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By B. M. Larsen

ATTEMPTING to review the fundamental aspects of segregation in steel ingots of all types in a paper of reasonable length, we encounter two difficulties: (I) the fact that a large number of different physical and chemical effects are involved, and (2) rather incomplete and confusing evidence on certain aspects of detail and mechanism in the freezing process in which the segregation effect is involved. The best solution seemed to be to link together most of the underlying factors into a simplified theoretical picture that appears to the writer to explain most of the observed data, in the hope that this will serve as a reasonably good target for discussion and criticism. Segregation effects, especially in steel ingots or castings, are often divided into " microscopic " and " macroscopic," depending on whether the variations in concentration of solutes? or dissolved elements in the iron occur as: (I) a periodic variation over the small distances between the nuclei and the surfaces of the primary grains, or (2) as a larger scale effect involving concentration gradients over distances of the order of several inches, more or less. The reason for this somewhat artificial division is, of course, that it is only the macroscopic scale effect that has much practical importance. About the only effect of practical importance that results from microscopic segregation is the banded structure often left in rolled sections, and even this is relatively harmless in most cases. However, the causes of microscopic segregation also underly the larger scale effect, so we must first consider matters such as the formation and growth of crystal nuclei, selective freezing and diffusion, and others that are fundamental to all segregation effects. UNDERCOOLING AND NUCLEI FORMATION It is probable that although the degree of undercooling is small in iron, as in metals in general, a certain amount of it takes place, and also that the number of crystal nuclei increases very rapidly with increased undercooling below the liquidus tempera¬ture. In practical terms this means that the nuclei number increases very rapidly with increased cooling or freezing rate, thus being dependent on the rate of heat flow out from the zone of crystallization. TEMPERATURE GRADIENTS AND HEAT DISSIPATION DURING FREEZING Each pound of steel evolves about 100 B.t.u. when freezing. In addition to this, the temperature gradient in the solidified portion (required to dissipate the heat as freezing progresses into the axis) necessitates a loss of heat required to cool the solid metal below its freezing range, which is equivalent to an amount of not so much less in magnitude. In a 5-ton ingot, the total would include about one million B.t.u. for freezing alone and about 0.4 to 0.5 million B.t.u. for the gradient, up to the end of the freezing period: Thus the rate of freezing depends primarily on the rate of heat dissipation. In the ordinary ingot shapes, the axial rate of growth of the solid

Jan 1, 1944

By E. Miller, J. M. Eldridge, K. L. Komarek

The thermodynamic properties of liquid Mg-Ge alloys have been determined between 1000°and 1500°K by an isopiestic method. Germanium specimens, heated in a temperature gradient and contained in covered graphite crucibles of special geometry, were equilibrated with magrtesium vapor in closed titanium tubes. The crucible design allowed free access of magnesium vapor to the samples during the equilibration to form alloys of magnesium and germanium, but prevented magnesium losses from the crucibles on quenching the titaniuin tubes to terminate the experimental runs, thus preserving the equilibrium alloy compositions. The activities and partial molar enthalpies of magnesium and the integral thermodynamic properties of the system were calculated from the experimental data. THE Mg-Ge phase diagram' shows one congruent melting compound, Mg2Ge, of essentially stoichio-metric composition, two eutectics, and very limited terminal solid solubilities. Very little information is available on the thermodynamic properties of the Mg-Ge system. The free energy of formation of Mg,Ge was recently deter-mined2 by a Knudsen cell technique in the temperature range 610° to 760°C. The standard enthalpy of formation of Mg,Ge was measured calorimetrically by Bever and coworkers.3 The present study was undertaken as part of a general investigation of the thermodynamic properties of the homologous series of Mg-Group IVB systems, i.e., Mg-Pb,4 Mg-Sn,5 Mg-Ge, and Mg-Si. An isopiestic technique was used which was developed by the authors5 for investigating the thermodynamic properties of liquid Mg-Sn alloys. Specimens of the nonvolatile component, contained in covered graphite crucibles, are heated in a temperature gradient in an evacuated and sealed titanium reaction tube, and equilibrated with magnesium vapor of known pressure. The method employs crucibles of special geometry which preserve the high-temperature equilibrium composition of liquid alloys having a highly volatile component such as magnesium on termination of the experimental runs by quenching the crucibles to room temperature. EXPERIMENTAL PROCEDURE First reduction germanium of 99.999+ pct purity (Eagle-Pitcher Co., Cincinnati, Ohio) and 99.99+ pct magnesium metal (Dominion Magnesium Ltd., Toronto, Canada) were used. The graphite crucibles were machined from high-density (1.92 g per cu cm) graphite rods (Basic Carbon Corp., Sanborn, N.Y.) which had a maximum ash content of less than 0.04 pct. The non-reactivity of graphite with germanium at the temperatures used in this study had been previously established by Scace and Sleck.6 The experimental procedure has been previously described in detail.5 The selection of a particular crucible geometry for a run was determined by a combination of imposed experimental conditions, the principle being that more tightly covered crucibles were required to preserve alloy compositions during quenching when higher magnesium pressures and higher specimen temperatures were used. Depending upon the composition range of the equilibrated alloys the source of the magnesium vapor was either pure magnesium or a two-phase mixture of Mg2Ge + Ge-rich liquid of known magnesium pressure. The experimental runs can be divided into the following three groups on the basis of crucible geometry and magnesium source material. Crucibles with Small Holes and Pure Magnesium Reservoirs. The crucible dimensions were identical to those of the Mg-Sn investigation5 except that the hole diameters were reduced to 0.010 in. because of the higher temperatures and higher magnesium pressures involved in the Mg-Ge system. During an equilibration run, magnesium vapor diffused from the reservoir to each specimen through the small holes, one drilled through the crucible lid and two others drilled through graphite baffles positioned vertically inside the crucible between the lid hole and the specimen. Since the magnesium pressure was high, i.e., in the range 117 to 277 Torr, during the equilibration time of approximately 24 hr, equilibration was not impeded by these holes. A specimen composition at equilibrium was fixed by the relative temperatures of the specimen and the reservoir, and by the thermodynamic properties of the system. Upon brine quenching the titanium reaction tube to end a run the vapor pressure of magnesium above the liquid alloys decreased exponentially with decreasing temperature, and the small cross-sectional areas of the holes (4.9 x 10"* sq cm) drastically reduced magnesium losses from the crucibles. Because of its low vapor pressure, germanium losses from crucibles during a run were at most 0.2 mg for pure germanium and correspondingly less for the alloys. This crucible geometry satisfactorily retained the equilibrium alloy compositions on quenching for magnesium-rich (from 3 to 33 at. pct Ge) alloys provided their temperatures were below the melting

Jan 1, 1967

By Elmer W. Pehrson

The term "survival" in the title means the preservation of a society in which men are free from the political and economic restraints that characterize totalitarian systems, be they communist, socialist or facist. It means the ability to withstand the enemy's offensives in the fields of propaganda, commercial competition and, if necessary, war. The temptation to substitute "victory" for "survival" is great but a realistic appraisal of the creeping socialism and demagoguery that pervade our time indicates that we may have to be content with survival in status quo. "Mineral strength" means assurance that adequate supplies will be available to meet all the contingencies of cold and hot wars. The overall mineral position of the U. S. viewed in the light of these premises is far from secure. It is true that we are the leading producing and consuming nation of the world, but the Soviet Union is gaining and the Sino-Soviet Bloc confronts us with a sobering potential. The emergence of the Common Market in Europe as an economic and political unit places a third independent entity into the competition. Our total mineral output continues on an up- ward trend but the reverse is true in certain strategic commodities. Moreover, consumption is moving ahead faster than production so that there is increasing dependence on imports which has significant adverse geopolitical connotations. There is widespread belief that our resources can at least maintain present levels of self-sufficiency during this critical period in world history, but social dreamers, the labor monopoly, and trade and taxation policies have discouraged aggressive activity in exploration and development, and access to essential foreign sources is threatened by a variety of circumstances. Our stockpiles, belatedly built up to achieve minimum protection against shortages in time of war, are under. political attack and threatened with partial destruction on the basis of what are at best uncertain assumptions regarding the new: look of global warfare.

Jan 11, 1962

By E. G. SINCLAIR

DRILLING wildcat wells in Wyoming differs a little from methods used in any other field. Here it is always advisable to start the hole as large as is convenient in order to carry each string of pipe as far as possible, so that drilling can be continued a thousand feet deeper if necessary, as there is always sand a few hundred feet ahead that really ought to be tested. This plan may seem ambitious, but if it is adhered to, it will save a great deal of trouble before the well is completed. In making the location, one representative from the operating department and one from the geological department should work together, so that the well may be in the best possible place for obtaining oil and the most feasible place to drill for the operating department. In Wyoming nearly all wells are drilled with standard tools, as with them a better log can be kept and better time made in completing the hole. The shales of Wyoming are very hard and do not mix well in a wet hole. The shale cuts into large pieces, too large to be circulated out of the hole, and forms a mat on the rotary which soon cuts off circulation. Then if this mat cannot be jarred from the bit, the drilling string has to be pulled and the mat cut off from the bit with a pick or an axe. I have seen standard tools come out of a wet hole with 10 to 16 in. of mat on the bottom of the bit. Rotary tools have drilled wells satisfactorily in the Big Muddy field and at Billy Creek, but in the other fields the wells have been drilled much more economically with cable tools.

Jan 1, 1926

By S. L. Hoyt

The writer has long been interested in seeking an explanation of the upper heat effect in the copper-tin alloys over the a + b range, first described in 1913. These notes are offered, not at all as the final explanation 'of this heat effect, but rather to indicate certain progress which has been made toward establishing what happens over this temperature interval. While working on the thermal analysis of the copper-rich kalchoids (copper-tin-zinc alloys), it was noted that those alloys containing major portions of tin and minor portions of zinc exhibited two marked heat effects, one at about 520' C. and the other at about 600" C., instead of the single effect which is generally observed in either of the two binary series. This matter was discussed with Dr. Guertler, who suggested that a heat effect at about 600" C. in the pure copper-tin alloys might be expected. This led to a more searching examination of the thermal critical points in the pure copper-tin alloys, with the result that a marked, although somewhat weak, heat effect was located at about 600. Somewhat later, this upper heat effect was discussed with Dr. Burgess, and it was requested that the Bureau of Standards make heating and cooling curves of one of these alloys for the purpose of removing any possible doubt as to the actual presence of the heat effect. Results obtained by the Bureau are given in Plate I. In an earlier paper1 differential curves were published showing that the heat effect occurred at constant temperature over the a + B range and increased in magnitude with the amount of B up to a point somewhat above 20 per cent. tin. No heat effect was noticed at this temperature in the eutectoid alloy. The existence of this heat effect seems to require a modification of the present copper-tin diagram in the a + B field, and it has been the object of the work here presented to secure the evidence upon which such a change should be based.

Jan 1, 1919

By C. S. Roberts

Four binary alloys in this system were creep tested at 300°' to 600°F. A photographic study of microstructural changes showed that the outstanding creep resistance results primarily from a potent precipitation hardening locally at grain boundaries. Twinning was correlated with the primary stage and nonbasal slip with the tertiary stage of creep. THE utility of the rare earth metals as ingredients of magnesium alloys destined for elevated temperature application has been recognized for about 15 years. A review of the early development of these alloys has been given by Leontis. 1,2 It has been only recently that a desire has arisen to understand basically their remarkable creep resistance. The present research had that object. The work of Leontis showed that the differences between the behavior of the individual magnesium-rare earth element binaries was of commercial significance. However, the variations were small compared to the overall difference in creep resistance between the group as a whole and the magnesium alloys of the Al-Zn type. It was decided to conduct this investigation with one binary system which would be representative of the magnesium-rare earth element alloy group. Cerium was chosen as the solute because of its near-middle position in the series and because of its availability in the commercially pure form. A previously published description of the creep behavior of electrolytic magnesium" serves as the background to this research. The experimental approach used in that investigation has been partially repeated here. A series of binary alloys was planned to include the following: 1—A dilute alloy which would contain the cerium almost entirely in solid solution. This would assess the solid solution effect. 2—An alloy which is nearly saturated at the selected solution heat treatment temperature, 1070°F. Here the effect of nearly maximum precip- itation would be obtained without the influence of undissolved Mg-Ce intermetallic. 3—An alloy containing slightly more cerium than is soluble at 1070°F. This would allow the investigation of the effect of a small amount of excess intermetallic. 4—A high cerium alloy in which the influence of a large volume of undissolved intermetallic may be examined. Experimental Details In order to specify compositions of the binary alloy series a knowledge of the solubility of commercially pure cerium in solid electrolytic magnesium and also of the composition of the terminal intermetallic phase was necessary. The latter has been proven to be approximately Mg,Ce by Voge14 and Haughton and Schofield.5 A series of both cast and extruded alloys were solution heat treated 24 hr at 1070°F for a solubility determination. Lineal analyses of the polished and etched microstructures were accomplished with the aid of a Hurlbut

Jan 1, 1955

By Jerry H. Service, F. L. Partlo

The following investigation was undertaken to develop a method for determining with reasonable accuracy the depth of overburdens of 100 ft. or less. Seismic methods seemed to offer good possibilities. The problem differed from that of the familiar salt-dome location in that the depth of overburden to be determined is much less than is encountered in oil prospecting. This means that a much shorter time interval must be measured with accuracy. Refraction methods seem at present to offer greater possibilities than reflection. The air sound persists for from 0.1 to 0.5 sec., because of echoes, and seismic reflections coming during this time are difficult to detect. A seismometer sensitive to vertical vibrations only offers possibilities and has been used here with some success. It is hoped that the application of this type of seismometer to reflection shooting in this region may be investigated still further. The apparatus used consisted of a carbon-button seismometer followed by a three-stage, transformer-coupled, vacuum-tube amplifier and a General Radio string oscillograph. Time marks are provided by a 1000-cycle, 600-r.p.m., synchronous motor provided with five spokes which intercept the light to the camera at 1/50 sec. intervals. This motor is driven by a two-stage vacuum-tube amplifier of 3 watt output, actuated by a tuning fork. The power supply for the seismometer amplifier is one 2-volt storage and one 45-volt B battery. The motor amplifier is powered by a 6-volt storage battery and 6 to 225-volt, 15-watt motor generator. The temperature-frequency characteristics of the tuning fork have been determined and for ordinary working temperatures the error in time that would be introduced is less than M millisecond for time intervals up to 100 milliseconds. The impact is produced by a sledge blow for surface distances less than 100 ft. and dynamite for greater distances. Two steel balls with wires attached form an electric circuit through a 1-ft. piece of railroad rail upon which they rest. When the rail is struck by the sledge the balls rebound, opening the circuit and indicating the time of impact by a break in the oscillograph record line as at A, Fig. 3. When dynamite

Jan 1, 1934

By N. Christensen, B. Augland, T. H. Johansen

Samples of an Fe-Nb alloy were brought to equilibriurtr with hydrogen-methane mixtures in the temperature range from 950° to 1050°C, and subsequently analyzed on their carbon contents. The solubility pvoduct L = [%Nb] [%C] may be represented by the equation Approximate solubilities indirectly assessed through hardness measurements have been included from a previous report. These data are shown to be in a fair agreement with the present solubility measurements. IN an investigation based on hardness measurements by de Kazinczy, Ms, and pachleitnerl the molal heat of solution of NbC was estimated to 11.5 kcal per mole. This value was considered rather small, and an investigation using a similar technique was carried out. The results indicated a heat of solution about 35 kcal per mole.2 At this stage it was decided to determine the solubility under conditions of true equilibrium . During the course of this work a similar investigation was published by Smith. 3 His heat of solution, 41.6 kcal per mole, is not very different from the value resulting from the present work (42.5 kcal per mole). Our solubility product, on the other hand, is at considerable variance with that reported by Smith. Possible reasons for these differences are discussed below. Mori, Tokizane, and saheki 7 have studied the behavior of niobium in commercial steels, with special attention to the formation of niobium carbide, nitride, and sulfide. Assuming a carbide composition Nbco.87 based on X-ray diffraction and chemical analysis of residues extracted from Fe-Nb-C-S alloys, the molal heat of solution of niobium carbide was estimated to 35.2 kcal per mole. MATERIALS AND EQUIPMENT The chemical analysis of the materials is given in Table I. Electrolytic iron* was used in the preparation of

Jan 1, 1968

By W. W. Gorr, R. Smith, E. H. Wyche

THE combination of high strength and corrosion resistance of cold-worked 18 Cr, 8 Ni steel has been advantageously utilized for some time, particularly in aircraft and rail car structures. There are, however, certain limitations on the use of such materials because the high strengths can be obtained only by cold-working, limiting the available products to sheets, strip, wire and tubes. The authors sought to overcome these limitations by resorting to precipitation-hardening, which has been used so successfully in nonferrous metallurgy but only to a limited extent in iron-base alloys. Accomplishment of this objective not only overcame the limitations, but also effected certain improvements in mechanical and other properties. This paper is an account of the development by Carnegie-Illinois Steel Corporation of a precipitation-hardening 18-8 stainless steel (called Stainless W? and tentatively identified as type 322). A description is given of its composition and metallurgical characteristics, heat-treatment, physical and mechanical properties and corrosion resistance. DEVELOPMENT OF THE NEW STEEL For a considerable length of time the authors were unable to determine the mechanism of the precipitation-hardening process that had been noted by Ffield 18,19 in 18-8 Ti or 18-8 Cb after cold-working and reheating to moderately elevated temperatures. All known variables were exhaustively studied, but with little success. However, results began to indicate that chemical composition was the most important variable, particularly the ratio of austenite-forming to ferrite-forming elements. The investigators 'then focused their attention upon the composition, and, in particular, upon the element titanium and its mode of alloying in the presence of other elements. A heat was obtained that could not be brought to the softness level of annealed 18-8. The response to cold-straining and aging* was very marked by previous standards, and, more important, cold-straining was found to be entirely unnecessary to produce the precipitation-hardening effect. The chemical composition of this heat was: C, 0.06 per cent; Mn, 0.54; P, 0.016; S, 0.016; Si, o.58; Ni, 7.28; Cr, 17.6o; Ti, 0.90; Al, 0.17. For some time the development work, particularly on composition, was carried

Jan 1, 1946

By B. N. Das, H. E. LaBelle, G. A. Wolf

ZnxHg1-xTe and GUPxAS1-x crystals have been grown from solution by a traveling heater method (THM). In a floating zone type fashion a solution zone sandwich of liquidus composition is made to migrate through feed material of solidus composition by a slow-speed movement of <0.25 mm per hr of the total charge through a stationary radiation or rf heater. ZnxHg1-xTe of composition 0 < x < 0.3 and GUPxAS1-x of composition 0.5 < x < 0.7 have thus been grown from their solution in liquid tellurium and gallium, respectively. A simplified analysis of heat and material transport is given. In this method, Proper adjustment of the temperature distribution along the liquid solution zone axis eliminates instability of the crystal growth front and constitutional supercooling. 1) ZnxHg1—xTe: The solid-solution telluride was grown in sealed quartz tubes at a temperature of 500 to 650°C. For first Preparations mechanical mixtures SINGLE crystals of solid solutions of III-V and II-VI compounds have been grown by various techniques from the melt, from the gaseous phase, or from solutions in of ZnTe and HgTe were used. X-ray determinations showed the resulting crystals to be homogeneous throughout their entire length, except for the end sections. The homogeneity is greatly improved by reusing the ingots obtained from first Preparations as feed material in subsequent crystal growth runs. Ingots of up to 4.5 cm have thus been obtained. 2) GaPxAs1-x: Crystals were grown in a EN crucible at a temperature of 1050°C. For first Preparation a mechanical mixture of Gap and GaAs was cemented together by a minimum amount of liquid gallium through "wet" grinding of Gap and GaAs crystals in the liquid metal and subsequent exuding of excess gallium by compacting of the charge in the EN crucible. Electron microprobe measurements using P-Ka and As-Ka radiation showed uniformity over a length of 0.4 cm. Properties of the various Preparations are described. liquid metals.&apos;-&apos; Their growth from the melt by passing a liquid zone of pseudobinary liquidus composition through a solid rod of solidus composition is generally a convenient method of growth of single crystals of solid solutions of homogeneous composition. This method loses much of its usefulness, however, if the melting point or the vapor pressure of the solid solution is high. In the case of a compound having a high melting

Jan 1, 1969

By J. H. Rushton, L. H. Mahony

Principles of fluid motion and turbulence which have been found to be of use in mixing and agitation problems are discussed, as well as suggested applications in extractive-metallurgy processes. Various types of impellers are described, together with other conditions that affect flow pattern and turbulence. The choice of equipment for particular requirements is considered, and equations for power input are given. Modern heavy-duty mixing and agitation equipment can take an increasingly important part in such extractive-metallurgy processes as solids handling, crystallizing and leaching, chemical operations, and flotation. Application of mixing and fluid-mechanics principles to extraction methods can lead to greater process rates and a resultant saving in time and money. MIXERS are being applied with increasing frequency to problems in the metallurgical industries. The increase represents in part the modernization of mechanical equipment used through the application of unitized drives, modern electric motors and speed reducers, and recently developed materials of construction. Some applications have resulted from process changes and the use of techniques for operations similar to those that have been demonstrated and proven in the chemical industry. Still more applications are being developed through the use of fluid-dynamics principles not previously recognized as applicable to these operations. It is the purpose of this paper to describe those principles of fluid motion and turbulence which have been found to be of use in mixing and agitation problems, and to suggest applications for them in the extractive-metallurgy processes. Modern mixing equipment has been designed to provide the fluid motion consistent with that best suited to different operations.&apos; When properly applied, these more efficient fluid-handling mixers result in lower process-production costs. Metallurgical operations usually involve large amounts of solids. The characteristics of the ore control the process and only enough liquid is added to provide sufficient fluidity for handling and processing. The reactive part of the ore, the mineral value to be extracted, is likely to be low in percentage, and the quantity of reagent required is similarly low, but excessive dilution makes additional reagent necessary and therefore is undesirable. Thus, the primary problems in minerals processing are to handle as high a concentration of solids as possible and to distribute reagents uniformly. These pulps, or slurries, are in a range of solids concentration where hindered settling rates apply, and care must be taken to agitate and mix sufficiently to maintain suspension and flow throughout the equipment. Such slurries have high densities which are the weighted average of the components and viscosities that are spoken of as "effective viscosities" but are difficult to evaluate. It is convenient to separate metallurgical operations involving mixers and agitators into three categories: solids handling, mechanical or physical operations, and chemical operations. In each of these categories fluid motion is required to maintain suspension, to distribute surface-active agents, to blend components and reactants, and to induce high rates of chemical reaction. After a discussion of some basic principles of mixing and agitation, examples of application to the three categories will follow. Fluid Motion The fundamental problems of mixing and agitation of liquids have to do with the mechanics of fluid streams and the means by which they are

Jan 1, 1955

By E. M. Wise

THE practice of dentistry, particularly the construction of artificial dentures and "bridges," involves a unique and difficult application of the precious-metal alloys. Appliances used in the mouth are continuously exposed to corrosive agencies which can hardly be described as mild, and must remain free from tarnish and be substantially immune to corrosion. Limitations with respect to space and weight demand high physical properties, while complexity of form requires ease of working. The high corrosion resistance required necessitates the use of alloys of high precious metal content. The usual expedient of resorting to mechanical working to produce the requisite strength and stiffness cannot be utilized because of the frequency of annealing and soldering operations. To meet these difficult conditions manufacturers of dental goods were early led, unknowingly perhaps, to the production of precipitation-hardening or temperable alloys. The excellent properties of iridium-platinum may have suggested the addition of platinum metals to the conventional gold-silver-copper alloys to produce greater strength and hardness. It was found that such quarternary alloys retained their high physical properties after passing through the usual soldering process; i, e., heating to 7500 to 8000 C. and cooling naturally in the air. Later it was discovered that they could be softened and rendered more ductile by heating to the same temperature and quenching, in water. These early examples of precipitation hardening, for years the common knowledge, of dental practitioners and laboratory technicians, escaped the attention of the scientific world and discovery of the transformation which was responsible for this hardening was discovered by the Russian investigators of the system Au-Cu, Kurnakow, Schemtschushny and Zasedatelev,(1) § although the optimum conditions for securing good properties in aged alloys were not given attention.

Jan 1, 1932

By R. A. Hadfield

It seems a specially fitting opportunity to present a paper on the alloys of iron and aluminum at the New York meeting of this Institute, owing to the fact that America has, more than any other country, originated and developed the manufacture of cheap aluminum. The Cowles, Castner, and Hall systems have all originated in the ever-busy brain of our cousin across the water. The problem of cheaply producing this valuable metal has been a difficult one, but to the writer it seems that the more arduous the task the greater the delight with which our American friend attempts to overcome the difficulties surrounding it, and the more vim he throws into the work. Another and equally striking proof of this is to be found in the recent appearance of the already wellknown remarkable work, The Mefallurgy of Steel, by Mr. H. M. Howe, of the Institute of Technology, Boston, Mass. It is to be hopel that this Institute will not be slow to recognize by some special mark its appreciation of this signally valuable and original work. The writer has been led to describe the following experiments, believing that so far no full and exact report has yet been presented to this Institute as to the effect of aluminum alloyed or combined with the metal iron. It has been a special object to make the material as far as possible a true alloy or combination of aluminum and iron, with as small quantities as possible of other disturbing ingredients, such as silicon, manganese, etc. In the material described in these experiments, the total amounts of other elements present (sulphur and phosphorus being disregarded as present in such small quantities) do not exceed about 0.5 per cent. Such material may therefore be probably taken as fairly illustrative of the effect of the metal aluminum upon iron. Since completing the experiments the writer

Jan 1, 1891

By Reinhardt Schuhmann JR

Metallurgical Engineering Volume I, by Reinhardt Schuhmann, Jr. Addison-Wesley Press. $7.50, 390 pp., 1952. -This first volume, engineering principles, of a two volume work, is intended by the author to meet a need for reorganization of instruction in extractive metallurgy. Its three main objectives are to organize the subject matter according to basic principles and unit processes; to integrate the underlying science of physical chemistry with metallurgical engineering; and to put greater emphasis on analysis and quantitative solution of engineering problems. Vol. I deals with unit processes, stoichiometry, thermodynamics, fuels, fluid flow, heat transfer, pyrometallurgical systems and refractories. Vol. II will take up the individual unit processes. Initiation and Growth of Explosion in Liquids and Solids, by F. P. Bowden and A. D. Yoffe. Cambridge University Press. $4.50, 104 pp., 1952.-The book is a study of decomposition by impact and by friction of explosive substances and deals mainly with the work of the authors and their collaborators. Research is still in progress but results thus far indicate that the mechanism of initiation is relatively simple. Findings are thoroughly discussed, and the latter part of the monograph describes the way in which a small nucleus of decomposition can grow into a large scale explosion.

Jan 1, 1952

By F. N. Speller

ASIDE from the Tuesday symposium on gases in metals, the Iron and Steel Division swung into action for the first time on the third day of the meeting with a discussion of iron and steel alloys. Dr. E. S. Davenport opened the discussion on Wednesday morning by presenting the paper written by himself in association with E. C. Bain and W. S. N. wiring on the equilibrium diagram of iron-manganese-carbon alloys. A written discussion by Mr. Scott showed qualitative agree- ment, but some quantitative disagreement. Messrs. Marsh and Sisco discussed the paper at length, pointing out non- agreement of certain conclusions with the phase rule. Dr. Krivobok, although differing with the authors on some points, stated that in his opinion the information collected would be valuable in the practical use of these alloys.

Jan 1, 1932

By E. S. Bumps, M. Baeyert, W. F. Craig

SOME time ago during a study of impact properties of tempered martensite,1 it was postulated that the consistently good ductility of tempered martensite might be caused by its relatively small and peculiarly shaped ferrite grains. The fer-rite grains of tempered martensite have approximately the same size and shape as the martensite "needles." Thus they form an interlocking mass of needle-shaped grains quite different from equiaxed or lamellar ferrite grain structures. When the common mechanical test methods are applied to steel, variations are often observed in the ductility of specimens that have closely similar hardness and tensile strength values. The ductility so measured appears to be structure dependent. When steel from the same heat has been heat treated to produce different structures with the same hardness, the elongation and reduction of area values from the tensile test and the transition temperature determined by the notched-bar impact test vary according to whether pearlite, tempered martensite, or other structural constituents were produced by the heat treatment. It has been widely recognized that tempered martensite gives a consistently good performance, when tempered to the same hardness as many other structures with which it has been compared. In recent years the isothermal transformation of austenite to specific structural products and the quantitative evaluation of the character of these products with respect to their nature and response to deformation has received considerable attention. The objective of the present study was to pursue somewhat further the dependence of ductility upon structure; specifically, it was desired to ascertain whether ferrite grain structure, including both shape and size of the grains, can account for the consistently good performance of tempered martensite in the notched-bar impact test. It was thought that a simple experiment would indicate whether the ferrite grain structure plays any part in the good ductility exhibited by tempered martensite in contrast to other steel structures with different types of ferrite grains. By determining the impact transition temperature, it was proposed to compare spheroidites having similar carbide particle size and spacing but obtained in such a manner that their ferrite grain structures would be very different. Spheroidite obtained by tempering martensite, with its small, needle-shaped grains, was to be compared with spheroidite from pearlite. If the latter is produced by sub-critical annealing, the ferrite grains correspond to the pearlite colonies. Thus, if the pearlite was not too coarse, the ferrite grains of spheroidite from pearlite are equiaxed in contrast to the needle-shaped grains of spheroidite from martensite. It was thought that the ferrite grain structure of spheroidite from martensite might depend to some extent upon the grain size of the prior austenite. The austenite grain boundaries limit the maximum attainable size of the martensite needles and thus of the ferrite grains in the derived spheroidite. In order to evaluate any possible influence of prior austehite grain size, spheroidites were to be prepared from martensites that had been formed from fine-grain austenite and also from coarsened austenite. As the carbide particle size and distribution were to be essentially alike in the various spheroidites, the difference would be in the ferrite grain size and shape. Thus any marked difference in transition temperature could be attributable to the character of the ferrite grain structure. There are certain considerations in assuming that these spheroidites would be equivalent in all respects except ferrite grain structure, and an attempt was made to take them into account. One of the considerations was the choice of the carbon content of the steel. An approximately eutectoid steel was selected for two reasons. First, the pearlitic structure would contain no proeutectoid ferrite which might complicate the picture by producing a non-uniform ferrite grain structure in the resulting spheroidite. Then, too, the high-carbon content would inhibit ferrite grain growth during the sub-critical treatment. Another factor to be taken into account was the choice of an alloying element to assure a martensitic structure throughout on quenching the impact specimens. Nickel was chosen, because it is a common alloying element and resides in the ferrite both upon its formation from austenite and throughout tempering. The formation of alloy carbides, or even a large solubility of the alloying element in cementite, would have complicated the interpretation by changing the composition of the ferrite .during spheroid-ization. The possibility of temper brittleness was minimized insofar as possible by using a tempering temperature as high as consistent with the 1 pct of nickel in the steel, namely, 1150°F. While it certainly is not claimed that no difference other than ferrite grain structure could exist between the spheroidites, nevertheless, reasonable precaution has been exercised within the limits of steel metallurgy. It is believed that any large difference in transition temperatures would reflect the difference in ferrite grain structure and that relatively good ductility in the spheroidites from mar-

Jan 1, 1951

W. ROWLAND Cox,* New York, N. Y. (written discussion?).-The process described by Mr. Malcolmson undoubtedly represents a great stride toward conservation of our natural resources. Without discussing the subject from an economic standpoint, I wish further to emphasize the fundamental principles of the Smith process in order that its economic value may be fully appreciated. The process is essentially a means of producing an ideal fuel, as regards its combustion qualities, by the removal of the so-called volatile matter from the coal, in the form of byproducts, which have value for other purposes far in excess of their fuel value. In other words, coals which contain. large amounts of gas, tar, and ammonia, and are not suitable for domestic or industrial fuel, or for treatment in byproduct coke ovens or gas retorts; because they possess poor coking qualities, can he prepared for commercial use by the. Smith process with a very high degree of efficiency. Much work has been done along this line, both in this country and in Europe, in developing a means of preparing coal, as the economic advantages have long been recognized. To the best of my knowledge, the Smith process is the only one that has proved its commercial adaptability. Distillation of coal at 900° to 1000° F. (480° to 540° C.) yields a large amount of tar and oils. The residue of the distillation, however, is a very friable semi-coke, wholly unsuitable for use as a fuel, unless it can be charged directly into a byproduct gas producer. The problem which confronted the inventor was then to convert this carbon residue into a commercial product, and it is in this step that the Smith process has overcome the obstacles which prevented a number of other methods from becoming commercially practicable.

Jan 10, 1918

By S. Sumski, M. B. Panish, R. T. Lynch

The liquidus isotherms in the gallium-rich corner of the Ga-Al-P phase diagram have been determined from 1000" to 1200°C and at I100°C the corresponding solidus isotherm was obtained. A simple thermody-namic treatment which permits calculation of the solidus and liquidus isotherms is discussed. A technique which was previously used for the growth of GaxAl1-xAs was used for the preparation of solution epitaxial layers of GaxAl1-xP and ALP. An approximate value of 2.49 i 0.05 ev for the band gap of Alp at 300°K was obtained and the ternary phase data were used to estimate a value of 36 kcal per mole for the heat of formation 0f Alp at that temperature. The Gap-A1P crystalline solid solution is one in which there exists the possibility of obtaining crystals with selected energy gaps, within the limits imposed by the energy gaps of Gap and Alp. Such crystals are of considerable interest because of their potential value for optoelectronic and other solid-state devices. Furthermore, it has been amply demonstrated for GaAs and GaP,&apos;-7 that device, or bulk materials grown from gallium solution generally have more efficient radiative recombination than materials prepared in other ways. This presumably due to the lower gallium vacancy concentration in such material.= Small crystals of GaXAl1-xP and A1P have been grown from solution,8-10 and A1P has been grown from the vapor," but neither have previously been grown by liquid epitaxy. In this paper we present the ternary liquidus-solidus phase diagram of the Ga-A1-P system in the region of primary interest for solution epitaxy, and discuss the thermodynamic implications of that phase diagram with particular reference to the liquidus and solidus isotherms in the gallium-rich corner of the GaxAl1-xP primary phase field and to the A1-P system. Several measurements of the absorption edge of GaxAl1-xP crystals have been made and the width of the forbidden gap of A1P has been estimated from these measurements. EXPERIMENTAL The differential thermal analysis technique used to determine the liquidus isotherms and the optical measurements used in this work are similar to those described previously12 for the Ga-Al-As system, ex- thermocouples in the thermopile for added sensitivity. The materials used were semiconductor grade Ga, Gap, and Al+ The composition and temperature range at which DTA studies could be done was quite restricted. The upper temperature was limited by the chrome l-alumel thermopile to about 1200°C, and the highest aluminum concentration to about 5 at. pct by low sensitivity caused by the reduced solubility of Gap with increasing aluminum concentration in the liquid. DTA studies were not possible at 1000°C and below because of the low sensitivity caused by low solubility of Gap in the Ga-A1-P system. The cooling rate for these studies was about 1°C per min. No heating studies were done because of limited sensitivity. Supercooling probably does occur, but our experience with other 111-V systems indicates that it is no greater than about 10 to 15.c. Solid solubilities were determined by analyzing epitaxial layers of GaxAl1-xP grown from the liquid, with an electron beam microprobe. The layers were grown on Gap seeds by a tipping technique in which the layer is grown over a short-temperature range (20" to 50°C) on the seed from a solution of known composition. The tipping technique reported by Nelsson1 for GaAs could not be used, particularly for solutions containing appreciable amounts of aluminum, because of the formation of an A1203 scum on the liquid surface. A system was therefore designed, which would effectively remove the oxides mechanically, so that uniform wetting and crystal growth could occur. This tipping technique has already been described in detail." The best control over the composition of the re-grown layer was obtained when the tipping was done at a temperature which corresponded to the temperature of first formation of solid for the solution being used. Generally, therefore, a solution was prepared by adding the amounts of Ga, Gap, and A1 required to yield a solution which would be completely liquid above the tipping temperature with solid precipitating below that temperature. For most of the work reported here, the 1100°C isotherm of the ternary was used. It was generally necessary to heat the solution to 50" to l00. C above the tipping temperature to dissolve all of the Gap in a reasonable length of time. The epitaxially grown layers were used both for optical transmission measurements to aid in the estimation of the way in which the absorption edge changed with aluminum concentration, and for the electron beam microprobe analyses to provide data for the determination of the solid solubility isotherm. RESULTS AND DISCUSSION Liquidus Isotherms in the Ga-A1-P Ternary Phase Diagram: Thermodynamic properties of the system. The only thermal effect studied in this work was that

Jan 1, 1970

By C. R. Simcoe, T. J. Koppenaal

The effect of direct and alternating currents on the quench aging behavior in an Al-4 pct Cu alloy has been investigated by use of resistivity measurements. The reaction rate increases with direct current density in the investigated range of 1000 to 3000 amps per sq cm. Alternating current of a specific frequency is observed to decrease the reaction rate by a factor of about two. ErDMANN-JESNITZER et al.,1,2 investigated the effect of direct and alternating current on the quench and strain aging behavior of low-carbon iron. In both cases they observed that direct current accelerates the aging reaction and that an alternating current can completely inhibit the aging process. The purpose of the present research was to investigate these phenomena in the quench aging behavior of an Al-4 pct Cu alloy and to determine the correlation, if any, between the increase in the observed reaction rate and possible heating effects accompanying the aging with direct current. EXPERIMENTAL PROCEDURE The aluminum-base alloy used in this investigation contained 3.98 wt pct Cu (1.72 at. pct) with impurities of 0.003 pct Si, 0.002 pct Fe, and 0.001 pct Mg. The alloy was rolled into a ribbon about 0.36 mm thick and 3.7 mm wide. The ribbon was split end from end with the ends being used as electrical contacts and the central unsplit section, about 5.3 cm in length, serving as the specimen. Solution treatment was accomplished by quenching from a salt bath at 520° ± 2°C into water at 25° ±0.5°C; the specimen was immediately transferred to a liquid nitrogen bath. All aging was done at 75° ± 0.2°C in a rapidly stirred ethylene glycol bath. Resistivity measurements were made by the double potentio-metric method employing a standard resistor; for purposes of convenience, the resistance measurements were made at 77°K. The transfer of the specimen from the aging bath to a liquid nitrogen dewar was accomplished in less than 1 sec. The aging kinteics were studied with the specimen being aged under the influence of direct current, alternating current, and without any type of current. The amount of heating caused by direct currents was investigated by soldering a thermocouple on the specimen surface and measuring the temperature change after applying various current densities. The temperature was observed to increase (from 75°C, the aging temperature) about 0.8°, 3.0°, and 8.5°C with direct currents of 1000, 2000, and 3000 amp per sq cm, respectively. When employing alternating current, the circuit was monitored with an oscilloscope and adjustments made to produce a normal sine-wave pattern. RESULTS Prior investigations3&apos;4 in the aging characteristics of A1-4 wt pct Cu have shown that the resistivity initially increases, reaches a maximum, and then decreases to values significantly lower than the as-quenched resistivity. This type of behavior is seen in Fig. 1 which shows the resistivity at 77°K as a function of aging time at 75°C observed in this investigation. At this aging temperature, the resistivity maximum is seen to occur in about 1 to 1-1/2 min and it further decreases to the as-quenched value in about 24 min. The behavior observed with the application of direct currents of 1000, 2000, and 3000 amp per sq cm during aging is shown in Fig. 2. With increasing current densities, (+) ?pmax decreases and the rate of the aging process increases. The time necessary to reach the as-quenched resistivity value decreases from 24 min for aging without current to about 16, 10, and 7 min for aging with 1000, 2000, and 3000 amp per sq cm direct current, respectively. Fig. 3 shows the results obtained when two changes were made during the aging with 2000 amp per sq cm

Jan 1, 1963

By W. D. Robertson, D. A. Koss, A. J. Goldman

THE significance of the hcp (E) structure, which appears when Fe-Cr-Ni alloys (stainless steels) are transformed martensitically, has been the subject of considerable study and speculation.&apos;-7 It has been proposed that the hcp structure is an intermediate phase in the transformation: fcc (austenite) — hcp (E) -bcc (0, martensite). However, recent studies by transmission electron microscopy6,7 have indicated that the hcp structure may be a consequence of the large shear strain (10 deg) associated with the fcc to bcc transformation. That is, the transformation to a bcc structure is accompanied by extensive dissociation of dislocations in the parent austenite, which has a low stacking-fault energy.&apos;-&apos;&apos; X-ray diffraction analysis of the transformed alloy reveals a pattern of lines corresponding to an hcp structure, together with the parent austenite and the bcc product. The fact that the hcp structure is observed only in association with the bcc product in these alloys1&apos;4&apos;6&apos;7 lends support to the conclusion that the hcp structure is a secondary product of the transformation. But, the evidence is circumstantial and more definite resolution of the two possibilities mains to be obtained. If the hcp structure is an intermediate product of the transformation, as in 1) above, then two distinct Ms temperatures should be observed, Ms and To evaluate this possibility, three different techniques that are particularly sensitive to the structural changes accompanying such transformations have been used in an attempt to detect two transformation temperatures in an Fe-15.1 Cr-11.7 Ni alloy: 1) high-sensitivity differential thermal analysis, 2) the temperature dependence of resonant frequency (elastic moduli), and 3) internal friction of cylindrical specimens vibrating in either longitudinal or torsional modes. To obtain the necessary sensitivity, a differential thermal analysis technique was developed for the purpose, Fig. 1. The differential temperature between a nickel standard and the specimen was amplified to produce a sensitivity of 0.02OC (0.7 v) in temperature difference. The specimen and the standard were surrounded by a copper block and the entire assembly was immersed in a solution of methyl and ethyl alcohol, freezing point, - 140OC, which provided the necessary thermal stability to reduce temperature fluctuations to negligible proportions. A cooling rate of about 1.5OC per min was obtained by bubbling liquid nitrogen through the liquid bath. In order to calibrate the experiment with respect to the evolution of heat in the transformation from fcc to hcp structures, differential cooling curves were obtained for an Fe-19.8 Mn alloy, which transforms martensitically to E.&apos;"-&apos; a Ms(e) temperature of 145°C was clearly defined by a temperature

Jan 1, 1964