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By Fred L. Morritz, Harold M. Manasevit, Richard Nolder, Arnold Miller

Experimental evidence is presented which confirnis the epitaxial relationship between the deposited silicon and the sapphire substrate. Four distinct modes of orientation relationships have been established. These have been shown to be Single-crystal gvowth retention as a function of surfaces oriented off ideal has been qualitatively indicated. Both full-circle goniometer X-ray techniques and replica electron microscopy have indicated varying amounts of microtwinning in the silicon. film, which may he caused by the mode of silicon formation. Parameters have been found where twin density is less than I pct. The early stages of' epitaxy of silicon m sapphire have been examined by electron-microscope techniques... and mechanisms have been proposed. THE first report of the deposition of single-crystal silicon on sapphire (single-crystal aluminum oxide) was made at the American Physical Society Meeting in Canada' by one of us and was subsequently published in the Journal of Applied physics.* This paper summarizes some of the work carried on in this area since that time, in addition to reviewing some of our earlier observations. The initial single-crystal deposits of silicon on sapphire reported were obtained on sapphire planes produced by cutting a sapphire rod perpendicular to its fastest growth direction, which is approximately 60 deg from the C axis. Direct correlations between the microstructure and X-ray data as to the single crystallinity as shown in Fig. 1 are evident. These deposits were identified as (111) silicon on the substrate oriented near the (1123) of sapphire. (Sapphire notations are designated according to the c over a ratio of 2.73.) It became evident that substrate quality and surface play an important part in successful epitaxy. For example, in Fig. 2 we observe an interesting

Jan 1, 1965

By J. W. Freeman, J. P. Rowe, R. F. Decker

HEAT-to-heat variations in properties of an alloy of constant nominal chemical composition have been a perplexing problem to the metallurgist. These heat-to-heat differences have been especially baffling in high-temperature metallurgy. In order to establish fundamental reasons for these heat-to-heat variations, the National Advisory Committee for Aeronautics has sponsored and financially assisted an extended research program on heat-resistant alloys at the University of Michigan. As part of the program to find the contribution of processing variables, Frey, Freeman, and white' studied effects of heat treating on nickel-base alloys and Ewing and reeman' investigated effects of hot-working practice on N155 alloy. To extend the program to the study of effects of melting practice on high-temperature properties, a 55 Ni-20 Cr-15 Co-4 Mo-3 Ti-3 pct A1 composition was selected for experimentation. The objective of this program was to establish the melting-practice variables which influenced the hot-working characteristics and creep-rupture properties and, at the same time, establish the metallurgical mechanisms for the effects. During the course of the investigation of practices using vacuum melting, it became increasingly evident through chemical analyses supplied by industrial concerns that a major variable was melt reaction with the crucible. This paper is devoted to the results of this phase of the melting-practice study. EXPERIMENTAL PROCEDURES Experimental 10-lb heats were induction melted in the University of Michigan vacuum-melting unit with the melting practices outlined in Table I. Aim analysis for the basic alloy, in wt pct, for all heats was as follows: Cr Co Mo Ti Al 20.0 15.0 4.0 3.1 3.1 Mn Si C Ni 0.12 0.12 0.08-0.15 Bal. Small amounts of boron and zirconium were added to certain heats as listed in Table I. These additions

Jan 1, 1959

By R. S. Dean

The commercial production of electrolytic manganese on a small scale commenced in 1939. The writer made a short report on the progress of production and utilization in Mining and Metallurgy for January 1941. Progress during the last two years, naturally, has been more rapid. In June 1940, Congressman (now Senator) Scrugham presented a proposal to Congress for an appropriation authorizing erection of a pilot plant for " the production of metallic manganese by electrolytic or other means." As a result of this, a pilot plant, having a capacity of a few hundred pounds per day was built at Boulder City, Nev. Subsequent appropriations permitted expansion of the plant to about a ton per day. Much has been learned in this plant about electrolytic manganese, and the product even in its small way has found war uses of considerable importance. Meanwhile, the Knoxville plant of the Electro Manganese Corporation, the sole commercial producer, was expanded to about 4 tons per day to supply needed material for the war program. Other proposals for commercial plants have not been favorably received by the War Production Board. The Bureau reported on one such proposal by the American Alloys and Chemical Corporation. Practice at BouldeR City The present practice, as carried out at Boulder City, which is being described in more detail in a current paper by the Bureau staff at Boulder City, starts with a manganese dioxide ore containing about 20 per cent manganese. Currently this ore comes from the Three Kids deposit near Las Vegas. The steps for the production of electrolytic manganese, in general, are as follows: 1. The manganese in the ore is reduced to MnO. 2. The MnO is dissolved from the ore in spent electrolyte, which contains about 38 to 47 grams per liter of free sulphuric acid, 135 grams per liter of ammonium sulphate, and 10 to 12 grams per liter of Mn as sulphate. In the leaching step the manganese is built back up to 32 to 36 grams per liter of Mn as sulphate; the pH is adjusted to neutral by means of gaseous ammonia and passed through thickeners. 3. The electrolyte is purified by adding H2S, which precipitates the heavy metals. After filtering, ferrous sulphate is added to the solution and oxidized with air and the solution is filtered and clarified on a precoat filter. 4. The purified catholyte is electrolyzed in a diaphragm cell using stainless-steel cathodes and lead-silver anodes. The current density is about 45 amp. per sq. ft. Current efficiencies of 60 to 65 per cent are regularly obtained.

Jan 1, 1944

By R. S. Dean

The commercial production of electrolytic manganese on a small scale commenced in 1939. The writer made a short report on the progress of production and utilization in Mining and Metallurgy for January 1941. Progress during the last two years, naturally, has been more rapid. In June 1940, Congressman (now Senator) Scrugham presented a proposal to Congress for an appropriation authorizing erection of a pilot plant for " the production of metallic manganese by electrolytic or other means." As a result of this, a pilot plant, having a capacity of a few hundred pounds per day was built at Boulder City, Nev. Subsequent appropriations permitted expansion of the plant to about a ton per day. Much has been learned in this plant about electrolytic manganese, and the product even in its small way has found war uses of considerable importance. Meanwhile, the Knoxville plant of the Electro Manganese Corporation, the sole commercial producer, was expanded to about 4 tons per day to supply needed material for the war program. Other proposals for commercial plants have not been favorably received by the War Production Board. The Bureau reported on one such proposal by the American Alloys and Chemical Corporation. Practice at BouldeR City The present practice, as carried out at Boulder City, which is being described in more detail in a current paper by the Bureau staff at Boulder City, starts with a manganese dioxide ore containing about 20 per cent manganese. Currently this ore comes from the Three Kids deposit near Las Vegas. The steps for the production of electrolytic manganese, in general, are as follows: 1. The manganese in the ore is reduced to MnO. 2. The MnO is dissolved from the ore in spent electrolyte, which contains about 38 to 47 grams per liter of free sulphuric acid, 135 grams per liter of ammonium sulphate, and 10 to 12 grams per liter of Mn as sulphate. In the leaching step the manganese is built back up to 32 to 36 grams per liter of Mn as sulphate; the pH is adjusted to neutral by means of gaseous ammonia and passed through thickeners. 3. The electrolyte is purified by adding H2S, which precipitates the heavy metals. After filtering, ferrous sulphate is added to the solution and oxidized with air and the solution is filtered and clarified on a precoat filter. 4. The purified catholyte is electrolyzed in a diaphragm cell using stainless-steel cathodes and lead-silver anodes. The current density is about 45 amp. per sq. ft. Current efficiencies of 60 to 65 per cent are regularly obtained.

Jan 1, 1944

By K. K. Clark, W. H. Somerton

The feasibility of reducing pressures needed to fracture formations by heating the borehole intensively has been investigated on a laboratory scale. Reductions in fracture pressures of heated Bandera, Berea and Boise sandstone cores were observed at various confining pressures, simulating reservoir stress conditions to a depth of 5,000 ft. Both permeable and impermeable borehole boundary conditions were tested. Three heating conditions were used in the tests. One group of samples was heated in a furnace to a temperature of 600C, cooled to room temperature., and then tested for fracture pressures. Two other groups of samples were heated with a borehole heater to maximum borehole wall temperatures of 625 and 792C, then cooled and tested. In all cases, heated samples showed substantial reductions in fracture pressures compared to unheated samples. The higher temperature borehole heated samples showed the greatest reduction, amounting to 70 per cent in the extreme case. In actual application to wells, it was concluded that fracture pressures may be reduced by 20 to 50 per cent by intensive borehole heating before fracturing. INTRODUCTION Hydraulic fracturing of oil and gas wells is an accepted and effective technique for increasing well productivity in many areas, but is notoriously unsuccessful in other areas. The technique becomes less interesting for production stimulation purposes when excessive fracture pressures are necessary. Formations which do fracture but require high pressures, probably form horizontal fractures. There is good evidence to indicate that some formations do not fracture at all, but yield plastically under high pressure. Thus, any technique which will make formations easier to fracture or will reduce fracture pressures is potentially interesting to petroleum producers. Horizontal fractures generally occur in planes of weakness, such as bedding planes, and at pressures equaling or exceeding the effective overburden stress. In the unusual case where planes of weakness do not exist, a slightly higher pressure must be applied to overcome the tensile strength of the rock. In general, high fluid-loss fracturing fluids are conducive to the formation of horizontal fractures.1 Vertical fractures, when they do occur, are initiated at pressures generally lower than overburden pressure and are favored by low fluid-loss fracturing fluids or impermeable boreholes. The pressure necessary to create a vertical fracture in an impermeable, elastic medium can be predicted from the so-called "thick-walled cylinder" equation: Pf = 2 or+ st.............(1) where pf = fracture pressure or = radial stress st = tensile strength of medium. This equation indicates that to fracture it is necessary to overcome a tangential compressive stress, induced by and equal to two times the radial confining stress, plus the tensile strength of the medium. If the above equation held strictly true for rocks, very little could be done to reduce fracture pressure. The tensile strength of the rock might be reduced somewhat, but any change in st would be small compared to the magnitude of the tangential stress at reasonable subsurface depths. Laboratory tests have shown that actual fracture pressures exceed values predicted from Eq. 1 by factors of 1.4 to 28.6.1,2 Eq. 1 thus does not properly describe the

Jan 1, 1966

By Frank M. Monroe, James R. Cost

The solubility of nitrogen in vanadium is determined from 275" to 575°C by measuring the height of the nitrogen internal friction peak of equilibrated V-N alloys. The proportionality constant at 275°C between the internal friction peak height (Q- 1) and the atom percent nitrogen in solution is found to be 0.095 per at. pct for nitrogen concentrations up to 0.8 at. pct. The heat of solution of the nitride in vanadium is 5500 cal per mole. The solubility of nitrogen in the Group V metals is discussed. LITTLE work has been performed on the vanadium-nitrogen terminal solid solution. Hahn1 found the solubility for nitrogen to be very small and reported the existence of a hexagonal phase of composition near that of V2N at the solubility limit. Rostoker and Yamarnoto2 reported the solubility to be at least 3.5 at. pct at the melting point and to be less than this value at 900°C. In addition, they reported from X-ray diffraction studies that nitrogen in solution produces tetragonality in the vanadium lattice. An X-ray study by Schonberg3 has confirmed the results of Hahn but indicated that the tetragonality observed by Rostoker and Yamamoto was due to the presence of oxygen in their specimens. Beatty4 has performed lattice parameter and hardness measurements on terminal solid solutions and found the upper limit of the solubility to be at least 0.66 at. pct N. No measurements have been made of the pressure-temperature-composition relationships (P-T-X) for the terminal solid solution. As a part of a research program on gas-metal equilibrium, an attempt was made to study the P-T-X relationships in the V-N system using both the internal friction and the gas equilibration methods which have been successful with the Nb(Cb)-N and Ta-N systems (see Ref. 5 for a review of this work). Extensive investigation, using the gas equilibration methods, showed this method not to be applicable with vanadium This was presumably due to the gettering action of vanadium sublimed on the walls of the Sieverts apparatus. Thus, the nitrogen pressure relationships with temperature and composition were not obtained. The internal friction methods were, however, found to be applicable, and the temperature-composition relationships are reported in this paper and compared with similar results for the Nb-N6 and Ta-N7 systems. The existence of a Snoek internal friction peak due to nitrogen in solution in vanadium has been clearly demonstrated. 8-10 Powers and Doyle found the peak to be at approximately 275°C for frequencies near 1 cps.8 In a subsequent paper10 they reported the proportionality constant at 275°C between the internal friction peak height (Q-1) and the concentration of ni- trogen in solution (in atom percent) as 0.06 per at. pct. The studies of Stanley and wert9 indicated qualitatively that the height of the Snoek peak decreased with aging at the peak temperature and thus suggested that internal friction methods were suitable for study of the solubility. EXPERIMENTAL METHOD The vanadium for this investigation was of particularly high purity. It was obtained from the Ames Laboratory of the U.S. Atomic Energy Commission, Ames, Iowa in the form of a 1/2-in. diam, three pass zone-refined ingot. The electrical resistivity ratio (p300ºk/p4ºk) was 160. The initial composition was determined as follows: Carbon 200 ppm Oxygen 150 ppm Chromium <50 pprn Iron 125 ppm Silicon <50 ppm Other metallic 100 pprn The initial vanadium ingot was fabricated to 30-mil wire by swaging and wire drawing without the need of intermediate annealing. Lengths of this wire were then further purified (particularly for oxygen) by outgassing at 10-6 torr at 1400°C for 4 hr. The outgassing treatment resulted in specimens with a bamboo grain structure and a lustrous appearance. Desired amounts of nitrogen were added to the outgassed wires in a Sieverts apparatus in which known amounts of nitrogen were equilibrated with the wire at 1300°C. Nitrogen concentrations were produced in the desired range from less than 1 to 10 at. pct N. Monitoring of the partial pressure of nitrogen in the Sieverts apparatus indicated that at 1300°C equilibrium between the nitrogen gas and the vanadium was obtained within 10 min. Relatively rapid cooling from the nitrogen addition temperature was obtained simply by turning off the specimen heating current and cooling to room temperature in the partial pressure of nitrogen. Internal friction measurements of wire specimens were made under forepump vacuum in a torsional pendulum at frequencies near 1 cps. The torsional pendulum was of low thermal inertia and was designed so that specimens could be heated both by a conventional tube furnace and by the joule heating of a separate current through the wire specimen." Use of a static atmosphere of helium gas as a quenching medium made it possible to cut the specimen current, rapidly cool the specimen to the measurement temperature, and make a measurement of the internal friction in less than 1 min. Because of the large solubility of vanadium for nitrogen, the internal friction peak heights were in some cases greater than Q-1 = 0.1. This high damping resulted in an estimated relative uncertainty in the damping measurements of approximately 10 pct. X-ray analyses made to identify the precipitated ni-

Jan 1, 1970

By Dean, R. S.

THE numerous theories of hardening which have been advanced in recent years are all satisfactory in accounting for some of the phenomena observed in hardening metals, but none so far presented account for all of the facts observed. Some years ago one of the authors, R. S. Dean,&apos; presented a theory to account for some of the properties accompanying work hardening. The present paper develops this theory further in the light of recent experimental work and extends it to other forms of hardening. Many of the ideas included have come from the writings and personally communicated thoughts of others. We have attempted to give proper credit in every case, but it is possible that we have not always done so. As an historical basis it is desirable here to review very briefly the hardening theories which have been current. The first comprehensive theory of work-hardening phenomena was due to Sir George Beilby.2 He contributed the idea that with cold work part of the structure of the metal was rendered amorphous and that-it was to this amorphous material that the cold-worked metal owed its difference in properties. According to Beilby&apos;s theory this amorphous material was a supercooled liquid and, therefore, had the characteristics of a vitreous material. That such a theory is not capable of explaining the property changes in metals has been repeatedly pointed out. This theory also allowed a slip to take place only once on a given plane, which, as has been pointed out by Jeffries and Archer13 is not consistent with the observed length of an, individual slip and the amount of elongation which can be obtained by wire drawing. The modifications, which have been proposed to this hypothesis to make it coincide with the experimental facts, have to a considerable extent robbed the theory of its clean-cut characteristics. The commonest of these modifications replaces the amorphous phase with an

Jan 1, 1927

By R. H. Martinson, E. Teghtsoonian

The effects of magnesium-rich surface layers of varying thickness on the mechanical properties of LiF have been studied. The yield stress, critical tensile stress, and work-hardening slope increase linearly with layer thickness, while the strain to fracture decreases yapidly with increasing layev thickness. The results of tension tests, supplemente!d by metallogvaphic evidence, indicate that the yield stress and the critical tensile stress of LiF are not determined by surface-source operation. DESPITE many studies, which have recently been reviewed,&apos; certain fundamental aspects of the plasticity of LiF remain obscure. For instance, one question still awaiting a satisfactory resolution is: does the nucleation and/or multiplication of dislocations in LiF occur preferentially near the crystal surface? It is now well-known that mobile dislocation half-loops are readily introduced into LiF by surface damage and that the mechanical properties of LiF are affected by such surface damage. However, it is not known whether, in the absence of large numbers of artificially introduced surface sources, dislocations arise more easily near the crystal surface than in the crystal interior. It is also not known to what extent existing mobile dislocations multiply preferentially near the crystal surface. The present work is an experimental study of these matters. A short investigation of the effect of magnesium -alloyed surface layers on the deformation of LiF single crystals has been published by Westwood.~ Some relevant conclusions drawn from this research are restated here for purposes of comparison with the present work. 1) Tests on as-cleaved, chemically polished, coated and uncoated specimens show that a coating can restrict the operation of artificially introduced surface sources, thereby raising the yield stress. A coating also decreases the initial rate of work hardening of as-cleaved LiF crystals by reducing the number of active dislocation sources, so that mutual dislocation interference effects are lessened. 2) A catastrophic breakthrough of groups of edge dislocations piled up against the coating can cause stress drops in the stress-strain curve. 3) A surface coating can act as a stable barrier to the egress of dislocations, causing pile-up,

Jan 1, 1965

By Charles Goodale

THE principles and theory on which the U. S. mining law of 1872 was based are well understood, and have been discussed at great length by many writers. The papers by Dr. R. W. Raymond1 in the Transactions of the American Institute of Mining Engineers have covered the subject very fully, with explanations of practical results in many adjudicated cases. It is believed that the following instance of the application of the law in recent years will have some weight in a discussion of proposed changes in our mining laws. The litigation between the St. Louis Mining & Milling Co., and the Montana Mining Co., Ltd., a British corporation, over portions of the Drumlummon lode covered more than 20 years, and resulted in a judgment for damages in favor of the St. Louis Co. of such an amount that the Montana Co. declined to pay the judgment, and therefore lost the entire property. The Drumlummon lode claim in the Marysville district, Mont., was located in 1876 by Thomas Cruse. When he staked out his claim, he assumed that the discovery on the Drumlummon vein, and another showing of mineral about 200 ft. distant, were on the same vein, and the center line of the claim was given a course of N. 57&apos;2&apos;E. Development of the Drumlummon vein soon showed that its strike was about N. 15 E., and that the other outcrop was on the North Star lode; so it was inevitable that the Drumlummon vein would cross one or both side lines of the location, and the Montana Co. found it advisable to acquire adjoining claims on both sides of the Drumlummon, in order to avoid possible litigation over apex rights. They bought the Marble Heart, but would not purchase the Hopeful (see Figs. 1 and 2), at the terms proposed for the reason that exploration in the Cruse level had shown the vein to be barren in that region. The owners of the Hopeful were sinking an incline from that claim in 1889, and the Montana Co. enjoined them, contending

Jan 5, 1914

By Eugene Stephenson

IN most instances the fluids produced from underground reservoirs have been described as they appear at the surface, and usually it has not been necessary to distinguish between surface and reservoir phases. More recently it has become imperative to recognize the fact that changes in phase may occur between the reservoir and the receiving unit. The simple terminology of "wet" and "dry" gases and "crude petro-leum oil" served our needs fairly well in the shallow, low-temperature and low-pressure fields. It has been left to the legislatures, regulatory com-missions, and courts to decide whether a field is or was a gas field, an oil field, or both. This they have done by direct definition and also by implication. For example, in Texas:1 (d) The term "gas well" is any well (a) which produces natural gas not associated or blended with crude petroleum oil at the time of production, or (b) which produces more than one hundred thousand (100,000) cubic feet of natural, gas to each barrel of crude petroleum oil from the same producing horizon, or (c) which produces natural gas from a formation or producing horizon productive of gas only encountered in a well bore through which crude petroleum oil is also produced through the inside of another string of casing. (e) The term "oil well" is any well which produces one (1) barrel or more of crude petroleum oil to each one hundred thousand (100,000) cubic feet of natural gas.

Jan 1, 1938

By G. B. Craig, B. Ramaswami

The temperature and strain rate dependence of the flow stress ratio and the stvain rate dependence qi the flow stress of annealed polycrystalline a zirconiur were determined over the temperature range 30 0" to 1000°K. Some evidence was found for strain aging and discontinuous flow in the temperature ranges 520" to 650°Kand650" to 760°K, respectively. The Cottvell-Stokes relationship was obtained when deformation occurred by twinning as well as slip. The flow stress ratio showed a strong dependence on temperature and strain rate above 800°K. The expevirnental evidence indicated that the rate-controllitzg mechanism for the deformation of a zirconium above 800°K was dislocation climb, and that the deformation was not thermally activated in the range 520" to 800°K. The stacking-fault energy of a zirconium was estimated to be about 250 ergs per sq cm. A knowledge of the temperature and strain rate dependence of the applied stress necessary to deform a crystalline solid is essential for understanding the thermally activated processes occurring during deformation.&apos; Several experimental techniques have been developed for studying these processes.273 One of the techniques is the deter mi nation of the strain rate dependence of the flow stress at constant temperature. In close-packed crystals, it has often been observed that the change in stress due to a change in the strain rate varies linearly with the flow stress, (~1,&apos; This relationship, known as the Cottre ll-Stokes law, is obeyed when deformation occurs by glide alone. However, when deformation occurs by twinning as well as glide, there is disagreement among different investigators on whether the Cottrell-Stokes law is observed. Whereas Thornton et ~1.~find departures from Cottrell-Stokes law when twinning occurs in copper, ~avis~ and sasinski? find that Cottrell-Stokes law is obeyed when deformation occurs by twinning as well as slip in cadmium and magnesium, respectively. One of the main objectives of this study is to determine whether the Cottrell-Stokes law is obeyed when deformation occurs by twinning as well as slip. The second technique that has been used extensively to study the thermally activated deformation of crystals is the determination of the ratio of the flow stresses, at identical dislocation structures and con-

Jan 1, 1968

By Frances Jane Cromwell, D. J. McAdam, G. W. Geil

INTRODUCTION IN a series of papers, the authors and their associates have shown that the technical cohesion limit is affected by the same four factors that affect the flow stress, namely, the stress system, plastic deformation, temperature, and the strain rate.16-28 Moreover, each of these factors affects the technical cohesion limit in the same way that it affects the flow stress.‡ The influence of any one of these factors may be represented by a curve of cohesion limits, although only one point on the curve may represent actual fracture. As the term "fracture stress" has come into use with the same significance as "technical cohesion limit," the authors are here using the shorter term with the understanding that it does not always refer to actual fracture. This paper presents the results of an investigation of the flow of notched and unnotched specimens between yield and fracture. A study has thus been made of the flow and fracture of metals as affected by the stress system, and of the ductility of metals as affected by the stress system throughout plastic deformation. Since two of the principal stresses were equal (S2 = S3), the stress systems can be represented in terms of the radial stress ratio, the ratio of the transverse radial stress S3 to the longitudinal stress Sl.* The results of the experiments are represented by a series of complete flow-stress curves for each of the metals investigated, and these diagrams have been used for the development of other diagrams of various types. Ludwik was the first to suggest that fracture occurs when the flow stress becomes equal to a technical cohesion limit. Although Ludwik was incorrect in his view that the technical cohesion limit depends only on the amount of plastic deformation and not on the stress system, he was correct in his view that the flow-stress curve for any stress system terminates at a point representing a technical cohesion limit. The authors have seen some recent references to assertions by other investigators that a point representing the fracture stress need not be on the flow-stress curve. The Ludwik principle, however, would seem to be axiomatic, provided that the flow stress and fracture stress are properly defined and that the fracture stress is properly determined. Disregard of this principle has led to some untenable theories of criteria for fracture. When a metal is very ductile, the conventional method of determining the ductility and fracture stress by dividing the breaking load by the sectional area after fracture, generally gives values that are much too high. With some metals and in some conditions, the fracture stress thus determined may be two or more times the

Jan 1, 1948

By H. I. Aaronson

ONLY limited studies have been made of pro-eutectoid a morphology in hypoeutectoid Ti-Cr alloys during previous investigations, 1-3 The nature of the eutectoid reaction, ß?a + TiCr2, has been considered in somewhat more detail.1,2,4,4 Inasmuch as the proeutectoid ferrite reaction in plain carbon steels has recently been extensively investigated in this laboratory, advantage has been taken of the opportunity to compare the morphologies developed in two rather different eutectoid systems in order to permit a preliminary estimate to be made of the degree of generality which may be ascribed to the various results obtained. Experimental Procedure The chemical analyses of the alloys used are given in Table I. The 7.22 pct Cr alloy was prepared by the Battelle Memorial Institute from iodide titanium and high purity chromium. The initial ingot was made by arc melting a master alloy and iodide titanium. The resultant ingot was twice remelted. by the consumable electrode technique. Upset forging at 950°C reduced the final ingot to 3/4 in. sq bars. The 10.94 pct Cr alloy was prepared by the Titanium Metals Corp. of America from sponge titanium and chromium of ordinary purity. This alloy was melted twice by the consumable electrode technique, forged at 1200° to a 3/4 in. sq bar, and rolled at 815°C to a 1/2 in. round. Specimens 1/4 in. x 1/4 in. x 1/16 in. were cut from the 7.22 pct Cr alloy; halves of disks 1/2 in. in dlam and 1/16 in. thick served as specimens of the 10.94 pct Cr alloy. These specimens were individually encapsulated in Vycor, Each capsule was evacuated three times to a pressure of 2 to 6 x lo-&apos; mm Hg and flushed twice with a reduced pressure of argon prior to sealing. The inclusion of two small packets of zirconium chips permitted the capsules to be outgassed and internally gettered, without heating the specimen, prior to heat treatment. The specimens were solution annealed for 40 min at 1000°C, isothermally reacted in deoxidized lead pots, and quenched in iced water. Most of the isothermal reaction treatments were carried out at 25" intervals between 725° and 550°C on specimens of the 7.22 pct Cr alloy and at 650°C on specimens of the 10.94 pct Cr alloy. Results and Discussion Morphologies of Proeutectoid a*—Kinetics of the ß?a Reaction: Fig. 1 shows the TTT-curves for the beginning of the proeutectoid a and the eutectoid reactions in the temperature range investigated in the 7.22 pct Cr alloy. The M, temperature in this alloy is below 0°C. The curve for the beginning of the proeutectoid a reaction is in good agreement with that of Frost, Parris, Hirsch, Doig, and Schwartz&apos; for a 7.54 pct Cr alloy, appears at considerably earlier reaction times than the corresponding curve presented by Rostoker4 for a 7 pct Cr alloy, and lies athwart the curve of Spachner and co-workers11 for an 8 pct Cr alloy. Differences in criteria for the beginning of the a reaction and the relatively high rate of this reaction at lower temperatures presumably account for some of these divergences and may also explain, in part, the apparent failure of an iodide-base 7.22 pct Cr alloy to react more slowly than sponge-base 7 to 8 pct Cr alloys. Grain Boundary Allotriomorphs: Crystals of this morphology nucleate at and grow preferentially and more or less smoothly along the matrix grain boundaries.5-7 Allotriomorphs are the first morphology to precipitate at most grain boundaries at reaction temperatures from 725°C, the highest temperature studied, at least through 575°C. Fig. 2 Shows typical allotriomorphs, formed during an early stage of transformation at 725°C. Grain boundary allotriomorphs are not the predc=iaant morphology at late reaction times at any temperature studied. However; from 725" through

Jan 1, 1958

By F. L. Wolf

The catenary system of line construction possesses so many desirable characteristics from the operating standpoint that it has wide application for all types of electric traction. Many steam roads are electrifying sections of their lines, and in most cases are operating both steam and electric locomotives over the same track. This means that the overhead catenary system is subjected to the severe corrosive action of locomotive smoke, and data concerning the resistance of various alloys to this form of corrosion are very desirable from every point of view. Reliable and specific information and data on the subject of corrosion due to steam and smoke from locomotives are extremely meager and, on this account, extensive service tests, together with accelerated tests, have been made on a number of commercial metals and alloys. The observations and data recorded in this paper are the result of a preliminary test which was started in 1923 and which has been carried on to the present time. The recognition of the need for even more detailed and accurate data has resulted in the undertaking of another test which has been in progress for about a year. The result of this test will be published in due course. Some years ago The Ohio Brass Co. was asked by one of the large steam railroad companies to furnish data on construction details for a catenary system which it was considering for one of its divisions. The selection of materials which would give the necessary physical characteristics as well as withstand the severe corrosive action of locomotive gases caused electrical railroad engineers considerable concern. At that time, there were available no specific or authentic data on these important questions: no systematic investigation of the problem appeared to have been made, even though it&apos;s importance was generally recognized. Such observations as had been made were crude in that they had been limited largely to visual inspection which too frequently is most misleading. However, the scattered information which was collected gave important clues as to how best to start an investigation. Technical literature was studied, metallurgical experts were consulted, and the problem was discussed with engineers who were in close contact

Jan 1, 1930

By R. L. Orr, J. D. G. Masse, Ralph Hultgren

The relative partial molar enthalpies of gold and tin in liquid Au-Sn alloys have been measured from Xsn = 0.474 to 0.510 at 696°K, slightly above the melting point of solid AuSn. Within an average precision of 6 cal per g-atom, the data are represented by two smooth curves, which satisfy the Gibbs-Duhem relationship and which do not show any anomalous behavior in the range of composition studied. The results give no support to the hypothesis that atomic associations in the equiatomic liquid alloy resemble those in solid AuSu. LITTLE has been firmly established as to the nature of atomic distribution in liquid metallic phases. A favored hypothesis assumes the existence of atomic groupings in the liquid phase which are similar to those in solid phases occurring at lower temperatures. Beginning with this hypothesis, it is often possible to adjust the values of certain parameters (such as degree of association) so that approximate agreement is achieved with certain features of the X-ray diffraction pattern of the liquid, even though many other possible structures might satisfy the data equally well. Thus, in this manner, the structure of liquid tin has been described as a dispersion of fragments of gray tin in a matrix of metallic tin.1 Four X-ray diffraction studies2"5 have been made of the liquid alloy of composition AuSn at temperatures slightly above the melting point of the solid. Each investigator concluded, on somewhat different grounds, that the liquid consisted to a large extent of arrays of atoms similar to the solid, with admixture of more disordered arrays. Solid AuSn has the nickel arsenide crystal structure: each tin atom has six nearest neighbors, all gold atoms; and each gold atom has six tin and two gold atoms as nearest neighbors. It remains highly ordered to the melting point. The liquid alloy has a large exothermic (?H700° K = -2700 cal per g-atom6) enthalpy of formation, favoring ordering and making the hypothetical molecular association not unreasonable. The possible existence of such solidlike arrays, or of a high degree of order that occurs preferentially at a specific composition in a liquid alloy, might also be revealed by thermodynamic behavior somewhat analogous to that in highly ordered solid alloy phases. The latter often exist over wide composition ranges, within which the highest degree of order occurs at the ideal composition for which the atomic fractions are equal to the fractions of sites which are "right" for each kind of atom. On departing from the ideal composition, the excess atoms occupy "wrong" positions, raising the internal energy and making it progressively easier for additional atoms to occupy "wrong" positions. Thus, on either side of the ideal composition, there should be a pronounced rise in the entropy and enthalpy, which would be shown particularly by the change in the relative partial molar enthalpies, ?Hi, since they depend strongly on d?H/dx. In the one case where accurate measurements have been made, the solid AuCu ordered phase, the structure becomes much less ordered as the composition deviates from the ideal, and relative partial molar enthalpies change sharply as shown by the data6 given in Table I. This suggests the possibility of finding similar pronounced changes in the relative partial molar enthalpies of gold and tin in liquid alloys near the composition AuSn if the postulated solidlike ar-

Jan 1, 1967

By Robert H. Hafner, Irvin R. Kramer

IN recent years considerable interest has been shown in surface-alloyed metals, particularly those of chromium (chromized steels), which have excellent corrosion [ ] resistance under a variety of severe conditions, and may undergo bending and flanging operations without spalling. An early method1 employed to produce a high-chromium case on steel was developed by Kelley in 1921. It consisted of heating a low-carbon steel in intimate contact with powdered chromium in the presence of hydrogen at temperatures sufficiently high to permit diffusion of chromium into the steel. The usefulness of this process was limited because the extremely high temperatures of 1200° to 1400°C. (2200° to 2550°°F,) caused excessive grain growth and warpage, Louenstein and Ulmer2 packed iron castings in ferrochromium and com- [ ] mon salt, and heated for approximately three hours at 930° to 1040°C. (1700° to 1900°F,). A recent and more practical method of depositing chromium on steel surfaces has been developed in Germany by Daeves, Becker and Steinberg3-8 and in Russia by Izgaryshev and Sarkisov.9 This process consists of passing gaseous chromium chloride over the steel to be chromized at temperatures of 900° to 1000°C., or packing them in a porous, ceramic material that previously had been saturated with chromium chloride. They reported obtaining a chromized layer, 0.004 in, thick, on low-carbon steels. Later, Daeves4 established a relationship between the carbon content

Jan 1, 1942

By William R. Chedsey

IN the last two years the E.C.P.D. committees having to do with the inspection of engineering schools for possible accrediting have been concerned with the engineering content of some of the mineral industries courses. Originally the discussion arose with regard to engineering geology, or geological engineering, afterward broadening to metallurgical engineering, ceramic engineering, agricultural engineering, and other branches not pertinent to this discussion. Some members of visiting committees took the attitude that they probably would have to accredit these types of training as included in the engineering group if they met the average standard set by the mining schools, though they questioned -whether they were really engineering.

Jan 1, 1939

Charles H. Morgan, Worcester, Mass. (communication to the Secretary): In connection with Mr. Douglas&apos;s mention of the continuous charcoal kiln used at Kopparberg, some further data concerning this important invention may be of interest. Before giving these, however, I will say a word or two concerning other features of Swedish practice. In 1894 I spent two days at Soderfers with Mr. Tom Bergendal, the manager of the works, and was specially interested in the gas-producers and wood-drying kiln, illustrated in the paper contributed to our Transactions by Mr. Odelstjerna in that year.* The wood-drying kiln is, however, quite different in design and construction from Ljungberg&apos;s charcoal kiln. In the summer of 1894 it was discovered that by placing the gas-producer as close as possible to the open-hearth furnace, and working the producer hot, ordinary weather-dried wood, still containing a considerable percentage of moisture, could be used to advantage in the melting-furnace. Hence, the dryingkiln was needed for wet wood only. One of the iron-works of the Udeholm Go. was the first to adopt the Lundin saw-dust gas-producer and condenser, enabling them to make gas from saw-dust containing 45 per cent. of moisture, and convey the gas from the condenser through wooden pipes to the Siemens steel-melting furnace.† This sawdust gas gave very satisfactory results in iron-works; but the proprietors experienced much trouble by reason of the pollution of rivers by the tar-water from the condenser. On my visit, in 1894,I found that the Udeholm Co. had put in for their steel-melting furnaces the same wood-gas producers

Jan 1, 1899

By V. G. Mooradian

THE diffusion of metal atoms into the crystal lattice of another metal and the assumption of regular positions to form a homogeneous alloy are some of the most fundamental phenomena of structural metallurgy. The mechanism of this process has been the subject of a great deal of study from many viewpoints, but the picture is still far from complete. It is generally believed that if one metal is to diffuse into another, the first must have some solubility in the second1. This means that the solvent must be able to accommodate the stranger atoms, either on points of its own lattice or in the interstices between, without losing its own crystal-lographic identity. It is also a general observation that cold-working is a distinct aid in the diffusion process, causing it to take place with greater rapidity at the same temperature or with the same speed at a lower temperature. There is considerable doubt, however, as to the real significance of the deformation in its effect on the diffusion mechanism. Several factors associated with the cold-working may be responsible for the increased diffusion rate. The plastic deformation causes a distor-tion of the solvent lattice, which may be an aid in the assimulation of atoms of another kind. There are many references2 in the literature that suggest that some distortion or "loosening" of the lattice is necessary for atomic migration and that diffusion cannot take place in the undis-

Jan 1, 1935

By E. D. Levine

A study was made to delineate the dislocation mechanistns controlling prismatic and basal slip at low temperatu.ves in titanium containing approximately 100 ppm interstitial impurities. Mechanical tests were performed on single crystals prepared from electron-beam zone-refined crystal bar by a thermal cycling technique. Measurements were made of critical shear stress and activation volume as functions of temperature. The study revealed that, for prismatic slip, two overlapping thermally activated processes aye rate-controlling below 300°K. From absolute zero to 220°K, reasonable agreement is obtained between experiment and the mechanism which involves overcoming 01. the Peierl&apos;s stress by the formation of double kinks in dislocation lines lying in close-packed directions. Between 220°and 300°K prismatic slip is controlled by a difierent thermally activated process which is characterized by a stronger temperature dependence of critical shear stress. Above 300OK, prismatic slip is controlled by an athermal process. Basal slip is controlled by a thermally activated process between 195&apos; and 400°K. An approximate analysis suggests that it is the Peierl&apos;s mechanism that is rate-controlling in this range. Below 195°K, the occurrence of mechanical twinning obscures the features of basal slip. Above &apos;400 X, basal slip is controlled by an athermal process. TITANIUM, an hcp metal with a less-than-ideal axial ratio of 1.587, deforms primarily by {1010}( 1210) slip at low temperatures.&apos;-3 The critical shear stress is strongly affected by the presence of interstitial impurities. For example, churchman3 reported that a decrease in the combined nitrogen plus oxygen content from 0.1 to 0.01 pct decreased the critical shear stress for prismatic slip from 9.19 to 1.4 kg per sq mm at room temperature. Basal slip, however, is less strongly affected by interstitials; Churchman&apos;s data for {0001}( 1210) slip show a smaller decrease in critical shear stress from 10.90 to 6.3 kg per sq mm at room temperature, for the same decrease in interstitial content. In the present study, an attempt has been made to delineate the dislocation mechanisms controlling prismatic and basal slip in titanium. In view of the strong effects that impurities may have on at least some of these mechanisms, experiments were performed on material of reasonably high purity, so that comparisons could be made with investigations on material of both lower and higher impurity contents. EXPERIMENTAL PROCEDURE Single crystals were prepared from 1/4-in.-diam electron-beam zone-refined crystal bar, furnished by Materials Research Corp. The analysis of the zone-refined material is given in Table I, indicating that the interstitial content is of the same order as the purer of the two materials investigated by Churchman. The Vickers diamond pyramid hardness number of this material was 85.6. This value agrees quite well with the correlation between hardness and interstitial content proposed by Ogden and Jaffee.4 On the basis of hardness, the material investigated in this study is, therefore, intermediate in purity between that studied by Churchman (Vpn = 97) and that studied by Spangler and Herman (Vpn = 62.4).5 Single crystals were grown by thermal cycling through the a-ß transformation. Two-in.-long by 1/2-in.-diam bars were heat-treated in vacuum for 4 hr at 1160°C. The temperature of the furnace was then lowered to 865°C, and the specimens were maintained at this temperature for 7 days. This procedure was repeated several times, resulting in the growth of individual crystals up to 14 in. in length. Specimens for testing in direct shear along either {l010}(1210) or {0001}(1210) were obtained by electrical-discharge machining. The specimens were in the form of cylinders 1/4 in. in diam by approximately 1/2 in. in length, with a reduced section 1/8 in. in diam and a in. in length. All specimens were electropol-ished subsequent to electrical-discharge machining. The ends of the test specimens were cemented in stainless-steel collars. Shear tests were conducted in an Instron Tensile Tester at various temperatures from 4.2° to 508°K. Measurements were made of critical shear stress and activation volume. The latter measurements were performed by measuring the change in flow stress upon cycling the strain rate between ?1 = 2.62 x 10-3 per sec and ?2 = 2.62 x 10-4 per sec. Activation volume, I)*, is defined as u* =ßkT [11

Jan 1, 1967