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William B. Cogswell, member of the Institute since 1872, died on June 7, 1921, at his home in New York City, after an illness of about six weeks occasioned by an infection of the middle car. Mr. Cogswell is survived by his wife, Mrs. Cora Brownell Cogswell; a son-in-law, and three grandchildren. His first wife died in 1877. William Cogswell was born at Oswego, Sept. 22, 1834, and was taken to Syracuse by his parents when he was four years old. He attended Hamilton Academy and private schools in Syracuse and Seneca Falls. In 1843, he visited England with his parents and brought back a set of drawing instruments, which led to a series of lessons in architecture under Luther Gifford, the only architect in Syracuse at the time. The boy drew many building plans and one set was used for the old Globe Hotel in Syracuse, erected in 1846 and 1847. In 1848, when only 14, he spent a year with a party that was surveying the route of the Syracuse & Oswego R. R. and relaying the tracks of the Utica & Syracuse R. R. He studied civil engineering at the Rensselaer Polytechnic Institute, Troy, for three years, but left that institution in 1852 without receiving his degree. Many years later, in 1884, the degree of C. E. was conferred upon him. During the three years following 1852, Mr. Cogswell served as an apprentice in machine shops at Lawrence, Mass., under the superintendence of John S. Hoadley. About 1856, he was made manager of the machinery department of the Marietta & Cincinnati R. R., at Chili-cothe, Ohio, and three years later became superintendent of the Broadway foundry at St. Louis, Mo. In 1860, in Syracuse, Mr. Cogswell was associated with William A. and A. Avery Sweet in the formation of Sweet Bros. & Co., which later became the Whitman & Barnes Mfg. Co. At the outbreak of the Civil War, Mr. Cogswell received a civilian appointment as mechanical engineer in the United States Navy. During 1860 he was located at Port Royal, S. C., having general supervision over the work of fitting up repair shops at five widely separated stations on the Atlantic seaboard and Gulf of Mexico. In this year his genius and resourcefulness were notably shown. He literally launched a naval machine shop, so that warships could be repaired without leaving, and thereby weakening, blockades against Southern ports. The machine shop was assembled by Mr. Cogswell and shipped by boat to Port Royal. There an old whaler was made over for machine shop purposes and Mr.

Jan 1, 1922

Anders Richard Akerman entered the eternal rest on Feb. 23, 1922, after a long and distinguished career. All mining men in Sweden arc mourning him, because he was one of their greatest and a leader in the scientific metallurgy of the iron. He was born April 18, 1837, in Stockholm, where his father, Joachim Akerman, was a professor at the Technical University, but the greater part of his childhood was spent in Falun, where the family moved after his father was made principal of the mining academy. He was at first taught by a tutor, but in 1851 entered the high school in Vesteras and the University of Uppsala in 1855, from which he graduated as a mining engineer on Dec. 11, 1860. A week later, he entered the service of the Department of Commerce and entered the mining academy at Falun, from which he graduated Dec. 15, 1862. The following May, he was accepted as a student in the metallurgical section of "Jernkontoret" (the "Iron Institute") and on Oct. 22, 1864, he was made an assistant in the same section. Thus begun the cooperation with the Iron Institute which was to continue for so many years and to bear such rich fruit. He had, however, previously received two requests from the Iron Institute: One to assist Prof. V. Eggertz in the preliminary work of preparing a handbook on blast-furnace practice, the other to make a complete index of the proceedings of the Iron Institute ("Jernkontorets Annaler") volumes 1817-1864, which index was published in 1866. On Oct. 19, 1865, Akerman was requested by "Jernkontoret" to give during 1866, lectures in the metallurgy of iron at the mining academy of Falun, as Prof. V. Eggertz wished to devote his entire time to the study of assaying. This request was renewed Oct. 15, 1867, for the year 1868, and on April 17, 1869, he was made instructor in metallurgy and mining at the Technical University, to which institution the higher education in mining engineering was transferred at that time. Akerman thus entered his career as a teacher, which lasted until the end of 1891. On May 11, 1877, he was appointed assistant professor in metallurgy and mining; on Sept. 7, 1883, he was appointed acting professor in the same department; and two weeks later was appointed dean of the mining college. On May 21, 1874, he was instructed by the Crown to inspect the mining schools in Filipstad and Falun. As a teacher, Akerman was very popular and his lectures were excellent, in form as well

Jan 1, 1922

By Wolfgang Pitsch

INVESTIGATIONS on the above topic have recently been published by Shapiro and Kraussl and Jana and wayman in this journal and by Kessler and Pitsch.- Parts of the results in these papers are in good agreement with each other but there are also some results which are substantially different. The main points of these differences shall be briefly discussed in this communication. Shapiro and Krauss' measured single-surface traces of the habit planes of reversed austenite plates formed within the martensite crystals and deduced from these measurements two distinct habit planes A = (0.174; 0.309; 0.935) and B = (0.375; 0.545; 0.749) within 3 deg. Kessler and pitsch4 found instead by two-surface analysis7 one habit plane n = {0.23; 0.62: 0.75) with a real scatter of 6 deg. The latter observation of a single habit plane apart from a certain scatter is in agreement with most of the investigations of martensite transformations. The differences between these two results are so great that they cannot be explained by experimental error. The purpose of this communication is to show that the A- and B-poles of Shapiro and Krauss are due to an erroneous interpretation of a single-surface trace analysis. The difficulties in the interpretation of such single-surface trace analyses are due to the high symmetry of cubic lattices, from which it follows that there are in general twenty-four equivalent possibilities of plotting a single-surface trace in a pole figure. All these possibilities must be taken into account, when putting different traces from different plates together in order to construct the habit plane. Alternatively the poles of all the traces may be plotted in a unit triangle. This is done in Fig. 1 with twenty-nine traces of different reversed austenite plates, all of this were measured by Shapiro and Krauss in the same plane of a single martensite ther traces taken from Fig. 13 in the Shapiro and Krauss paper' which were determined by electron diffraction. The traces in Figs. 1 and 2 have to be compared with the habits A, B, and n which are under discussion. Therefore the great circles of the poles A, B, and n are plotted in Figs. 3, 4, and 5 together with a 3-deg scatter region for poles A, B and a 6-deg scatter region for pole n. Comparing Figs. 1 and 2 with Figs. 3, 4, and 5 one finds the statements which

Jan 1, 1969

By W. P. Blake

Forging under the hydraulic press, which was introduced by Haswell in the year 1861, at the machine shops of the Imperial State Railway Company of Austria, has since been greatly improved, so that at the present time there are very few parts of machines which cannot be produced in this way, and at no greater cost than iron castings. The process is now used at Vienna chiefly for such parts of locomotives as cross-heads, link-bars, axle-box frames, etc., especially where the form is intricate, and there are many angles and projections. These objects weigh from 50 to 150 lb. or more, and it is claimed for them that they are not only much cheaper than ordinary forgings, but are much more regular in form and stronger. The results which Mr. Haswell has attained, after years of patient experimenting, were well shown in the Austrian Department of the Vienna Exhibition by a collection of the pressed objects in iron and steel, just as they left the moulds, with some of them cut asunder longitudinally and the surfaces etched, so as to show the internal structure or direction of the grain. Through the courtesy of Mr. Haswell and his son I saw the hydraulic presses in full operation at the works, drawing down large Bessemer ingots, cutting them up into blocks of convenient size, and forming various park of locomotives. They have two large hydraulic presses in use; the largest, with a piston 24 inches diameter, gives 1200 tons pressure, and the second, with an 18-inch piston, gives 600 tons pressure. The pressure in the pumps is 600 atmospheres. The action is vertical; the piston descends upon the work, and for forging ingots is armed with a hammer-like head. An ingot of No. 7 soft Bessemer steel, which was forged in my presence, weighed 2030 lbs. One end being placed upon the anvil, the piston is brought slowly down and crowded into the mass as if it were putty or dough, forcing it each way, but chiefly in the direction of the length of the ingot, this being the narrowest section of the anvil and hammer. The piston is then raised and the ingot is moved forward for a second squeeze, and so on, until the first half of the ingot has been reduced in thickness, when it is turned on edge and the operation is repeated. The ingot is then turned end for end and forged until the whole length has been re-

Anders Richard Akerman entered the eternal rest on Feb. 23, 1922, after a long and distinguished career. All mining men in Sweden arc mourning him, because he was one of their greatest and a leader in the scientific metallurgy of the iron. He was born April 18, 1837, in Stockholm, where his father, Joachim Akerman, was a professor at the Technical University, but the greater part of his childhood was spent in Falun, where the family moved after his father was made principal of the mining academy. He was at first taught by a tutor, but in 1851 entered the high school in Vesteras and the University of Uppsala in 1855, from which he graduated as a mining engineer on Dec. 11, 1860. A week later, he entered the service of the Department of Commerce and entered the mining academy at Falun, from which he graduated Dec. 15, 1862. The following May, he was accepted as a student in the metallurgical section of "Jernkontoret" (the "Iron Institute") and on Oct. 22, 1864, he was made an assistant in the same section. Thus begun the cooperation with the Iron Institute which was to continue for so many years and to bear such rich fruit. He had, however, previously received two requests from the Iron Institute: One to assist Prof. V. Eggertz in the preliminary work of preparing a handbook on blast-furnace practice, the other to make a complete index of the proceedings of the Iron Institute ("Jernkontorets Annaler") volumes 1817-1864, which index was published in 1866. On Oct. 19, 1865, Akerman was requested by "Jernkontoret" to give during 1866, lectures in the metallurgy of iron at the mining academy of Falun, as Prof. V. Eggertz wished to devote his entire time to the study of assaying. This request was renewed Oct. 15, 1867, for the year 1868, and on April 17, 1869, he was made instructor in metallurgy and mining at the Technical University, to which institution the higher education in mining engineering was transferred at that time. Akerman thus entered his career as a teacher, which lasted until the end of 1891. On May 11, 1877, he was appointed assistant professor in metallurgy and mining; on Sept. 7, 1883, he was appointed acting professor in the same department; and two weeks later was appointed dean of the mining college. On May 21, 1874, he was instructed by the Crown to inspect the mining schools in Filipstad and Falun. As a teacher, Akerman was very popular and his lectures were excellent, in form as well

Jan 1, 1922

By P. W. Neurath, R. E. Waite

INFORMATION is available on the effect of stress on permeability, coercive force, and hysteresis for a variety of materials' but for the technically important grain-oriented 3 pct Si-Fe' the stress effects are not adequately covered in the literature; in addition, most of the stress data do not permit estimation of what would happen to the 60 cycle watt losses of the material under stress. Direct measurement of these effects therefore has been made and appears to be of considerable theoretical as well as practical interest. Losses were measured on the central 25 cm portion of 40~3~0.035 cm samples which could be stressed in a small tensile machine built for this purpose. Under tension the following effects, illustrated in the figures by a particular example, were observed: 1—"Unstrained" material of commercially acceptable loss level shows no change or a small increase in loss at low elastic stresses. For the sample shown in the figures, this is illustrated during the initial run, where a 7 pct increase is observed (Fig. 1). 2—There is no additional change in loss when the sample is further strained up to the elastic limit (Fig. 1). Within that limit the loss-stress curve is reversible. This is not illustrated in Fig. 1. 3—Even in the plastic range only small increases in loss are observed as long as the sample is kept under stress (Fig. 2, point N); often no increase can be observed (Fig. 1). 4—A large increase in watt losses is observed after removal of the stress subsequent to plastic deformation (Figs. 1 and 2). 5—All, or nearly all, of the foregoing increase in loss due to plastic deformation can be eliminated by a reapplication of tensile stress but returns upon removal of this stress. This is illustrated in the third run (Fig. 3). This run remains within the elastic limit and shows the reversibility of the stress-loss curve under this condition. These findings have been confirmed on large Samples (approximately 200~10~0.035 cm and larger) except that under 1 no initial increase in loss was ever observed on these. The accuracy of the watt loss measurements is of the order of 1 pct. Neither bending of the sample in the tensioning device nor a redistribution of flux along the width of the sample accounts for these results. They therefore must be explained on the basis of either a change in the domain configuration due to stress or a change in the domain wall mobility. Acknowledgment The assistance of Mr. Robert L. TenBroeck with the instrumentation is gratefully acknowledged.

Jan 1, 1956

By Glenn A. Marsh, George Bernard

It is often assumed that aerated oil field brines which are to be injected underground contain dissolved oxygen in amounts which will cause appreciable corrosion. Through the use of a new portable dissolved oxygen meter, accurate determinations were made at three brine conditioning plants. At two older plants, dissolved oxygen concentration in the final treated brine was found to he almost zero In spite of aeration during the conditioning process. At a new plant, dissolved oxygen was initially present but disappeared soon after the brine was "inoculated" with oxygen-free brine from one of the other plants. Corrosion tests at the two older plants have substantiated predictions that the brines would lint be corrosive. These results show that mechanical deaeration may not always be required in brine treating plants. INTRODUCTION The present work was undertaken to add to our knowledge of aeration and deaeration of oil field brines in brine conditioning plants. It is commonly assumed that brines which are exposed to the air soon become more or less saturated with dissolved oxygen. Since oxygen-containing brines are known to be corrosive, precautions are often taken to keep air out of brine through the use of closed systems or mechanical deaeration. The study of oxygen in brine has been seriously hampered in the past because of the lack of a suitable analytical tool. The standard Winkler method for the determination of dis-solved oxygen is satisfactory for use in fresh water, but not in many oil field brines. Corrections have to be made for a number of reducing substances such as ferrous iron and hydrogen sulfide which are commonly present in natural brines. Very often the correction factors are much greater in magnitude than the amounts of oxygen which are to be determined, and consequently erroneous results are obtained. Also. erratic Winkler data are obtained when appreciable concentrations of calcium and magnesium salts are present. The first step in carrying out a systematic study involved designing a portable dissolved oxygen apparatus which would operate in natural brines. Subsequently, this apparatus was used in three brine conditioning plants. Dissolved oxygen data obtained here, and certain corrosion rate data, illustrate the interesting behavior of oxygen in these oil field brines. APPARATUS A portable dissolved oxygen meter described in detail elsewhere,' was developed specifically for use with oil field brines. It is a polarographic apparatus employing a small rotating platinum electrode (cathode) and calomel reference electrode (anode). A potential of 0.7 volts is applied across the electrodes while they are immersed in the brine to be tested. 4References given at end of paper.

Jan 1, 1952

By J. M. Dahl, L. H. Van Vlack

STAFF: Editor, Gerhard Derge Associate Editor, Paul G. Shewman Carnegie lnstitute of Technology Schenley Park Pittsburgh, Pa. 15213 Editorial Assistant, M. A. Redmerski Production Editor, Otto T. Johnson THE METALLURGICAL SOCIETY: Jack H. Scoff, President; Richard C. Cole, Post-President; Harold B. Emerick, President-Elect; Ralph L. Hennebach, Treasurer; Robert W. Shearman, Secretary; Donald A. Parks, Assistant Secretary; Leslie S. Wilcoxson, Assistant Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: R. E. Lund, Chairman; T. E. Dancy, H. B. Emerick, P. R. Gouwens, R. E. Grace, J. H. Jackson, H. H. Johnson, A. E. Lee, Jr., R. R. Nosh, R. D. Pehlke, and Paul Queneau. Review and selection of monuscripts is under the supervision of the following Publications Committees: Extractive Metollurgy Division: R. E. Grace, Chairman; G. M. Bell, D. W. Bridges, J. M. Cigon, G. W. Healy, T. A. Henrie, R. D. Holli-day, C. E. O'Neill, C. S. Sami s, A. W. Schlech-ten, and Charles Shull . Iron and Steel Division: R. D. Pehlke, Chairman; T. P. Floridis, Arnulf Muon, G. R. St. Pierre, E. T. Tuckdogon, L. H.Von Vlack, and J. M. Uys. Institute of Metals Division: H. H. Johnson, Jr., Chairman; J. B. Clark, Vice Chairman; M. R. Achter, G. F. Bolling, J. O. Brittain, G. P. Conard, II, L. A. Girifolco. G. T. Hahn, J.P. Hirth, L. Himmel, G. T. Horne, George Krauss, C. F. Leitton, Jr., J. D. Livingston, R. D. Monning, H. M. Otte, S. V. Radcliffe, R. E. Reed-Hill, H. C. Rogers, O. Sherby, M. T. Simnod, G. R. Speich, E. A. Steigerwold, R. A. Swolin, W. A. Tiller, W. R. Upthegrove, J. B. Wagner, Jr., Derek Walton, H. W. Weart, W. W. Webb, and D. WiIsdorf. Published monthly by the American lnstitute of Mining, Metollurgicol, and Petroleum Engineers, Inc., 345 East 47th Street, New York, N. Y. 10017. Telephone PLAZA 2-6800. Subscription $30 per year for non-AIME members in United States and North, South, and Central America; $32, foreign; $7.50 for AlME members. Single copies, $6.00, single copies foreign, $6.50. The AlME is not responsible for any statement mode or opinion expressed in its publications . . . Copyright 1965 by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. . . . Registered cable address, AlME New York . . . Indexed in Engineering Index, lndustrial Arts Index, and Chemical Abstracts . . Second class postage paid at New York, N. Y., and Ann Arbor, Mich. Volume 233, Number 1.

Jan 1, 1965

By William Sellers

tested without knowing anything of their chemical composition. I had these pieces separately placed upon 10-inch bearings under a 7-gross ton lianlrner, a piece of 2½-inch round iron laid upon them as a fuller, and the hammer allotved to fall from 20 inches above the fuller, which, according to Haswell, gave a ldow of 67.75 gross tons. The pieces were then turned orcr, the fuller placed upon the convex surface, and the harnnler allowed to fall from 13 inches above the fuller, giving a blow of 58.46 gross tons. You will see that the rails do aot show ally bigrls of ruptnre, and their color at the points of torture prove them to have been absolutely cold when the test was made. I thirk these rails ought to be reasonably safe in the track. As you see by this piece of the head of one of these rails, I had it plarred, and then some teeth cut in it by a cold clrisel, and one-half of them pounded down with a hammer. The teeth of my rack did not break off. The analyses of these rails substquently made are: I. 11. Carbon,... 0.110 0.880 Silicon,..0.050 0.058 Phosphorus ,..0.086 0.082 Manganese,.. 0.042 0 840 In conclusion, I will say that Dr. Dudley's paper as a contribu tion to our knowledge of steel rails is valuable and interesting, but I protest against his conclusions king reoeived as manufacturing or comtnercial axioms. From its being presented in the form-of a report to the leading railroad of the country from one of its trusted officers, as well as from the tone of the concluding deductions, it is liable to be so received by railroad men. If any railroad com pany desires rails made under either of Dr. Dudley's formulas, and are willing to pay a price large enough to cover the loss in making them, dl and good; but so long as the rail makers are compelled to gwrrantee the wear of their rails for a given number of years, justice reqnires that. the composition of the steel from which these rails are made should be left to them. WILLIAM SELLERS, PHILADELPHIA: The very interesting paper upon the wear of steel rails that has just been read preseak the record of a series of investigations that are extreniely valuable, and the deduction that bas been drawn from the results noted seems to be unavoidable; the tests, however, to which it is proposed steel rails shall be subjected hereafter, with a view to determine their quality, sllould

Jan 1, 1881

By A. U. Seybolt, J. L. Walter

The effects of the addition of 0.5 pct ThO2 (by volume) on the grain structure and texture of heavily rolled tungsten sheet were studied. Powder metallurgy ingots were rolled to sheet, 0.001 in. thick, and samples were annealed at temperatures from 1200" to 2500°C. The heating rate to the anneal temperature was varied from 3°C per min to 6500°C per min. The orientations of the largest grains were determined by X-ray diffraction. The disposition and loss of the ThO2 particles were determined by electron transmission microscopy and the activation energy for remozlal of the thorium was measured by mass spec-troscopy. Heating rates below about 800 C per min produced large, highly elongated grains. Higher heating rates produced much smaller, less elongated grains. The grain structure and texture of the slowly heated samples were identical to the structures and textures of heavily rolled tungsten foil conventionally doped with aluminum, silicon, and potassium but the recrystallization temperature was about 200°C lower. There was stringer-like dispersion of larger ThO2, particles superimposed on a uniform dispersion of fine particles. The particles increased in size and decreased in number with time at temperature. The loss of particles was accompanied by formation of grain boundary voids and surface pits. The activation energy for removal of the ThO2 was about 40 kcal per mole. THE addition of small amounts of aluminum, silicon, and potassium to tungsten has a profound effect on the grain structure of heavily rolled sheet1 or drawn wire."4 Thus, "doped" tungsten sheet, rolled to 0.001 in. and recrystallized, develops a structure consisting of large, highly elongated grains of a specific preferred orientation.' It has been shown that the elongated grain structure was caused by a dispersion of particles, identified as mullite (Al6si2O13),1,4 in strings parallel to the rolling direction in sheet or to the wire axis. Identical results were obtained for iron which was doped with glass and rolled to 99 pct reduction of thickness and recrystallized.5 Again, the glass particles were disposed in strings parallel to the rolling direction. The strings retarded boundary migration in the lateral direction but grain growth was able to proceed relatively unhindered along the direction parallel to the strings.1,5 In both the doped tungsten and the glass-doped iron, the particles were highly plastic during the high-temperature deformation. Since mullite melts at about 1800°C and the glass employed melts at about 810ºC, the particles were probably molten during the recrystallization anneals (above 1800°C for the doped tungsten and 850°C for the glass-doped iron). There are indications in the literature that particles not plastic at hot-working temperatures (up to about 1550°C for tungsten) may also impart elongated grain structures by primary recrystallization of worked alloys. Examples are dispersions of tantalum carbide in chromium,6 and ThO2 in nickel where elongation ratios of recrystallization grains of up to 20:l were obtained.7 Strings of ThO2 particles in W-ThO2 wire have been seen by Rieck.8 In view of the available evidence, it was of interest to extend the previous studies of doped tungsten and glass-doped iron to include W-ThO2 sheet materials. Of specific interest was the grain structure, preferred orientation, recrystallization temperature, and disposition of the thoria particles. EXPERIMENTAL PROCEDURE A) Material Preparation. About 380 g of blue tungsten oxide (approximate composition WO3) was wet with a sufficient amount of aqueous solution of Th(N03)4 to provide 0.5 vol pct ThO2. The wet mixture was stirred to distribute the doping material uniformly throughout the powder. Stirring was continued while the mixture was heated until it was completely dry. The dried, doped mixture was then reduced to tungsten powder by heating at 850°C for 2 hr in a stream of dry hydrogen. The doped tungsten powder was hydropressed in a rubber sack at pressures of 50,000 psi to produce an ingot approximately 2 cm diam by about 5 cm long. Next, the pressed cylinder was heated in hydrogen for 2 hr at 1350°C to render it strong enough for machining. The cylinder was machined to a square cross section of 1.6 by 1.6 cm with rounded corners. Finally, the bar was heated for 2 hr at 2150°C in hydrogen to provide a sufficiently dense mate rial to withstand the hot-rolling operation. Prior to rolling, the ingot was reduced in thickness by about 20 pct by forging at 1550°C. This served to increase the density of the material and to widen it slightly for better rolling characteristics. The forged ingot was then rolled at 1550°C to a reduction of 45 pct of thickness, following which the rolling temperature was reduced to 1300°C and the slab rolled, with several reheats, to 0.050 in. Further reduction was accomplished at 800°C in tungsten sheet packs to a total reduction of about 99.85 pct. B) Annealing Treatment and Observation of Structure. Small samples of the rolled foil were annealed in one of two ways. Some of the samples were suspended in a covered tungsten can and annealed at temperatures from 1200" to 2200°C for various times in vacuum of l0-7 to 10-6 mm Hg. The can was heated by induction and temperatures were determined by optical pyrometry

Jan 1, 1970

By W. O. Philbrook, L. D. Kirkbride

IN the normal operation of the iron blast furnace, reduction of the iron oxides is accomplished almost entirely above the tuyeres.' Blast furnace slags usually contain less than 0.5 pct FeO, although higher values may occur with abnormal operation. There is reason to conjecture, however, that incompletely reduced ore may sometimes reach the hearth and enter the slag as a result of heavy slips or, perhaps, even from cores of excessively large lumps of a charge material of poor reducibility. The possibility of reoxidation of iron droplets falling in front of the tuyeres has been considered by several writers. It would be of interest, to know how rapidly iron oxides reaching the slag for any of these reasons could be reduced by reaction with coke or with the high carbon liquid iron in the hearth. In comparison with the hundreds of papers that have appeared on various aspects of the reduction of solid iron oxides by gases and in the presence of several forms of carbon, little work has been published on the reductioin of liquid oxides or slags. Dancey measured rates of reaction of the pure liquid oxides, both FeO and Fe,O,, with molten iron containing about 4.3 pct C. The oxide was dropped into the cup formed in the upper surface of the iron by rotating the crucible and melt. Under these conditions, reduction of either FeO or Fe,O., was completed in less than 10 sec. The present study was concerned with the reduction of FeO from blast furnace-type slags containing less than 5 pct FeO and melted over carbon-saturated iron in stationary graphite crucibles. The results were considerably different from those found by Dancey, as will be discussed later. Although this work is of interest in relation to hearth reactions in the blast furnace, interpretations must be made with caution because the experimental conditions do not duplicate those within a furnace and may not even lead to the same reaction mechanism. The authors were motivated in undertaking this work by an additional interest—the part played by FeO reduction in the mechanism of de-sulphurization of iron by slags under similar experimental conditions. Derge, Philbrook, and Goldman eveloped detailed experimental evidence to support a three-step mechanism for desulphurization like that originally proposed by Holbrook and Joseph' (These reactions are written in molecular form for convenience, but this is not intended to imply the existence of molecules of FeS in the bulk metal phase nor to deny the likelihood of ionic reactions in the slag.) Earlier work by Chang and Goldman" had shown that the overall reaction follows first-order kinetics with respect to sulphur and that the rate of reaction is proportional to the slag-metal interface area, which observations have been confirmed by subsequent work. Later studiese,' have established the influence of al.loying elements on the first and last steps of the reaction. This paper reports a study of step 3 alone, uncomplicated by the simultaneous process of sulphur transfer. Apparatus and Procedure The experiments were made in a conventional high frequency induction furnace powered by a 35 kva Hg spark gap converter. The graphite crucibles used for most of the runs were 14 cm (5.5 in.) deep and 4.8 cm (1.9 in.) ID with 0.75 cm (0.3 in.) wall. An insulating cover with a small opening for withdrawing samples was used to minimize heat loss and infiltration of air into the furnace. The crucible was charged with 300 g of carbon-saturated iron and either 65 or 100 g of prefused slag analyzing 38.0 pct SiO,, 15.4 pct A10 and 47.1 pct CaO. To obtain the cleanest possible interface at the start of the reaction, the metal and slag were brought to temperature together to prevent the rejection of kish graphite that would have been caused by the chilling effect of a large addition of cold slag to carbon-saturated iron. After temperature control had been established, the desired amount of iron oxide was added in the form of a prefused slag of composition 73.6 pct FeO, 7.7 pct AWX and 19.0 pct SiOl. This slag addition was observed to be molten in somewhat less than 1 min, and a very vigorous reaction proceeded for 1 to 2 min after its introduction. Zero time was taken as 2 min after the ferrous silicate slag addition. Slag samples weighing about 0.5 g each were taken periodically by a copper chill sampler." The weight of the initial slag was large relative to the weight of samples removed, so that the slag weight never varied by more than 5 pct during any run. Temperature was measured by a calibrated W/Mo thermocouple immersed in the metal, with a graphite tip cemented over the fused silica protection tube to prevent attack by slag and metal. After some difficulties with uncertain temperatures during the first two runs, the practice adopted to position the thermocouple for reproducible results was to lower the protection tube to touch the bottom of the crucible and then raise it 0.5 cm. The apparent temperature gradient between the bottom of the crucible and the top of the slag was found to be 15°C (27°F). but much of this spread was probably the result of inadequate immersion of the protection tube to off-set conduction losses along the graphite tip when the thermocouple was inserted only into the slag. The temperature of the bath was controlled within 25°C (9°F) during a run.

Jan 1, 1957

By M. J. Marcinkowski, Gordon E. Lakso

An extensive investigation has been made of the deformation behavior associated with the Fe3Si super-lattice using transmission electron microscopy techniques. Above 243°K the stress-strain curve exhibits three stages. Stage I occurs at a very low stress level and is related to the generation of perfect superlat-tice dislocations. Stage II is characterized by an extremely rapid rate of work hardening and is associated with the Taylor type locking of these superlattice dislocations. Finally Stage III is related to dynamic recovery processes since the work hardening rate is very small. Below 243ºK, only Stage I is observed, but it occurs at a much higher stress level. This latter observation is related to the generation of imperfect dislocations in Stage I with the consequent production of second nearest neighbor antiphase boundaries. The reason for this is that insufficient thermal energy is available at these low temperatures to generate the complete and perfect superlattice dislocations. It has been shown that the fully ordered FeCo alloys, i.e., those possessing the B2 type structure, exhibit three distinct stages of work hardening whereas the corresponding disordered alloys show only one.&apos;" This difference in behavior between the disordered and ordered alloys has been attributed to the fact that dislocations in the former case travel only as ordinary 1/2ao(111) types whereas in the latter case the move through the lattice as coupled 1/2a0(111) dislocations separated by an antiphase boundary (APB), i.e., the so-called superlattice dislocation. Although some preliminary work has been carried out concerning plastic deformation in ordered alloys possessing the DO3 type superlattice,3 no detailed analysis similar to that described in Refs. 1 and 2 has been attempted. Specifically, it has been suggested that the superlattice dislocation in this particular type structure should consist of four ordinary 1/2ao<111> types bound together by first and second nearest-neighbor APB&apos;s. Fe3A1 and Fe3Si are the two classic alloys possessing the DO3 type lattice; however, because of the somewhat higher ordering energies associated with the FesSi alloy, which in turn assures that dislocations will travel through the lattice as perfect superlattice dislocations under at least some conditions, it was chosen for the present investigation. Because of the extreme brittleness of Fe3Si, all deformation was done in compression. Stress-strain curves were obtained using both polycrystalline samples as well as single crystals. In the latter case the crystals were oriented so that deformation could be controlled either by single or double slip. They were then wafered parallel to and at various angles to the operative slip planes. These wafers were in turn examined by transmission electron microscopy (TEM) techniques in order to determine the extent of the interaction from the dislocation configuration contained therein. EXPERIMENTAL PROCEDURE The alloys used in this investigation were arc melted under helium from electrolytic iron of greater than 99.90 wt pct purity and transistor grade silicon of 99.99 wt pct purity. A typical analysis of interstitial impurities showed 120 ppm 0, 15 ppm N, and 65 ppm C Because of the extremely low ductility of the Fe3Si alloys, it was necessary to spark cut 0.230-in. diam polycrystalline cylinders 0.400 in. long from arc-melted fingers using a thin-walled brass tube as a cutting tool. The polycrystalline alloys could not be recrystallized since very little strain was induced in preparation. However they were annealed at 1273°C for 15 min in evacuated vycor capsules to relieve any cooling stresses that may have developed during solidification and then air cooled. The resulting grain size of the alloy was 0.50 mm. According to warlimont4 1273ºC is just within the single phase field where FesSi possesses the DO3 type lattice. In addition because of this high critical ordering tem-ature, air cooling from this temperature was believed sufficient to fully order all of the Fe3Si samples used in the present investigation. For the same reason, no attempt was made to achieve any degree of disorder by quenching. In fact, rapid quenching from 1123°K caused cracking. Such cracking was first suggested by sato5 with respect to the experimental observations of Glaser and Ivanick.6 Single crystal compression specimens were spark cut from single crystal ingots grown in a Bridgman type furnace. The iron and silicon for the crystals was prealloyed by arc-melting two 130-g buttons which were cut into small pieces before remelting in the furnace. This procedure resulted in a long-range inhomogeneity of 0.5 at. pct Si between the top and bottom of the 2-in.-long single crystal ingot, which was assumed to be negligible in the present investigation. The single crystals, after orienting and spark-cutting, were about 0.37 in. by 0.37 in. in cross section and about 0.5 in. long. True stress-strain curves were obtained using an Instron Tensile Testing machine in conjunction with techniques described previously. 1,7 The strain rate was 0.05 in. per in. per min. Prior to testing, the ends of all the compression cylinders were hand polished using a special jig to insure parallelism after which the sides of the samples were electrochemically polished to eliminate stress risers and to facilitate slip line observations. Test temperatures between 77" and 823°K were obtained using various cooling and heating media as described in Ref. 7 while at the upper end of this temperature range, a mixture of equal

Jan 1, 1970

By M. R. Lorenz

Efficient visible light emission from p-n junctions in semiconductors is currently achieved in the four materials, Sic, GaP, ]Ga1-xAs and GaAs1-x,. Recent advances in materials preparation and p-n junction formation are briefly reviewed. The radiative recombination processes in the different materials depend largely on the band structure and the impurity states of each material. The spectral distribution of the emission ranges from the blue in Sic, to green in Gap, yellow in Sic and red in Gap, Ga1-x AlxAs and GaAs1-x Px. The origin of the various processes are discussed. The conversion of the electrical power into optical power and the measurement of the conversion efficiency are reviewed. The currently maximum quantum efficiencies at 300°K are: 3 pct in GaP(red), 1 pct in SiC(yellow), 0.1 pct in GaP(green), 0.2 pct in Ga1-x AlxAs at 66001, and 0.1 pct in GaAs1-x Px at 6800. The brightness and the interplay of the quantum efficiency and the luminous efficiency are given detailed consideration. VISIBLE light generated by the application of a direct current to a semiconductor crystal was first observed by Lossev1 in 1923. Light emission came from naturally occurring junctions in Sic crystals but little was known then with regard to the mechanism of charge transport and light emission. Some nearly 30 years later and with a vastly increased understanding of semiconductors the phenomenon of electroluminescence was studied in more detail, for example in p-n junctions of germanium.2 In these early studies, the efficiency of converting the electron current into a photon current was very low and therefore aroused little interest toward practical application. More recently it became apparent that in certain materials, for instance GaAs, and under certain conditions, the conversion efficiency was not low at all.3 The subsequent discovery of the p-n junction laser4-6 provided the impetus for increased studies of electroluminescence. Light emitted from GaAs occurs in the infrared region of the electromagnetic spectrum and is not visible to the eye. At nearly the same time the use of GaAs1-xPx led to laser action at low temperatures which was visible to the eye.7 Later a red light emitting diode, made from Gap, was reportedS which emitted incoherent radiation at 300°K with an external quantum efficiency of about 1.5 pct. The fact that such efficient devices were obtainable led to a more concentrated effort in the search for highly efficient room-temperature semiconductor light sources. It is some of this later work on p-n junction luminescence with which we will be concerned here. Since our aim is centered on visible light, with hv =1.8 ev ( ?=7000?), only the wider band gap semiconductors are of interest, i.e., Eg 1 1.8 ev. Although many compounds meet this criterion, only a limited number of those are also good semiconductors, i.e. contain low resistance n and p regions. Some of the more promising candidates are listed in Table I. We will only be concerned with light generation from a p-n junction. This limitation excludes essentially the group II-VI binary compounds, although we will briefly review the case of ZnTe and the solid solution ZnTe1-xSex. As we will show they may contain a p-n junction but only of a special kind. Most of the discussion will deal with the four materials, Sic, Gap, Gal-xAlxAs, and GaAs1-xPx. These appear to be at the present time the best visible light emitting semiconductors. In the following sections we will briefly consider: 1) the electrical properties of p-n junctions; 2) some recent advances in materials preparation; 3) the formation of p-n junctions; and then in somewhat greater detail we will consider: 4) the various radiative recombination processes; 5) the measurement and observation of the external quantum efficiency; 6) the luminous efficiency; 7) the brightness of light emitting diodes (LED&apos;S). THE P-N JUNCTION The p-n junction in a semiconductor crystal is the interface between two differently doped regions. More specifically the p region is doped predominantly with acceptor impurities and the n region contains predominantly donor impurities. The energy band structure of a degenerate p-n junction at thermal equilibrium is shown in Fig. l(a). The excess electrons on the n side of the junction are confined to this region by the barrier potential Eg. Similarly the excess holes on the p-side of the junction are confined to the p-region by a similar potential barrier. If we now apply a dc voltage V such that the p region is made positive and the n region negative, the barrier potential EB is reduced by the applied voltage, V and the junction is said to be forward biased. With the barrier potential lowered, electrons and holes can drift toward the p region and n region, respectively, see Fig. l(b). The current voltage characteristics of p-n junctions in most wide band gap materials can be described by the relation: J = Joexp(eV/BkT) [1] where the functional form of Jo is determined by the recombination mechanism. Jo is generally a complicated parameter which depends on a number of different factors including temperature, junction width, bias voltage, and carrier lifetimes. The parameter B also depends on the recombination mechanism but

Jan 1, 1970

By H. E. Cline

Mechanical properties of the eutectic between CoAl and cobalt were measured over a range of- temnperatures and strain rates for a variety of microstructures produced by directional solidification and by thermo-mechanical processing. Directional solidification led to rodlike, lamellar, and irregular microstructures. The unusually high volume fraction of the cobalt-rich rods and the lurge spacing of the rods were explained by the phase diagram. The hot-worked structure consisted of fibers of COAL in a cobalt-rich matrix. The roonl- tevlperature strength of the uvrought material increased with decreasing grain size but the 1000°C strength decreased with decreasing pain size. At high temperatures the directionally solidified tnaterial was stronger and less strain-rate-sensitice than the hot-rolled material. The fine-grained hot-worked ma-terial became superplastic at high temperatures, with tensile elongations greater than 850 pct, while at root temperature this material was ductile and impact-resistant because of the ductile matrix. Fracture occurred in the directionally solidified material at elevated temperatures by inter phase separation and at roorn temperature by cracks in the intermetallic phase. Growth of these cracks was impeded by the ductile cobalt-rich phase. It was found that the CoAl intermetallic remains ordered at elevated temperatures. DIRECTIONAL solidification of eutectic alloys has been used to produce structures consisting of parallel rods or lamellae. Although the spacing of the phases depends on the growth rate, it has been observed to be of the order of 1 µ in many eutectics. A strong intermetallic phase has been used to reinforce a ductile matrix in the rod eutectic A1-Al3Ni and the lamellar eutectic Al-Al2cu.1 The microstructure of the eutectics A1-A13Ni and A1-A12Cu remained aligned after samples of these alloys were exposed to temperatures just below their melting points for long times. Stability of the microstructure at elevated temperatures makes directionally solidified eutectics a candidate for high-temperature applications. Recently Thompson4 has developed the Ni-NiMo eutectic containing 40 pct NiMo lamellae, giving a tensile strength superior to nickel-base superalloys. Unfortunately, this eutectic oxidizes rapidly at elevated temperatures. By mechanically processing a two-phase structure, one may reach strengths as high as 700,000 psi, as demonstrated by drawn pearlite.5 In this case the strengthening mechanism was thought to be related to the fine substructure formed during deformation.5 However, a heavily worked structure may recrystallize and coarsen at elevated temperatures. Some worked eutectics such as Al-Al2Cu,6 Pb-Sn,7 and Sn-Bi7 have shown unusually large elongations in tension when tested at elevated temperatures. This phenomenon of large extension, called "superplasticity", was related to the fine grain size of wrought two-phase alloys at elevated temperatures. A mode of deformation of "superplastic" material has been shown to be grain boundary sliding,&apos; which has also been observed during creep of polycrystalline materials.9 The Co-A1 system was chosen for this investigation after examining the phase diagrams of binary eutectics." The high melting point of 1400°C, the aluminum content which was expected to give oxidation resistance, and the properties of the intermetallic CoAl were the chief factors influencing this choice. This eutectic consists of a mixture of the intermetallic CoAl and a cobalt-rich solid solution. The intermetallic CoAl has a large range of solubility and a CsCl structure." From the similarity between CoAl and NiAl one would expect CoAl to be ordered at elevated temperatures; however, specific heat measurements" show a transition at 800°C. West-brookL2 has measured the hot hardness of CoAl and found a rapid decrease in hardness above 600°C. The tensile properties and stress rupture properties of as-cast CoAl-Co eutectic were measured by Ashbrook and wallace13 who report a room-temperature tensile elongation of less than 1 pct. I) EXPERIMENTAL A) Sample Preparation. Experimental materials were prepared by directional solidification, by hot working, and by powder processing. The starting materials were electrolytic 99.9 pct pure cobalt and 99.99 pct pure aluminum. 1) Directional Solidification. A vertical Bridgman apparatus heated by induction was used to directionally solidify cylindrical ingots $ in. in diam and 5 in. long. The apparatus was first evacuated and then an argon atmosphere was introduced to retard evaporation. The ingots were contained in an alumina crucible inside a graphite susceptor that rested on a movable water-cooled base. The base was lowered out of the induction coil at a constant rate. Eight of the ingots were solidified using a drive rate of 2.5 cm per hr, two of the ingots at 1.2 cm per hr, and one ingot at 10 cm per hr. The eutectic composition Co 10 wt pct A1 was used in all but one ingot which had the composition of the stoichiometric CoAl intermetallic, Co 32 wt pct Al. 2) Mechanical Processing. At 1000°C the eutectic Co 10 wt pct A1 is a mixture of an intermetallic phase, Co 21 wt pct Al, and a cobalt-rich phase, Co 5 wt pct Al.10 These phases differ from the stoichiometric CO 32 wt pct A1 and pure cobalt because of the large solubility of this eutectic at elevated temperatures." Four rectangular slab ingots, 4 by 1 by 12 in. high, of Co 10 wt pct Al, Co 5 wt pct Al, Co 21 wt pct Al, and Co 32 wt pct A1 were cast for hot rolling. The cobalt was first vacuum-melted, H2-treated for 20 min,

Jan 1, 1968

By J. W. Cuthbertson, R. A. Cresswell

THE constitution of Cu-rich alloys with 1.5 to 13.5 pct Sn and 0.25 to 3.0 pct Be and the precipitation-hardening characteristics of alloys with 1.5 to 13.5 pct Sn and 0.25 to 1.0 pct Be have been examined. The hardness and tensile strength of the alloys examined increase markedly after solution treatment at 700°C followed by heat treatment at temperatures between 200" and 450°C. By a combination of cold work and heat treatment, hardness values similar to those exhibited by commercial Be-Cu alloys containing 2.25 pct Be can be obtained with ternary alloys containing 9 pct Sn and 0.75 pct Be and containing 10 pct Sn and 0.5 pct Be. Marked hardening effects occur with alloys containing even less beryllium. By heat treatment alone, a hardness value of 310 diamond pyramid hardness can be obtained from an alloy containing 10 pct Sn and 0.75 pct Be. Preliminary tensile tests have shown that an ultimate tensile strength of 110,000 psi with an elongation of 23 pct is obtainable by precipitation hardening an alloy with 8 pct Sn and 0.75 pct Be. The precipitation-hardening process has been followed microscopically for certain alloys and the inference is that, while the initial hardening effect is probably explained by the precipitation of the ß phase of the Cu-Be system, further hardening, proceeding at a much slower rate, also occurs, apparently as a result of precipitation of phases of the Cu-Sn system, particularly precipitation of the 6 phase at temperatures below 350". The presence of the e phase of the Cu-Sn system in certain alloys at temperatures below 350°C has been confirmed. Tin-bronzes are widely used in engineering applications where a combination of high strength and good resistance to corrosion is wanted. The maximum strength is induced in these alloys by cold working, and it would be an advantage for many purposes if high strength could be achieved alternatively by an age-hardening process. While Cu-Sn alloys have a good fatigue resistance they can be surpassed in this respect by Cu-Be, but the use of the latter alloy is limited by its high cost. If, by adding beryllium to tin-bronze, the properties of the respective binary alloys could to some extent be combined, a most attractive alloy should result. As pointed out by Raynor,¹ beryllium is on the borderline of the zone of favorable size factors for copper, and the solid solubility of beryllium in copper is consequently much more restricted than if the size factor were strongly favorable. The size factor is sufficiently favorable, however, to permit an increase in solid solubility with rise in temperature, and there is thus a composition range in which CU- Be alloys are susceptible to hardening by precipitation heat treatment. Although the a phase of the Cu-Sn system is similarly susceptible to precipitation treatment, the time necessary to establish equilibrium in commercial alloys of this type is usually so great that age hardening becomes impracticable. The addition of beryllium to Cu-Sn alloys would appear to offer a means of conferring on the latter useful age-hardening properties. Masing and Dahl² and others have, in fact, shown that the addition of beryllium to Cu-Sn a solid solutions renders these alloys susceptible to precipitation hardening and after such hardening confers on them an encouraging improvement in physical properties. If this improvement could be achieved by the addition of substantially smaller amounts of beryllium than are customarily found in binary Cu-Be alloys, the ternary alloys should possess economic advantages which might make them more attractive than the binary alloy for some applications. Binary Systems Copper-Tin: The constitution of these alloys is now reasonably well known and is summarized in the equilibrium diagram published by Raynor.³ The following observations, due to Raynor,¹ on the structure of those phases of the Cu-Sn system that are likely to be found in the ternary alloy system will facilitate the subsequent discussion on the examination of that system. The ß phase is an electron compound at the electron-atom ratio 3:2 and has a body-centered cubic crystal structure. This phase is stable only down to 586°C, at which temperature it decomposes eutectoidally into the a and y phases. The y phase has a structure that is also based on the cubic system. This phase is stable down to 520°C, at which temperature it decomposes eutectoidally into the a and d phases. The d phase is an electron compound (Cu³¹Sn8) which has a crystal structure analogous to that of 7 brass. This phase is stable from 590" to 350°C; on prolonged annealing at the latter temperature it breaks down into a mixture of the a and E phases. The e phase is an electron compound (Cu³Sn) having the electron-atom ratio 7:4. Its structure may be regarded as a superlattice based on the close-packed hexagonal system. This phase is stable from 676°C to room temperature. The primary solid solubility of tin in copper increases to a maximum of 15.8 pct as the temperature falls from that of the peritectic reaction to 586°C. The solid solubility remains constant from 586" to 520°C. At lower temperatures the solubility decreases progressively. Below 350°C the fall in solubility is pronounced and is associated with the precipitation of the e phase. This precipitation is very sluggish and does not normally occur under service conditions. Copper-Beryllium: The Cu-Be system has been investigated by Borchers&apos; and others. Raynor5 summarized the present state of information on it.

Jan 1, 1952

By R. J. Fruehan

The oxygen activity and concentration were measured in Fe-Cr-0 melts in equilibrium with an oxide phase at 1600°C (2912°F). The activity was determined by ,use of the following solid oxide -electrolyte galvanic cell CY-Cr8,(s) I ZrOz(CaO) I Fe-CY-G(saturated)(l) The oxygen concentration decreases with increasing Cr concentration to about 270 ppm 0 at about 7pct CY and then increases gradually. The activity coefficient of oxygen (fo) decreases with increasing Cr. In melts containing up to about 20 pct Cr, log f is approximately a linear function of wt pct Cr with a slope (e q 2) of —0.037. The activity of chromium was calculated and found to exhibit a small negative deviation from Raoult&apos;s law. From the activity and solubility data for low chromium melts, the free energy of formation of chromite, FeCr204, was found to be -79.8kcal per mole where pure liquid chromium and oxygen at I wt pct in Fe are the standard states. ThE effect of chromium on the chemical behavior of dissolved oxygen in liquid iron is of great importance in controlling the deoxidation of steels containing a significant amount of chromium. Chen and chipman&apos; equilibrated Fe-Cr melts in the presence and absence of slag with hydrogen-water vapor mixtures. They concluded that at 1595°C chromite was the oxide phase in equilibrium with Fe-Cr alloys containing less than 5.5 pct Cr while at higher chromium concentration Cr,O, was the stable phase. In the composition range 0 to 10 pct Cr they found that the interaction coefficient, was equal to -0.041. Turk-dogan,&apos; Schenck and Steinmetz,, and pargeter4 measured egr) in a similar manner and found the value to be -0.064,-0.04, and -0.052, respectively. McLean and Be11 evaluated egr) from their data on the equilibrium of Fe-Cr-Al-0 alloys with H2/H20 mixtures and found it to be -0.058. However, McLean and Bell&apos;s value should only be considered an estimate because the effect of aluminum on the activity coefficient of oxygen is about a hundred times greater than that of chromium. Consequently, an error in the value of egl) used, which at the present time is not well-known, or an error in aluminum analysis, which is present in very small quantities, will result in a significant error in egr). Fischer et a1.6 determined the interaction coefficient (eEr) in Fe-Cr-0 melts not in equilibrium with an oxide phase and containing less than 18 wt pct Cr at 1600°C electrochemically. They determined a value of -0.031 for egr). Hilty et aL7 measured the oxygen content of Fe-Cr melts in equilibrium with an oxide phase containing up to 50 pct Cr. They found that the solubility of oxygen decreased as the chromium content increased to about 6 pct Cr and then increased gradually. They concluded that the equilibrium oxide phase was chromite below 3 pct Cr, distorted spinel from 3 to 9 pct Cr, and Cr,04 above 9 pct Cr. Adachi and lwamotoa also investigated this system, but did not find Cr30,. They X-rayed the equilibrium oxide phases and did not find the presence of Cr,O,. They also X-rayed the oxide phase extracted from a 65 pct Cr melt which was heat treated and did not find metallic chromium as would be expected if Cr3O4 were the equilibrium oxide phase as indicated by the reaction : 3Cr3O4 — 4Cr2O:, + Cr [lj It was the purpose of the present investigation to determine the effect of chromium on the activity coefficient of oxygen in Fe-Cr melts by measuring the activity and solubility of oxygen equilibrated with an oxide phase in the composition range 0.18 to 50.5 wt pct Cr at 1600°C (2912°F). The activity of oxygen in the melts was determined by use of the following galvanic cell: The relationship between the partial pressure of oxygen in equilibrium with the melt and the reversible electromotive force of the cell (E) is where 11 = 4, F is the Faraday constant, pb, is the oxygen pressure in equilibrium with the meit and is the oxygen pressure in equilibrium with Cr203 as determined from the free energy data compiled by Elliott et al? The oxide phase in equilibrium with pure chromium was assumed to be Cr If Cr30, were the equilibrium phase the activities derived would be approximately the same, since the best estimated free energy of formation of Cr,O,, if it does exist, is approximately % the free energy of formation of The activity of chromium in Fe-Cr alloys at 1600° C was also determined from the measured electromotive force. The activity of chromium (aCr) is related to the electromotive force as follows: , The oxide phase in equilibrium with pure chromium and Fe-Cr melts from 10 to 52 pct is assumed to be Cr203 so that n equals three. If future work proves the existence of Crs04 in equilibrium with Fe-Cr melts and pure chromium, the experimental results can be reevaluated using a value of $ for n in Eq. 141. A value of ^ for n will make the activities about 10 pct higher. In order for Eqs. 131 and [4J to be valid the electrolyte, ZrOa(CaO), must exhibit predominantly ionic conduction at the temperature and oxygen partial pressure of its use. Previous work1&apos; has demonstrated that ZrOz(Ca0) is predonlinantly an ionic conductor

Jan 1, 1970

By R. I. Jaffee, H. R. Ogden, D. J. Maykuth

IN THE past year, Jaffee and Campbell&apos; and Finlay and Snyder2 reported on the mechanical properties of titanium-base alloys, some of which were in the same ranges of composition as are covered in this paper. In this paper, evidence confirming that given by Finlay and Snyder on the effects of carbon, oxygen, and nitrogen on titanium will be presented; and, in addition, new data will be given on the effects of these elements on the flow properties and phase transformation of titanium. Materials and Preparation of Alloys The preparation and general properties of iodide titanium have been adequately described elsewhere.&apos; , As-deposited iodide titanium rod, prepared at Battelle, of Vickers hardness less than 90 was employed as the base metal in the present work. This was the same material as that used by Finlay and Snyder.2 The probable analysis reported by them for standard quality metal holds here also: N 0.005 pct, 0 0.01 pct, C 0.03 pct, Fe <0.04 pct, A1 <0.05 pct, Si <0.03 pct, and Ti 99.85 pct. Carbon was added in the form of flake graphite supplied by the Joseph Dixon Crucible Co. Oxygen was added in the form of c.p. grade TiO, powder, produced by J. T. Baker Chemical Co. Nitrogen was added in Ti3N4 powder, supplied by the Remington Arms Co. Individual ingots weighed 7 or 8 g. Carbon, oxygen, or nitrogen was added by placing the corresponding powder in a capsule made from as-deposited iodide titanium rods and melting the capsule with the balance of the charge. The charge was are-melted with a tungsten electrode on a water-cooled copper hearth under a partial vacuum of very pure argon (99.92 pct minimum). Melting was practically contamination free. Vick-ers hardness increases of less than 10 points were normal for unalloyed iodide titanium control melts. Nitrogen analyses of are-melted iodide titanium showed a nitrogen content of 0.005 pct, about the same as is present in the as-deposited rod. No tungsten pickup was found in a melt of iodide titanium analyzed for tungsten. Weight losses in melting nitrogen-free alloys were very small and varied consistently from nil to 0.015 g (0 to 0.2 pct). This permitted the use of nominal composition for these alloys. Chemical analyses made for carbon, which can be analyzed conveniently by combustion methods, justified this procedure. Where nitrogen was added, considerable splattering took place. Here it was necessary to analyze for nitrogen by the Kjeldahl method. The ingots were hot rolled at 850°C to about 0.045 in. thick. After hot rolling, the strips were descaled by mechanical grinding, and then given a cold reduction of 5 to 10 pct to insure a uniform thickness throughout the length of the specimen. The edge strips and the tensile strips were annealed in a vacuum of 1x10-4 mm Hg pressure for 3 1/2 hr at 850°C and furnace cooled. Methods of Investigation Hardness Measurements: At least five Vickers hardness measurements were taken using a 10-kg load on each sample in the following conditions: (1) top and bottom of each ingot, (2) top and bottom surface of as-rolled and annealed sheet, and (3) on cross-section of annealed sheet and all quenched specimens. Tensile Tests: Tensile tests were conducted on Baldwin-Southwark testing machines having load ranges of 600 or 2000 lb. Tests were made on 1-in. gauge-length specimens, 3 1/4-in. overall length, 1/2 in. wide, 0.040 in. thick, with a reduced section 1 1/4 in. long and 0.250 in. wide. Two SR-4, A-7 strain gauges, one mounted on each side of the specimen, were used to measure the strain over a limited range to determine the modulus of elasticity. After the modulus of elasticity readings had been taken, load vs. strain readings were taken, using only one strain gauge, at increments of 0.0001 in. until the yield points were passed and then at 0.001-in. increments to the limit of the strain-gauge indicator (0.02 in.). Strain readings above 0.02 in. per in. were taken every 0.01 in., using dividers to measure the strain between the 1-in. gauge marks until the maximum load had been reached. Crosshead speed, when using the SR-4 gauges, was 0.005 in. per min, and, when using dividers, 0.01 in. per min. Flow Curves: Flow curves were determined using the true stress-true strain data obtained during the tension test. The usefulness of this type of information has been dealt with very adequately elsewhere by L. R. Jackson,&apos; J. H. Hollomon,6 and many others. Flow curves of true stress vs. true strain could be converted to the more conventional cold-work curve of 0.2 pct offset yield strength vs. percentage of cold reduction by means of the transformation, 1/1 = 1/1-R, where R is the fraction reduction in cold working. Thus, the true strains corresponding to percentage reduction can be calculated, and the 0.2 pct offset yield strengths scaled off the — 6 curve by taking the true stresses corresponding to the values of 6 + 0.002 strain. Heat Treatment: For the transformation studies, the alloys were heat treated in a horizontal-tube furnace using a dried 99.92 pct argon atmosphere, and quenched into water. Essentially no contamination was found after several hours of heat treatment at temperatures up to 1050°C. Metallography: Specimens were prepared in the

Jan 1, 1951

By E. Miller, K. L. Komarek, M. Ettenberg

The activity of aluminum in solid Co-A1 alloys has been measured by an isopiestic technique between 850° and 1200°C from 45 to 80 at. pct Al. The activity shows a Precipitous decrease around the stoichzornetric composition of CoAl. Free energies of mixing have been calculated over a limited composition range. Considering an antistructure-vacancy defect mechanism, the degree of intrinsic disorder, a , in CoAl was related to the alunminum activity. Excellent agreement between the calculated and experimental activity curves was obtained for a = 1.25 x 10-4. ThERMODYNAMIC properties of solid aluminum-transition metal alloy are being studied in an investigation of disordering in ordered compounds. In a continuing series of investigations, activities of solid Fe-1,&apos; Ni-A1, kd r-A13 alloys have been measured. From the results for Fe-A1 and Ni-A1, the degree of intrinsic disorder for the equiatomic compounds was calculated2 using equations derived by Wagner and chottk. From the results for Cr-A1 the degree of intrinsic disorder was calculated from equations derived by Orr.&apos; In this paper, the results of the study of Co-A1 alloys are described. Published activity data in the Co-A1 system has been limited to liquid alloys at 1600°C.° A heat capacity study7 of stoichiometric CoAl indicated that a second-order phase transformation occurs at 790° C, attributed to an order-disorder reaction. Oelsen and Middel,&apos; employing the calorimetric mixing of pure liquid metals, obtained heats of formation for compositions from 6 to 90 at. pct Co. Heats of formation for 50 and 78 at. pct Co alloys have also been measured by acid solution calrimetr. The Co-A1 phase diagram, as compiled by Hansen and Anderko,lo is in good agreement with more recent X-ray evidence. The method for measuring activities of aluminum in this study is essentially that employed in the studies of the Fe-1,&apos; i-Al, and r-A13 systems. This isopiestic method entails placing cobalt specimens, in a temperature gradient, in a sealed alumina system containing a pure liquid aluminum source of fixed vapor pressure. The specimens are equilibrated, cooled to room temperature, and their final compositions determined. From the measured temperature of the specimens and the known vapor pressure of pure aluminum the activities of aluminum in the alloy can be calculated. EXPERIMENTAL PROCEDURE The cobalt was 3-mil-thick sheet of 99.9 pct purity (herritt Gordon Mines Ltd., anada). The major impurities were 0.1 pct Ni, 0.014 pct C, 0.018 pct Fe, 0.004 pct S, and 0.005 pct Cu. The aluminum metal had a purity of 99.99 pct (Aluminum Corp. of America) and all alumina parts were 99.7 pct A1,O3 (Triangle RR Grade, Morganite Refractories, Inc.) with major impurities 0.05 pct SiOz, 0.1 pct Fe203, 0.2 pct NazO, and 0.05 pCt K20. Runs 1 to 3 were made with annular cobalt specimens (12 mm ID by 21 mm OD) punched from the sheet. The specimens were deburred and degreased in carbon tetrachloride and in acetone. The samples, each weighing about 150 mg, were then positioned along an alumina rod, a in. OD by 14 in. long, separated by alumina spacers, i in. ID by | in. OD by & in. long. The lower end of the rod was placed in a hole drilled in the center of an 80-g aluminum cylinder. This assembly was put into an alumina crucible, 1+ in. ID by 13 in. OD by 3+ in. high, and the position of each sample was measured to within 50.5 mm relative to the bottom of the crucible. An alumina tube, 28.5 mm ID by 35.5 mm OD by 14 in. long, closed at the top, was slipped over the whole assembly, so that it fitted snugly into the bottom crucible. The entire reaction assembly was tied with molybdenum wire and lowered into a mullite tube, closed at the bottom. A quartz thermocouple tube, closed at one end, containing a t/Pt-10 pct Rh thermocouple, calibrated according to the specifications of the National Bureau of standards,&apos;&apos; was placed along the reaction assembly inside the mullite tube. The temperature of each specimen could be determined by gradually raising the thermocouple and measuring the temperature gradient along the reaction assembly. The combined error in temperature measurement and sample position resulted in a total error of Q°C in the recorded temperature of each sample. The mullite tube was sealed at the top by a water-cooled brass head, connected to a conventional glass vacuum system. The aluminum reservoir is heated to its melting point sealing the alumina system containing the samples. During this process the pressure is maintained below 0.01 li Hg. During subsequent heating to establish the proper temperature gradient and throughout the entire run the pressure is maintained below 2 1 Hg by means of a two-stage mechanical pump. Equilibration runs lasted from 4 to 6 weeks and were terminated by air cooling. The temperature of the liquid aluminum reservoir was brought below its melting point in less than 20 min. For runs 4 and 5, alloy buttons with 49 and 69 at. pct A1 were prepared from the initial high-purity metals by arc melting under purified argon. The alloy buttons were comminuted to powder with an alumina mortar and pestle until the powder passed through a 400-mesh screen, particle size 0.0014 in. Portions of this powder weighing between 50 and 200 mg were placed in small alumina trays, 25 by 15 by 5 mm, which were then

Jan 1, 1969

By Garth M. Crosby, F. McIntosh Galbraith, Bronson Stringham

THE Hercules mine is located in the northeastern section of the Coeur d&apos;Alene district, approximately 1 1/2 miles north of the town of Burke, Idaho. Surface indications of the ore deposit were first discovered in 1886, but regular mine production was not started until 1902 and was continuous until April 1925, when the known ore had been extracted. Incomplete records show that from 1912 until operations were suspended the mine produced 2 1/2 million tons of ore containing 9.4 pct lead and 7.7 oz of silver per ton, together with an estimated 2 pct zinc, 0.3 pct copper, and 20 pct iron. This operation was the first in. a series of mining enterprises culminating in October 1947 with the consolidation of Day Mines, Inc. In the same year it was decided to unwater the levels below the collar of the Hercules shaft in the hope of finding some indication of a recurrence of ore. The unwatering operation has been described in a. previous paper.&apos; The initial exploration, following recapture of the workings, showed sufficient promise to warrant a detailed study of the mineralogy with modern techniques. The general geo1ogy of the Coeur d&apos;Alene district, including a detailed description of the rock types encountered, has been comprehensively treated by Ransome and Calkins&apos; in their classic paper, and only local background description, therefore, is felt to be appropriate here. The Hercules deposit transects a portion of the trough of a broad south-trending synclinorium which has been greatly complicated by faulting. More locally, it lies within a block of ground bounded on the east; by the O&apos;Neil Gulch fault, a steep north-south overthrust of considerable magnitude, and on the west by a monzonite stock, the outcrop of which is 1/2 mile or more wide and 5 miles long. The country rock is composed of thin to medium-bedded argillites and argillaceous quartz-ites of the Prichard and Burke formations, the oldest members of the Pre-cambrian Belt Series of sediments in the area, believed to be of Algonkian age. The contact between them is a conformable gradation. The argillite is colored gray to tannish-gray and is fine-grained, compact, and generally massive in structure. Under the microscope the unaltered argillite is seen to be composed principally of anhedral quartz and a few feldspar grains which were at one time presumably partly rounded sand grains, but as a result of recrystallization and cementation by silica, the interstices are now almost obliterated and quartz grains show crenulate boundaries. The sizes of these crystals vary from 0.5 mm down to 0.1 mm in greatest dimension. In all specimens sericite comprises 10 to 20 pct of the rock and is present abundantly between most of the grains as flakes or shreds which vary considerably in size. Sometimes they form a fine felt-like mat or aggregate, and sometimes flakes are seen which appear to be good muscovite. In some specimens, separated rhombic-shaped carbonate grains are abundant, and in some instances these have been changed to sericite. Mining operations to date have explored the Hercules vein to a maximum vertical depth of 3600 ft below its outcrop, and along a maximum strike-length of 3600 ft on certain of the lower mine levels. The main orebody is irregular in outline, extending over a variable strike-length of 400 to 1500 ft; and it is intersected by a strong transverse fault that has been traced from the surface to the bottom level. This has been named the Hercules fault, and apart from the vein itself, it is the most prominent structural feature in the mine. There is good evidence that it existed prior to the introduction of ore solutions and may have influenced ore deposition, but it was also the locus of important post-ore displacement and shows a progressive right-handed horizontal component reaching 200 ft on the deeper levels. Its vertical component is not definitely known but may be considerably greater. The fault strikes 20° N to 50° E and dips westerly at angles of 70" to 45", flattening in dip where it crosses the original orebody from east to west between 1000 and 1600 ft below the surface. At about 3000 ft in depth the Hercules fault is joined by a vertical fault of similar strike, and the major post-ore dis-placement below their junction is taken up along this vertical branch of the structure, now called the Mercury fault. Recent work has been concentrated in this vicinity. Another structural feature of special geologic interest, though of little economic importance, is the occurrence of a porphyritic dike in this area. This lies a short distance above the Hercules fault, essentially parallel to it, and is 5 to 15 ft in thickness. It appears at first glance to cut the mineralization, suggesting push-apart relationship, but small stringers of the vein minerals have been observed to penetrate the dike for a matter of inches at several points. The dike is thought to be related to the monzonite intrusion. A vertical longitudinal projection of the mine is shown in Fig. 1, which illustrates most of the features discussed above. The Hercules vein was deposited along the course of a strong, persistent shear zone that now appears as a braided network of gouge seams running through more or less crushed and shattered country rock. It strikes 70° N to 80° W and dips southerly at an average of 75". Barren parts of the structure vary in width from less than 1 ft to more than 15 ft. The width of mineralized segments may be double that. Although the evidence is not conclusive, pre-mineral, normal movement along the zone may be 1000 or 1500 ft. The horizontal component is unknown. Post-ore movement appears to have been

Jan 1, 1954

By Don L. Kendall, Martin G. Buehler

A simple physical model has been developed to fit carrier-removal data in silicon irradiated near room temperature with reactor spectrum neutrons. Commonly observed donor and acceptor defect energy levels are assumed to be introduced linearly with neutron fluence. The donor levels (in ev) are Ev + 0.16, Ev + 0.27, and Ev + 0.31 and the acceptor levels are Ec - 0.55, Ec - 0.40, and Ec - 0.1 7, where Ev and Ec are the valence and conduction band energies, respectively. The introduction rates of each level are adjusted to fit literature initial carrier-removal rate data. When normalized with respect to the Ev +0.27 level, the relative values of introduction rates are 5.3, 1.0, 3.1, 1.0, 2.0, and 20.0, respectively for the six levels indicated above. To fit p-f (hole concentration vs neutron fluence) and n-f (electron concentration us neutron fluence) data, the introduction rates are multiplied by a factor which preserves the relative values given above. This factor depends upon irradiation temperature, reactor energy spectrum, neutron fluence calibration, and oxygen content of silicon. An extensive study of the effect of neutrons on carrier-removal in silicon irradiated with reactor spectrum neutrons (E > 10 kev) has been given by Stein and Gereth1 (SG) and Curtis, Bass, and Germano&apos; (CBG). They measured initial carrier-removal rates for both p- and n-type silicon over an impurity range typical of silicon devices. In this work, we attempt to fit a simple theory to this data to establish a usable relationship between hole and electron concentration, p and n, respectively, and neutron fluence f. The p-f and n-f relations are needed to assist in the design of neutron tolerant silicon devices and are needed to clarify presently used empirical resistivity-fluence relationships.3 Neutron damage in silicon produces a variety of defects ranging from simple point defects to defect clusters. For the purpose of this treatment, we assume that simple point defects dominate carrier-removal effects. In contrast to this view, stein4 has proposed that defect clusters are responsible for a significant portion of carrier-removal effects. In the following section, it is shown that the carrier-removal effect in n-type silicon with an electron concentration less than 1015 cm-3 can be explained adequately by assuming that the divacancy is the dominant defect and that its introduction rate is independent of the electron concentration. For electron concentrations greater than 1015 cm-= an additional acceptor defect center is needed, and for simplicity the A-center (vacancy-oxygen pair) has been chosen. Although the E-center (vacancy-phosphorus pair) can account for some of the results, the A-center was chosen because the E-center requires a more involved treatment which the presently available data do not justify. In p-type silicon three radiation-induced donor levels are assumed, namely the divacancy and two other centers of unspecified nature located at Ev + 0.16 ev and Ev to 0.31 ev. The donor divacancy at Ev + 0.27 ev is assumed to be introduced at the same rate in p-type as in n-type. However, this rate is too low to fit p-type initial carrier-removal data. The dominant centers in p-type silicon are assumed to be the Ev + 0.16 ev and Ev + 0.31 ev levels where the latter is not the divacancy. The introduction rates are chosen to fit initial carrier-removal rate data. Assuming that the introduction rates are independent of Fermi level, the ratio between them is fixed for subsequent p-f and n-f calculations. Using the same ratios, the initial carrier-removal rate data1,2 as well as p-f and n-f data1,5 can be fit provided the absolute value of the introduction rates are adjusted to account for irradiation temperature, reactor energy spectrum, neutron fluence calculation, and the oxygen content of silicon. THEORETICAL ANALYSIS This analysis is basically the same as that used by Hi116 to analyze electron damage in silicon except we express the degree to which an impurity level is ionized not in terms of the Fermi level, but in terms of carrier concentration. Landis and pearson7 have used the latter approach to analyze y-damage in silicon. Neutron-induced defects responsible for carrier-removal at room temperature are assumed to be simple point defects with no interaction between defects so that they may be represented by discrete energy levels. It is also assumed that no constituent of a defect complex is used up and defects stabilize shortly after irradiation. Defects are assumed to be introduced linearly with fluence according to the product Rtf where Rt is the defect introduction rate and f the neutron fluence. Taking into account the ionization of defects according to Fermi statistics, and considering charge neutrality where minority carriers are neglected, the n-f relation is where no is the preirradiation electron concentration. The parameter Nt is the electron concentration at which the ionized defect concentration is one-half the total defect concentration (Rtf) or where Et is the defect energy level. For silicon at 300°K, ni = 1.45 X 1010 cm-3 and Ei = Ev+ 0.542 ev which was determined using Ec — Ev = 1.11 ev and me* = 1.07 mo and mh* = 0.558m0. The spin degeneracy factor, which usually appears as a number multiplying the Nt/n term of Eq. [1], is taken as unity. In effect, this factor has been incorporated into the defect en-

Jan 1, 1970