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By William R. Webster

This is a subject which our Institute has made peculiarly its own. In the first volume of its Transactions the analysis of steel received attention, and every subsequent volume has borne witness to the acuteness and industry of our members in the investigation of this subject. The keynote mas struck, in this as in so many other lines of progress, by A. L. Holley, in his paper on " Tests of Steel," read at the Easton meeting of October, 1873 (Trans., ii., 116)—an essay which may rank as a classic by reason of .its elegant form, logical force, and clear prevision of all the bearings of its theme, Taken together with the brief report of the discussion which followed it (in which Dr. Drown emphasized the effects of heat-treatment and mechanical handling, and Dr. Sterry Hunt the importance of minute variations in chemical composition, and of possible isomeric and allotropic conditions), it constitutes, after the lapse of twenty-five years, an admirable and adequate introduction to the long list of technical papers which have succeeded it. Three years later came the epoch-making papers of Dr. C. B. Dudley on the relation between the chemical composition and physical properties of steel rails, which, with the voluminous discussion they evoked, constitute a special volume, published by the Institute, and full of useful suggestions. If Dr. Dudley could be induced to resume this investigation, he would doubtless be able to solve many points still uncertain or disputed. But I cannot undertake to review the history of this subject, as represented in our Transactions—still less to restate all the contributions to it which have been made in books or in papers before other technical societies, since the initiative was taken by the Institute. My more modest purpose is to indi-

Jan 1, 1899

By W. S. Owen, T. Bell

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

Jan 1, 1968

By B. Chalmers, L. Bäckerud

The growth temperature of dendrite tips has been measured in a binary alloy system, Al-Cu, as a function of rate of formation of solid phase. Metallographic examination has rerealed the dendritic structure dereloped during different stages of the freezing process and factors influencing the undercooling, such as solute buildup, surface tension, and kinetic effects, have been estimated. Practical implications of the results are discussed. THE development of a dendritic growth pattern during the solidification of metals and alloys has an influence at least equal to that of grain size on the properties of the casting or ingot being produced. and consequently much interest has been devoted to the study of this phenomenon. A review of the knowledge gathered up to 1964 has been given by Chalmers.' Among recent publications in the area the works of Jackson et al 2 and Flemings and his coworkers3,4 are of special interest. This work is an experimental study of the factors which influence the development of a dendritic pattern during the solidification of a typical binary alloy system, A1-Cu, when there is no heat source in the liquid. This means that the temperature and the temperature gradient are controlled by the heat extraction from and latent heat evolved by the growing crystals. EXPERIMENTAL PROCEDURE Samples were prepared from a master alloy made up of aluminum, 99.995 pct, and copper. 99.99 pct, of the concentrations given below and of sufficient size to fill cylindrical graphite molds of 35 mm ID and 35 mm height. Bottom. wall. and lid of the graphite molds were all of 6 mm thickness, Fig. 1. Thin ceramic thermocouple shields could be introduced at different positions in the sample through holes in the lid. The assembly was heated in a small vertical resistance furnace to a suitable temperature. 700° to 720°C. which is well above the melting point of the sample. It was thereafter taken out of the furnace and chilled at selected rates, and the temperature changes in the sample were recorded. For high sensitivity in the temperature recordings, a reference thermocouple was held in a solidifying pure aluminum melt. which was very well insulated and therefore was at a constant temperature. 660°C, for nearly half an hour. The thermocouples were connected so that the difference voltage was fed into the recorder of which the most sensitive range was 1 mV. Temperature variations could be read to within 0.l°C. The thermocouples used were of the Chromel-Alumel type (28- or 38-gage wires) and the recorder a two-pen Moseley strip chart recorder. The different rates of chilling were obtained in the following way. a) The graphite crucible was wrapped in one or two layers of an insulating. feltlike material (Fiberfrax paper from the Carborundum Co.). The drop in temperature per unit time after complete solidification could thereby be varied from 8" to 18°C per min. This corresponds to a rate of heat extraction in the given samples from 0.08 to 0.17 cal cm-' sec-I. 6) The bare graphite mold was placed free on a piece of firebrick. The measured temperature drop was around 50°C per min (-0.5 cal cm-" ' sec- I). c) By blowing compressed air through a tube with many holes surrounding the mold in a ring shape. the rate of heat transfer could be raised to 150' to 200°C per min (-1.7 cal cm-3 sec- I). d) Cooling rates around 1000 C per mill (-9.4 cal cm-3 sec-l) were obtained by substituting the air in the device used in c by water. The range of cooling rates used in these experiments correspond to technical casting processes from slow solidification as obtained in sand molds to very rapid freezing which occurs in some continuous casting and welding processes. EXPERIMENTAL RESULTS The A1-Cu system was chosen for the experiments: the relevant part of the phase diagram is reproduced in Fig. 2. Observation of the Center Temperature. When a thermocouple is inserted in the center of the melt. the type of cooling curves obtained at slow solidification rates differs little from numerous published curves from similar systems. and the solidification pattern

Jan 1, 1970

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 T. Egleston

THE materials containing copper which are refined in the United States, are, for the most part, the native, coppers of Lake Superior. Until quite recently but little pig copper was made for sale, and that came principally from the pure sulphurous ores of New England and the South, and was generally sold to refineries not far from the ore furnaces. A small amount found its way into the market which was produced either as the by-product of the treatment of gold and silver ores, or as the result of the treatment of impure copper ores; but both these grades, on account of the impurities they contained, were looked on with suspicion, and were not sought for. All the grapes of pig copper are sold by the unit of copper contents, a great reduction being made in the price when impurities are present. There are at the present time only three works which treat native copper, the two of the Detroit and Lake Superior Copper Company, and the works of C. G. Hussey & Co., in Pittsburgh. There are a few works which smelt sulphurous ores and refine their pig; besides these there are a few small works where pig copper is refined only. Some of these purchase black copper, refine scrap, or simply refine such grades of ingot copper as are found in the market, but mostly that from Lake; Superior, for the purpose of getting it into such shapes that can be handled commercially to advantage, such as in making large plates or high grades of wire for electrical purposes. A number of such works are situated in the Naugatuek Valley and elsewhere in New England. The recent discovery, of valuable ores in Arizona makes it probable that within a few years the refining of copper in the United States will make great developments. Up to the time of the discovery of the mines on Lake Superior, only a very small quantity of native copper had ever been found, not sufficient to justify the erection of works for its special treatment. It had, besides, never been found in very Large masses, so that the discovery of great-blocks of it presented serious difficulties, not only in mining it,† but in bringing it into a merchantable condition. It seemed a very simple process to melt these large masses, * Road at the Lake Superior Meeting, August, 1880. †Transactions American Institute Mining Engineers, vol. vi, page 2S2.

Jan 1, 1881

By R. F. Domagala, M. Hansen, D. J. McPherson

Iodide zirconium was combined with calculated amounts of nitrided zirconium sponge and arc melted to prepare alloys in the 0 to 6 wt pct N region. Annealing treatments were carried out at 21 temperature levels. Metallographic examination of the heat-treated specimens permitted construction of the binary phase diagram from 0 to 6 pct N. Features of the diagram include the peritectic formation of both a and ß solid solutions. The maximum solubility of nitrogen is 0.8 pct in 8 zirconium and 4.8 pct in a zirconium. An X-ray study of nitrided materials was made in the range 6 to 13 wt pct N region because serious nitrogen losses were experienced when attempts were made to arc melt these high nitrogen alloys. PHASE relationships in the Zr-N system have been determined. Due to the inability to retain nitrogen in nitrogen-rich alloys subjected to arc melting, definitive work was possible only in the range 0 to 6 wt pct (0 to 30 atomic pct) N. Sufficient complementary X-ray work was done to permit construction of the binary phase diagram up to 13.3 wt pct (50 atomic pct) N (ZrN). Small ingots were prepared by arc melting master alloys with enough zirconium to produce an alloy of the desired composition. Following pretreatment, alloys were annealed at temperature levels between 600" and 2020°C. Determination of the phase boundaries was then accomplished by metallographic evaluation of specimens quenched from the various temperatures. Incipient melting techniques were used to corroborate solidus curves, and X-ray diffraction was employed to study the nitrogen-rich region of the a + ZrN phase field. Materials Westinghouse Grade 1 iodide zirconium crystal bar served as the base material for this investigation. The as-received bars were lightly sandblasted, pickled in a 20 pct HN0-5 pct HF aqueous solution, rinsed in water and acetone, and dried. They were rolled to about 1/32 in. strip and acid-pickled, followed by water and then acetone rinses. The material was sheared to approximately 1/4 in. squares, cleaned with acetone, and stored for use. Pure zirconium nitride is not commercially available, according to correspondence with possible suppliers. A literature survey indicated that nitrogen may be introduced into zirconium metal by passing nitrogen or ammonia gas over zirconium at an elevated temperature. After considerable experimentation, a train was devised whereby high quality nitrogen was passed through a series of bubblers to remove the last traces of oxygen, through an H,SO, bubbler and a cold trap to remove moisture, and finally over zirconium within a resistance furnace. Hand-picked Bureau of Mines magnesium-reduced zirconium sponge proved more amenable to nitriding than the crystal bar. The nitrogen used was extra pure gas purchased from Linde Air Products Co. The first two bubblers through which the gas was passed contained a solution suggested by L. F. Fieser" as being ideal for removing the last traces of oxygen from nitrogen. The solution contains 20 g KOH, 2 g sodium-anthraquinone ,9-sulphonate, and 15 g NaHSO, dissolved in 100 ml water. It is blood-red and turns brown when contaminated with oxygen. A saturated lead acetate solution, next in the series of bubblers, removed any H2S which might have formed in the 0, removal stage. An H,SO, bubbler and cold trap removed moisture before the nitrogen was passed over the zirconium. The zirconium was contained in a stainless steel screen within a Vycor or quartz tube in a resistance furnace. Unreacted nitrogen passed out of the system through a mercury bubbler. A nitriding run was performed in the following manner: Zirconium was placed in the screen within the furnace tube. The unit was assembled, suitably clamped off, and evacuated to remove the air and moisture within the tube and that trapped by the zirconium sponge. The unit was flushed with nitrogen and evacuated twice. After nitrogen was allowed to pass over the zirconium for about 30 min, the furnace was turned on; several hours were required to reach temperature. The reaction was allowed to continue at temperature for about 4 hr and the screen was then withdrawn from the hot zone of the furnace by means of a Nichrome or Kanthal rod. The screen and its contents were allowed to cool at the end of the tube and were then removed. At 800°C no more than about 5 pct N could be introduced into the sponge zirconium. This material was designated M-1 (master alloy No. 1) and reserved for the preparation of alloys in the dilute nitrogen region. A second set of experiments was conducted at 1000°C; no more than 7.2 pct N could be introduced into the zirconium at this temperature. Enough material (M-2) of this nitrogen content was prepared to produce a second set of alloys to complement the first and to provide alloys in the 0 to 6 wt pct N range. It was hoped that a diffusion anneal plus a re-nitriding might yield a material of higher nitrogen content. The material containing about 7 pct N was therefore given a homogenization treatment at 1000°C for 6 hr under an argon atmosphere. It was

Jan 1, 1957

By Henry Schaefer

Solution by electric analogy of performance problems of reservoirs containing oil and gas has heretofore depended upon a process of successive approximations based on material-balance calculations, because of variation in fluid compressibility. By the addition or subtraction of electric condenser capacity, the analogy network can be adjusted automatically for changing compressibility due to evolution of gas in the reservoir. The addition of a condenser is accomplished by an electronic circuit, which is described; subtracting a condenser is done by merely opening the electrical circuit by means of a relay. Introduction V. Paschkis and H. D. Baker1 first developed in this country a method of applying the analogy of flow of electric current in noninductive circuits to solution of heat-flow problems and suggested its application for certain other problems, such as flow of fluids or mass transfer and chemical diffusion. Necessary details for applying the analogy to flow of fluids in porous media were developed by IV. A. Bruce;= he classified3 the types of analysis and predictions that can be made by the analogy in class I, when the reservoir contains oil but no gas for the period under consideration; in Class 2, when both oil and gas exist in the free state in the reservoir sometime during the period under consideration. Duplication of bottom-hole pressure history and predictions for class I reservoirs can be obtained directly by electric analogy. Until now, the solution of problems pertaining to reservoirs in class 2 was obtained by successive approximations along with material-balance calculations. The object of this paper is to present a method for simplifying the application of electric analogy to class 2 reservoirs, resulting in a solution of these problems as direct as is possible for class I reservoirs. This is accomplished by an electronic control circuit, which adjusts the analogy network for changing compressibilities of fluids contained in the reservoirs. Analogy Network In electrical phenomena the analogy to two-dimensional fluid flow in a porous media is that of current flow through an ideal conducting sheet. This sheet, perfectly insulated on both sides, has resistance and capacitance uniformly distributed throughout its area but is of negligible inductance. The need for having the surface boundaries perfectly insulated is that good correspondence may be had with a permeable fluid-conducting stratum bounded above and below by impermeable media. 111 actual application the ideal conducting sheet, which has distributed parameters, is replaced by a network having lumped values of resistance and capacitance—the resistances are series elements and the capacitances are shunt elements. The larger the number of lumped

Jan 1, 1947

By Henry Schaefer

Solution by electric analogy of performance problems of reservoirs containing oil and gas has heretofore depended upon a process of successive approximations based on material-balance calculations, because of variation in fluid compressibility. By the addition or subtraction of electric condenser capacity, the analogy network can be adjusted automatically for changing compressibility due to evolution of gas in the reservoir. The addition of a condenser is accomplished by an electronic circuit, which is described; subtracting a condenser is done by merely opening the electrical circuit by means of a relay. Introduction V. Paschkis and H. D. Baker1 first developed in this country a method of applying the analogy of flow of electric current in noninductive circuits to solution of heat-flow problems and suggested its application for certain other problems, such as flow of fluids or mass transfer and chemical diffusion. Necessary details for applying the analogy to flow of fluids in porous media were developed by IV. A. Bruce;= he classified3 the types of analysis and predictions that can be made by the analogy in class I, when the reservoir contains oil but no gas for the period under consideration; in Class 2, when both oil and gas exist in the free state in the reservoir sometime during the period under consideration. Duplication of bottom-hole pressure history and predictions for class I reservoirs can be obtained directly by electric analogy. Until now, the solution of problems pertaining to reservoirs in class 2 was obtained by successive approximations along with material-balance calculations. The object of this paper is to present a method for simplifying the application of electric analogy to class 2 reservoirs, resulting in a solution of these problems as direct as is possible for class I reservoirs. This is accomplished by an electronic control circuit, which adjusts the analogy network for changing compressibilities of fluids contained in the reservoirs. Analogy Network In electrical phenomena the analogy to two-dimensional fluid flow in a porous media is that of current flow through an ideal conducting sheet. This sheet, perfectly insulated on both sides, has resistance and capacitance uniformly distributed throughout its area but is of negligible inductance. The need for having the surface boundaries perfectly insulated is that good correspondence may be had with a permeable fluid-conducting stratum bounded above and below by impermeable media. 111 actual application the ideal conducting sheet, which has distributed parameters, is replaced by a network having lumped values of resistance and capacitance—the resistances are series elements and the capacitances are shunt elements. The larger the number of lumped

Jan 1, 1947

By F. E. Werner, B. L. Averbach, Morris Cohen

THAT bainite formed near the M, temperature bears a striking r esemblance to martensite tempered at the same temperature has been shown by the electron microscope.' By means of electron diffraction,' it has been established that carbide and cementite are present in bainite formed at 500°F (260°C); these carbides are also found in martensite tempered at 500°F (260°C).' The investigation reported here is concerned with an X-ray study of the matrix phases in lower bainite and tempered martensite. These phases have turned out to be dissimilar in structure; the matrix of bainite is body-centered-cubic while that of tempered martensite is body-centered-tetragonal. A vacuum-melted Fe-C alloy containing 1.43 pct C was studied. Specimens of 16 in. diam were sealed in evacuated silica tubing and austenitized at 2300°F (1260°C) for 24 hr. One specimen was quenched into a salt bath at 410°+7 °F (210°+4°C), held for 16 hr, and cooled to room temperature. The structure consisted of about 90 to 95 pct bainite, the re: mainder being martensite and retained austenite. A second specimen was quenched from the austen-itizing temperature into iced brine and then into liquid nitrogen. It consisted of about 90 pct martensite and 10 pct retained austenite. The latter specimen was tempered for 10 hr at 410°+2°F (210°+1°C). The specimens were then fractured along prior austenite grain boundaries (grain size about 2 mm diam) by light tapping with a hammer. Single aus-tenite grains, mostly transformed, were etched to about 0.5 mm diam and mounted in a Unicam single crystal goniometer, which allowed both rotation and oscillation of the sample. Lattice parameters were measured by the technique of Kurdjumov and Lyssak. This method takes advantage of the fact that martensite and lower bainite are related to austenite by the Kurdjumov-sachs orientation relationships Thus, the (002) and the (200) (020) reflections can be recorded separately, permitting the c and a parameters to be determined without interference from overlapping reflections. According to these findings, the matrix phase in bainite is body-centered-cubic and, within experimental error, has the same lattice parameter as ferrite (2.866A). On the other hand, martensite, tempered as above, retains some tetragonality, with a c/a ratio of 1.005t0.002. Most workers in the past have assumed that bainite is generated from austenite as a supersaturated phase, but the nature of this product has not been established. The question arises as to whether bainite initially has a tetragonal structure and then tempers to cubic, or if it forms directly as a cubic structure. If it forms with a tetragonal lattice, it might well be expected to temper to the cubic phase at about the same rate as tetragonal martensite. The martensitic specimen used here was given approximately the same tempering exposure, 10 hr at 410°F, as suffered by the greater part of the bainite during the isothermal transformation. About 50 pct bainite was formed in 6 hr at 410°F. On tempering at this temperature, martensite reduces its tetragonality within a few minutes to a value corresponding to 0.30 pct C.' Further decomposition proceeds slowly, and after 10 hr the c/a ratio is still appreciable, i.e., 1.005. Thus, even if the bainite were to form as a tetragonal phase with a tetragonality corresponding to only 0.30 pct C, which might be assumed to coexist with e carbide, it would not be expected to become cubic in this time. It seems very likely, therefore, that bainite forms irom austenite as a body-centered-cubic phase and does not pass through a tetragonal transition. The carbon content of the cubic phase has not been determined, but it could easily be as high as 0.1 pct, within the experimental uncertainty of the lattice-parameter measurements. It has been postulated that retained austenite decomposes on tempering into the same product as martensite tempered at the same temperature. There is now considerable doubt on this point. The isothermal transformation product of both primary and retained austenite at the temperature in question here is bainite," and the present findings show that bainite and tempered martensite do not have the same matrix. Acknowledgments The authors would like to acknowledge the financial support of the Instrumentation Laboratory, Massachusetts Institute of Technology, and the United States Air Force.

Jan 1, 1957

By L. H. Levenson, Charles S. Barrett

Plastic flow in metal crystals and the changes in orientation resulting from it are generally understood to take place by the following fundamental mechanisms: (1) slip on crystallographic planes, (2) homogeneous crystal rotation resulting from the slip, (3) bending of the 1attice between the planes of slip, and, under certain circumstances, (4) twinning. This paper and a preceding one on iron subjected to uniaxial compression1 concern two additional processes that must now be added to this list: (5) the formation of deformation bands, and (6) the bending and rotation of these bands. The present investigation yields a new understanding and definiteness to the common terms so loosely used when speaking of cold-worked metals —('grain fragmentation," "elongated grains," and "deformation twins," "deformation bands," "etch bands," or "X-bands." Bands have been noted on the polished and etched surfaces of cold-worked metals by various investigators for more than 25 years, ‡ yet their nature and their significance have been so little understood that they are not treated in the most comprehensive modern texts on the deformation of crystals. The experiments in this series show that they are one of the fundamental processes in the deformation of metals, of importance in the development of preferred orientations, in work-hardening (since they have the effect of reducing the effective grain size and interfering with slip), and in the recrystallization process. The present experiments were performed on the same stock of material that was used in the earlier compression experiments1—hydrogen-purified mild steel in which the carbon content had been reduced to the limit detectable under the microscope and in which single crystals could be grown by a strain-anneal treatment.2

Jan 1, 1939

By Charles S. Barrett, L. H. Levenson

Plastic flow in metal crystals and the changes in orientation resulting from it are generally understood to take place by the following fundamental mechanisms: (1) slip on crystallographic planes, (2) homogeneous crystal rotation resulting from the slip, (3) bending of the 1attice between the planes of slip, and, under certain circumstances, (4) twinning. This paper and a preceding one on iron subjected to uniaxial compression1 concern two additional processes that must now be added to this list: (5) the formation of deformation bands, and (6) the bending and rotation of these bands. The present investigation yields a new understanding and definiteness to the common terms so loosely used when speaking of cold-worked metals —('grain fragmentation," "elongated grains," and "deformation twins," "deformation bands," "etch bands," or "X-bands." Bands have been noted on the polished and etched surfaces of cold-worked metals by various investigators for more than 25 years, ‡ yet their nature and their significance have been so little understood that they are not treated in the most comprehensive modern texts on the deformation of crystals. The experiments in this series show that they are one of the fundamental processes in the deformation of metals, of importance in the development of preferred orientations, in work-hardening (since they have the effect of reducing the effective grain size and interfering with slip), and in the recrystallization process. The present experiments were performed on the same stock of material that was used in the earlier compression experiments1—hydrogen-purified mild steel in which the carbon content had been reduced to the limit detectable under the microscope and in which single crystals could be grown by a strain-anneal treatment.2

Jan 1, 1939

By Irving B. Cadoff, Stojan M. Zalar

AgInTe2, CuInTe2, and all Proportions of CuxAg1-xInTe, forMed homogeneous single phase alloys after direct solidification from the nielt. X-ray analysis indicated a zinc-blel~de strzccture typical of the chalcopyrite compounds, and the electrical resistivity and Sccbeck coefficient values were in the semiconducting range. AuInTe, and AuxA4g,-, InTe, formed by what appeared to be a peritectic reaction (the thermal analysis curves showing more than one arrest) and were conseyue~ztly polyphase. Substitution of copper into AgIrzTe, resulted in a continuous transition in the room tenzperature Seebeck coefficient from the negative AgIzTe, to the positive CuInTe,. A zero coefficient was obtained at about Cuo.55 Ago.45 InTe, . The temperatzire variation was similar to that observed for the stoichiometric compounds, that zs, tendency towards "p" concEuction at elevated temperatures. The thernzoelectric figure of merit for the compo~uzds, as determined by the Putley -Harmnn method were in the range 10- to 10-7 "K-l; the thermal conductivities in the order of 0.15 cal per sec-cm-oK. INCREASED interest in semiconducting intermetallic substances is expanding much of recent research from simple binary compounds into polyatomic systems and solid solutions. Ternary compounds A' represent a covalent extension of the binary semiconductors Within the a tin isoelec-tronic series, Ag-Cd-In-Sn-Sb-Te-I, divalent cadmium atoms in CdTe are being substituted for by monovalent silver and trivalent indium atoms to form the compound AgInTe, . By cross-substitution with elements of other isoelectronic series, a great number of ternary compounds A 'B"'c? is possible. In all of them, however, a necessary though not sufficient condition for the covalent, semiconducting bond—that there be four sharing orbital electrons per atom—must be fulfilled. In AgInTe,, each silver or indium atom is tetrahedrally surrounded by four tellurium atoms, while each tellurium atom is co-valently bound to two silver and two indium atoms. Synthetic chalcopyrites A'B"'c~ were first recognized as potential semiconduct&rs by Goodman and Douglas.' Austin, Goodman, and Pengelly discuss preparation difficulties and some electronic measurements on AgInS, , AgInSe, CuInSe, , AgInTe, , and CuInTe,. Chalcopyrites A B c2v are mentioned in papers attempting to classify and predict semiconducting behavior of intermetallic compounds; on the basis of saturated tetrahedral sp3 bonds,3 by specific selection criteria,' and by crystallographic considerations."

Jan 1, 1962

By H. Hansen, A. U. Seybolt, P. Yurcisin, B. W. Roberts

The Bi-Mn phase diagram in the region near BiMn was investigated, using principally thermal analysis and changes in magnetization with temperature. Of chief interest are the findings related to the magnetic transformation in Bi-Mn. THE Bi-Mn system is of both theoretical and practical interest because of the occurrence of the compound BiMn which exhibits unusual ferromagnetic properties. Because the Bi-Mn phase diagram reviewed by Hansen' (see Fig. 1) in 1936 is based on work done by BekierY in 1914 and by Siebe" in 1919, which left considerable doubt about the nature of the diagram. it appeared desirable as an aid in understanding the alloying characteristics and magnetic behavior to examine the pertinent regions of the phase diagram. The most interesting reaction is the peritectic at 445°C which forms BiMn by the reaction: Liquid + Mn(sulfield) ? BiMn(sol field) There is also a eutectic at 262° C between pure bismuth and BiMn. Hansen draws in BiMn dotted, since in 1936 evidence for its existence was uncertain. Experimental Materials—Preparation of Alloys Electrolytic manganese of about 99.97 pet purity and bismuth of 99.99 + pet purity were used as starting materials.

Jan 1, 1957

Jan 1, 1904

By E. A. Gulbransen, J. W. Hickman

IN a previous paper1 the authors have investigated the structure of the oxide films formed on most of the metals that make up the alloys of this study. The metals were studied in order to provide basic information on the structures, both physical and chemical, of the oxide films and to determine how these structures are effected by the temperature, time of oxidation, and surface preparation. It was felt that an understanding of the physical and chemical structure as well as the stability of the oxide film might furnish clues as to the nature of the reaction process and the protective quality of the film. The oxidation of the metals was studied over the temperature range 300° to 700°C. except for copper, where the range selected was 100° to 500°C. The results of these studies were presented in graphical form as existence diagram, of the oxides on a time-temperature scale. For some of the metals the existence diagrams were simple and showed few chemical transitions, but there were numerous cases where the physical state of the oxide surface was a function of time and temperature. In general the physical state of the oxide surface changed with increasing temperature so as to increase the sharpness of the diffraction patterns and to cause orientation effects to be more pronounced. Deviations in lattice parameters from X-ray values were noted. In general these deviations were of positive nature and may be due to solid solution of the metal in the oxide lattice. This effect might be expected in thin oxide films. In a study of the oxidation of alloys containing two or more metals, there may arise the complicating factor of identification of the oxides formed. A thorough understanding of the oxides formed on the pure metals, therefore, was, essential before investigation of the oxidation of alloys. In this paper it is our purpose to present a study of the following problems: I The existence diagrams of various alloys. [2.] The effect of the structure of the [ying] metal on the existence diagram of Iron. 3. The effect of the percentage of chromium on the oxides formed on Fe-Cr alloys. 4. The relationships, if any, between the oxides formed and the protective quality of the oxides. The following alloys are included in this study: alloys of iron with body- centered cubic, face-centered cubic and other metals, 13 Cr-Fe, 18-8 stainless steel, K42B1 Nichrome V, Hipernik, Inconel, Stellite " 21," Refractaloy, Kovar, mild steel, a series of Cr-Fe alloys and a series of Co-Fe alloys. Since many of the commercial alloys in this list contain more than two metals, various complicating factors in the identification of the oxides formed may arise.

Jan 1, 1946

By Ernest Burchard

A RECONAISSANCE of the chrome and manganese'1ore deposits of Culm was made in the spring of 191s by Albert Burch representative of the U. S. Bureau of Mines and the writer representing the U. S. Geological Survey. The object of the study was to obtain authentic information for use of the: United States Government as to the location, character, size, and availability of the Cuban deposits of the ores of these important steel-alloy metals. The Cuban Government courteously detailed Sr. E. I. Montoulieu, a mining engineer connected with the Treasury Department, to act as escort and associate throughout the work on the Island. Mr. George A. Wright, of Baracoa, Cuba, a mining engineer especially familiar with the chromite deposits of Oriente Province, was a member of the party from Feb. 25 to Mar. 20. It was possible to visit most of, the chrome-ore deposits that seemed to be of promise, but there was not sufficient time to visit all that were brought to our attention, some of which may have merit. Furthermore, no attempt was made to examine the extensive chromiferous iron-ore deposits of the Mayari, Moa, and Cubitas districts, as these deposits cannot be regarded as sources of chromium except indirectly. At the close of the field work the essential data concerning the quantity and quality of ore probably available for shipment during 1918 and 1919, in the event of the continuation of the European war, and of the tonnage of ore in reserve, were furnished to such Government bureaus as were interested, including the Shipping Board and the War Industries Board, and as soon as chemical analyses of the chrome ores could .be obtained, a press bulletin on the subject was published by the Geological Survey. In the present paper the engineering data, and tonnage estimates contained in the unpublished notes of Mr. Burch have been freely used, and their helpfulness is hereby gratefully acknowledged. Many thanks are due Senor Montoulieu and Mr. Wright for their valuable work in the field; to the officials of the Spanish American Iron Co. and of the various other companies; and to individuals holding chromite claims, for courteously facilitating the work of the party. In the study of material for the present paper, chemical analyses have been made by R. C. Wells and petrographic determinations and descriptions were furnished by Miss E. F. Bliss, both of the U. S. Geological Survey.

Jan 9, 1919

By R. W. Kraft, L. D. Graham

The process of' spheroidization, or more properly coarsening, of Al-CuAl,eutectic alloy specimens with various initial microstructures was studied by quantitative metallographic and X-ray diffraction techniques. By measuring the rale at which specimens with a very fine dispersion of phases (produced by quenching molten droplets of the alloy in water) coarsened it uias determined that the rate-controlling mechanism for coarsening was diffusion, probably of aluminum in the aluminum-rich phase. The lamellae in specimens with a high degree of microstructural and cr-ystallog/uphic anisotropy (produced hy unidirectional solidification of ingots) thickened during heat treatment by recession of the CuAl, platelets from jaulted regzons, yet the specinlens retained a very high degree of. anisotropy after prolonged heat treatments at a temperature within 8°C of the eutectic temperature. In such specimens the crystallographic orientation relationship between the phases remained constant and no change in the crystallographic substructure occurred. Based on these observations a model was developed for the coarsening—or rate of' thicken-ing—oj- the lamellar structures which predicts that the rate of decrease of interface area is proportional to the square of lamellar interface area. Experiments with degenerate and very coarse lamellar microstruc -tures preduced by extremely slow unidirectional solidification) indicate that initial microstructure is a most important factor governing the final micro-structure after heat treatment. The particle size and shape of dispersed phases are important parameters affecting the properties of a wide variety of two-phase materials. As is well-known, varietythe dispersed-phase particles tend to coarsen at appropriately high temperatures because the interface energy of the system is reduced by the concomitant reduction in interface area. The phenomenon of

Jan 1, 1967

By John J. Egan, A. B. Kinzel, Walter Crafts

The demands of the petroleum and chemical industries for steels to be used in pressure vessels and similar structures at artificially low temperatures are continually increasing, and the writing of proper specifications with suitable tests becomes increasingly important. Likewise, the selection of suitable steels for such applications is of increasing concern to the metallurgist. It is generally recognized that highly alloyed steels of the austenitic stainless type retain their properties even at very low temperatures and represent the best technological solution of the low-temperature steel problem. However, in many instances less expensive carbon or low-alloy steels suitable for service within limited temperature ranges are available. The problem thus becomes one of defining the various factors involved in the production and fabrication of these less expensive steels and determining the temperature ranges in which their properties justify engineering application. Most of the applications involve welded structures, and the heat effect of welding as well as the nature of the weld metal are matters of prime concern. The first problem that the metallurgist faces is the determination of the type of test to be used as a criterion of the performance of the steel in low-temperature service. It has been generally recognized that the static properties of steel as determined in the ordinary tensile test undergo a gradual and relatively slight change as the temperature of test is lowered in the range of current interest; i.e., from room temperature to minus 120' C. It is further generally recognized that the behavior of steel under impact involving notch sensitivity is definitely affected at the lower temperatures. While the major subject of this paper is the effect of grain-refining deoxidizers, of low-alloy additions and of welding on the low-temperature notched-bar impact properties, an inquiry into the general behavior of steel under low-temperature impact testing is included. This is a pertinent portion of the investigation and the results thereof are

Jan 1, 1937

By Edwin R. Phelps, Charles W. Porterfield

BACKGROUND OF SURFACE MINING Surface mining refers to the process of removing the material (over- burden) overlying a coal seam and exposing the coal so that it can be loaded out and conveyed by trucks or other methods to the preparation plant or other facility. Surface mining has not always been important in the coal industry. In the early 1900s, almost all of the coal mined in the United States was mined by underground methods. In 1900, about 192 Mt (212 million st) of bituminous coal mere mined and less than 1% was mined by surface methods. The development and use of larger equipment has allowed surface mining to gain prominence throughout the years. Table 1 shows the total production of coal by mining method in the United States for ten-pear periods since 1920 and indicates the growth of surface-mined coal production. Surface mining will undoubtedly continue to account for a large percentage of the coal production in the US for many years because: 1) The capacity of surface mining excavators has continued to increase. Today, mining companies are using shovels (see Fig. 1) which are able to move up to 137.6 m3 (180 cu pd) in each bite and draglines (see Fig. 2) which move up to 168.2 m3 (220 cu pd) in each bucketful. 2) Increasing tonnage from the thick western coal seams is being produced by surface mining methods. 3) Surface mining has normally had lower costs and a better safety record than underground mining. 4) Surface mining normally recovers a much higher percentage of the coal reserve than can recovered by underground mining. 5) Some coal measures call best be extracted by surface mining

Jan 1, 1981

By Robert T. Howard, Morris Cohen

THE purpose of this paper is to direct attention to the lower part of the austenite transformation diagram, or TTT curves, where considerable uncertainty still exists as to the blending of the bainite and martensite reactions. The dissimilarities between these two low temperature trans- formations have been summarized recently by Troiano and Greninger.1 Of particular importance to the present work is the fact that martensite formation, unlike bainite formation, is not suppressed by the fastest quenching rates attainable. However, most of the investigations in this direction have been concerned primarily with the start of the martensite transformation [(M,)] during cooling, rather than with the quantitative aspects of the subsequent reaction on either further cooling or isothermal holding. Several years ago, Cohen2 suggested a form of transformation diagram which reconciled, at least schematically, the isothermal characteristics of the bainite transformation with the insuppressible nature of the martensite transfoi mation. In essence, the diagram consisted of a family of horizontal lines (representing the progress of the austenite-martensite reaction during quenching) which were interrupted in point of time by the bainite family of C-curves extending down from higher temperatures. This picture received later support by metallographic3 and dilatmetric4,5 studies, but the techniques employed were not sufficiently critical to substantiate some of the details. Elmendorf6 and Grange and Steward7 have shown that the Greninger-Troiano metallographic techniques may be used not only for [M,] determinations, but for studying the course of further austenite decomposition. In fact, the latter investigators have observed the amount of martensite formed as a function of temperature below [M,] in fourteen commercial steels. In the present paper, the Greninger- Troiano technique has been combined with the lineal method of Howard and Cohen9 to provide a unique, quantitative treatment of the austenite-martensite reaction. Furthermore, isothermal transformations have been similarly measured on holding at temperatures above and below M,, thus permitting a fairly detailed presentation of the lower part of the conventional austenite transformation diagram. EXPERIMENTAL DETAILS Materials The steels, listed in Table I, were selected for study because they exhibit a satisfactory range of M, temperatures and have not received as much attention as the lower carbon grades. They were prepared as 30 lb induction furnace heats in the laboratories of the Vanadium-Alloys

Jan 1, 1947