni stainless steel. Transmission electron microscopy showed that the reverse transfarmation, martensite to austenite, perpetuated the dense defect substructure of the martensite produced by the direct transformation, austenite to 'martensite, and reproduced the retained austenite matrix orientation. A general precipitation of lathlike M,,C, particles was noted to be present in, and is suggested as cause for, regions of martensite that Izad formed after a complete cycle of transformation. The habit plane of the precipitate particles was found to be within 5 a plane previously established as the habit of nitride precipitates of similar morphology in bcc iron. The direct transformation of austenite (y) to martensite (a) in metastable 300 series stainless steels has received considerable attention in the past,'-8 and the martensite product given special emphasis in recent years,9"*u but little information has been published about the reverse martensitic transformation during which bcc a martensite is converted to fcc y austenite."-" The reversal mechanism and the resulting crystallographic relationship between parent and product austenite are of fundamental concern. The reversal product, fully austenitic, and hereafter referred to as reversed austenite, exhibits a defect structure far different from its virgin counterpart. Some studies have been reported in which the structure of reversed austenite in iron nickel alloys is compared to annealed austenite with respect to austenite strengtheningM and Stabilization.' The martensite in these Fe-Ni alloys, however, shows a basic difference from that produced in stainless steels. Structurally, the Fe-Ni martensite is profusely twinned," while the (low-carbon) Fe-Cr-Ni martensite contains a high density of tangled dislocations and is apparently twin-free.I0 reediis" has recently shown in an Fe-16 Cr-12 Ni stainless alloy that this typical martensitic defect structure and the reverse transformation directly influence the structure of the reversal product. He found that much of the reversed austenite had returned to the orientation of the virgin austenite and that fine twins were formed in the austenite after the reverse transformation. This investigation was undertaken in order to describe as completely as possible the structural changes produced by a cycle of transformation in a typical 18-8 stainless steel. EXPERIMENTAL PROCEDURE The 301 stainless steel under investigation (17.44 Cr, 7.75 Ni, 0.80 Mn, 0.60 Si, 0.40 Mo, 0.40 Cu, 0.08 C, 0.03 N, bal Fe)was received as 0.060-in.-thick

Jan 1, 1968

By A. H. Daane, J. J. Hanak, F. H. Spedding

IN the study of the rare earths at the authors' laboratory, methods have been devised for preparing pure rare earths and many of their properties'- have been determined. Very little information is found in the literature on the properties of europium metal, which is the scarcest of the naturally occurring rare earths. Since we have recently prepared europium in appreciable quantities, we are in a position to describe the method of preparation and some of the properties of this metal. Metallic europium was first prepared by Klemm and Bommera who heated a mixture of potassium and EuC1, in vacuo, and obtained a mixture of europium metal and KC1. Trombe4 electrolyzed a molten salt bath containing NaC1, KC1 and EuC1, and collected the europium in a molten cadmium electrode as a cadmium alloy. The cadmium was subsequently removed by distillation but the properties of the residue indicate that pure europium was not obtained. McCoy attempted to prepare europium by distilling mercury from europium amalgam, but the stability of the Eu-Hg intermetallic compounds prevented a complete separation of the two elements. The preparation of very pure europium was suggested by previous work in this laboratory1,4 in which ytterbium and samarium were prepared by heating the respective sesquioxides with lanthanum metal turnings to 1450°C in vacuo and distilling ytterbium and samarium from the mixtures. Subsequently, small test experiments showed that europium also could be prepared by this method. A more detailed version of this method was used in the work described in this paper. Klemm and Bommer3 found by X-ray analysis that the metal had a body-centered cubic (bcc) structure with a lattice constant a, = 4.582 ± 0.00A (converted from kX units), with a bulk density of 5.30 g per cu cm. They found europium to be weakly ferromagnetic. Spedding, et al,7 found a,, to be 4.606 ± 0.001A. Barrett' showed that the bcc structure persists throughout the temperature range 5 to 3000K with a, at 5, 78, and 300°K being 4.551 ± 0.003, 4.551 ± 0.004 and 4.577 ± 0.001A, respectively. Trombe1 described europium as being iron gray, malleable, about as hard as neodymium and not attacked by cold water. He estimated the melting point to be between 1100 and 1200°C. Previous work in this laboratory indicated that the pure metal corrodes rapidly in air and reacts with cold

Jan 1, 1959

By G. F. Jenkins

The word asbestos is a broad term that has been accepted and applied to a number of fibrous mineral silicates found in nature. They are incombustible and can be separated by mechanical means into fibers of various lengths and thicknesses, but differ in chemical composition and other properties. It is generally recognized that there are six varieties of asbestos; the finely fibrous form of serpentine known as chrysotile, and five minerals of the amphibole group, i.e., amosite (not fully recognized as a mineral species name but accepted in asbestos terminology), anthophyllite, crocidolite, tremolite and actinolite. (Figs 1-4.) Physical and Other Properties The structures of asbestos fibers have been studied intensely in recent years. X-ray diffraction patterns 1 to 15 have been used as a means of identification and classification. The amphibole group structures have been fairly well established while the serpentine group has been the subject of many investigations during the past six years. Low-angle X-ray scattering techniques5 have shown that the chrysotile fibrils are "hexagonally close packed" and parallel to each other, having cross-sectional diameters varying from 180Å* units to 300Å units, while the amphibole fibers are many times larger in cross section. The electron micrographs of chrysotile asbestos (Figs 1-4) have also indicated that the fibrils might be in the form of a hollow tube. This point has been the subject of considerable controversy by a number of investigators.7 to 16 Density measurements17 made on a sample of high quality Arizona fiber did not indicate that the fiber had a hollow tube structure; however, the so-called "sheet structure" of the fibril could be distorted in such a way that it gives the appearance of a hollow tube in the electron microscope. It is of interest to quote one investigator, F. L. Pundsack,17 in this connection: Although the empirical composition of chrysotile is 3MgO.2SiO2.2H20, the true unit cell[#] composition is best represented as Mg12(OH)16Si8O20. This cell has dimensions of a= 5.3Å, b = 9.2 Å, and c = 14.6 Å where the "a" direction is the fiber axis. The calculated density of this unit is 2.56 g/cc, a value in close agreement with experimentally determined density values for chrysotile. The exact manner in which the unit cells of asbestos are stacked together to build up a single fiber of chrysotile is not known, but from various

Jan 1, 1960

By J.W. Halley

The effects of tin on steel have become increasingly important because of the necessity of using poorly detinned scrap, tin cans, and terne plate, in the open hearth. Since a tin can contains about 1.5 per cent tin, it would be possible to have up to 0.75 per cent tin in steel made with a 50 per cent scrap charge. In order to use tin-containing scrap, it is necessary to know the effect of tin on various grades of steel. The following investigation is by no means comprehensive but covers a number of steels in which tin content is important. Published Work A number of investigations of the effects of tin on rolling quality and physical properties have been published. It has been found that tin increases strength and hardness and reduces ductility and notched impact resistance. The decrease' in ductility and notched impact resistance becomes more marked as the carbon decreases. McKimml found no change in Olsen ductility, Kockwell hardness, yield strength, tensile strength or elongation in cold-reduced strip containing up to 0.124 per cent tin. A tin content of 0.1j per cent gave difficulties in rolling and increased the hardness but 0.21 per cent tin showed no change in properties from material containing very little tin. No explanation of this contradiction is offered. Andrew and Peile2 investigated steels containing 0.10 to 0.25 per cent carbon and up to 0.63 per cent tin. They found an increase in tensile strength of from 100 to 200 lb. per sq. in. for each 0.01 per cent tin on normalized samples. The elongation and reduction of area were decreased and the notched impact resistance was reduced markedly. Quenched and drawn samples did not show embrittling if water-quenched from the draw temperature of 1148°F. (620°C.). They could find no evidence of tin under the microscope. Whitely and Braithwaite3 investigated the effect of tin on rail steel containing 0.55 to 0.60 per cent carbon. They found that 0.08 per cent tin caused a marked decrease in elongation, notched impact resistance and the degree of bend. The tensile strength was increased in some tests and not in others. Bolsover and Barraclough4 investigated the effect of tin up to 0. 50 per cent on a 0.35 per cent carbon steel and on several alloy steels with from 0.30 to 0.40 per cent carbon. They found a comparatively uniform decrease in notched impact resistance with increasing tin on quenched and drawn samples. If the samples were quenched from the drawing temperature or reheated to the drawing temperature and quenched, the embrittling was much less severe. Steels containing molybdenum suffered much less embrittlement than other steels. Experimental WoRk Effect of Tin on Low-carbon Rimmed Steel Increasing quantities of tin were added to four ingots of a heat of the following ladle analysis: carbon, 0.08 per cent; manganese, 0.39; phosphorus, 0.009; sulphur, 0.025.

Jan 1, 1943

By R. M. Hudson

The removal of nitrogen from a nitrogenized low-carbon sheet steel that contained 0.011 wt pct N was determined during heat treatment in Hz-N, mixtures. TIze process followed a first-order rate law; that is, plots of the logarithm of nitrogen content in steel were linear with the time of treatment at a given temperature. The rate of removal increased with an increase in temperature from 900" to 1300°F. By 1400°F the rate in dry hydrogen had decreased to a value intermediate between the rates at 1200" and at 1300°F; in wet (2.47 vol pct water vapor) hydrogen the rate at 1400°F was less than the rate at 1300°F and nearly the same as the rate at 1200OF. The rate at a given temperature increased as the 3/2 power of hydrogen concentration in the atmosphere. While wet atmosplzeres were generally more effective than the corresponding dry atmosplzeres, the effect of water vapor was much less pronounced than the influence of hydrogen content. NITROGEN is the principal agent in the strain aging of ferrite, the effect of carbon being secondary.' To eliminate the return of the yield point after straining and aging, it is claimed2 that the amount of nitrogen in solution in steel must be reduced to 0.0002 wt pct. Strong nitride-forming elements (titanium, vanadium, zirconium, and aluminum) can act to eliminate strain aging by combining with nitrogen. It is extremely difficult to decrease the nitrogen content in commercial steels to the low level required by conventional coil annealing because of the poor contact between the strip surface and the reactive atmosphere. However, a variety of gas-metal reactions can be effected by use of the open-coil annealing method,3 in which the metal surface is fully exposed to the atmosphere. With this possibility in mind, the Applied Research Laboratory has studied the influence of time, temperature, and atmosphere composition on the removal of nitrogen from low-carbon sheet steel. MATERIALS AND EXPERIMENTAL WORK Samples from a commercial nitrogenized low-carbon steel (0.010 in. thick) in the cold-reduced condition were used. The chemical composition of this steel is given in Table I. The gas mixtures used are listed in Table 11. The moisture content in the "wet" annealing atmospheres was controlled at a +70°F dew point (2.47 vol pct water vapor) by passing the gas mixture through a glass tube packed with a solid mixture of 10 pct anhydrous oxalic acid and 90 pct oxalic acid dihydrate held at 127°F; this technique has been described previously.4 For "dry" atmospheres, the gas mixtures were passed through a cold trap immersed in liquid nitrogen. A hinged-top Hevi-Duty electric furnace was used with a Vycor-glass furnace tube. When the furnace was at the desired temperature, the gas mixture was passed through the furnace at a flow rate between 1.1 and 1.2 cfh; coupons (size 3 by 3/4 in.) of the steel were pulled into the center of the Vycor-glass

Jan 1, 1964