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By M. Murakami, Y. Murakami, O. Kawano

The formation and growth of Guinier-Preston zones in Al-Zn alloys containing 4.4, 6.8, 9.7, and 12.4 at. pct zn have been studied by the X-ray small-angle scattering method. Particular attention was paid to the effects of small amounts of third elements silver, silicon, and magnesium on the formation and growth of G.P. zones. It was noticed that an appreciable number of G.P. zones were formed during the course of rapid cooling and that the size, volume fraction, and number of these G.P. zones were influenced by the existence of the third elements. During subsequent aging it was also found that the addition of both silver and silicon lowered the temperature for the growth of G.P. zones, whereas the addition of magnesium raised it. These results were explained in terms of the mutual interactions among zinc atoms, vacancies, and the third elements. A number of studies on the formation and growth of Guinier-Preston zones in Al-Zn alloys have been reported.1-4 Panseri and Federighii have found that the initial stages of zone growth take place at temperatures as low as around -100°C. For investigation of the mechanism of the initial stages of zone growth, growth studies must be carried out at low temperatures. In order to investigate the possibility of the formation of G.P. zones by the nucleation mechanism or the spinodal decomposition during quenching which was reported by Rundman and Hilliard,5 the examination of the as-quenched structure must be performed. In this paper the investigation of the early stages of the formation and growth were determined by means of the X-ray small-angle scattering method. With this technique, change of X-ray scattering intensities was measured while quenched specimens were heated slowly from liquid-nitrogen temperature to room temperature. At as-quenched state and after heated to room temperature, investigation of zone size, volume fraction, and zone number per unit volume was carried out. Measurements on these specimens yielded information on the early stages of zone formation and growth. Measurements were made also on specimens quenched to and aged at room temperature. From these measurements the previously reported model6 for the later stages of growth is confirmed; namely, the larger zones grow at the expense of smaller ones. Three elements, silver, silicon, and magnesium, were chosen as the third elements for the following reasons: Silver. In the binary A1-Ag alloy the spherical disordered 77' zones were observed immediately after quenching.7 Therefore, in the Al-Zn-Ag alloys, it is suggested that silver atoms might induce cluster formation during quenching. Also, since the migration energy of the zinc atoms was found to be raised by the addition of silver atoms,' silver atoms may have a great effect of the zinc diffusion, especially during low-temperature agings. Silicon. The effects of the addition of silicon atoms were found to be marked, especially at low-tempera-ture aging. In the binary Zn-Si system, no mutual solid solubilities between silicon and zinc9 and no in-termetallic compounds10 are reported to exist. Shashkov and Buynov11 investigated the behavior of silicon atoms in Al-Zn alloys and showed that silicon was not in the G.P. zones. The interaction between silicon atoms and vacancies is strong enough to increase the quenched-in vacancy concentration.* Magnesium. Magnesium atoms are reported to trap quenched-in vacancies and after much longer aging times these trapped vacancies will become free and act as diffusion carriers.13 Therefore at intermediate aging times, the diffusion of zinc atoms in Al-Zn-Mg alloys will be slower than in the binary Al-Zn alloys, whereas at longer times zinc diffusion will become faster. EXPERIMENTAL PROCEDURE The alloys used in this investigation had compositions of 4.4, 6.8, 9.7, and 12.4 at. pct Zn with or without 0.1 and 0.5 at. pct Ag, Si, or Mg. The alloys were prepared from high-purity aluminum, zinc, silver, silicon, and magnesium, with each metal having a purity better than 99.99 pct. The analyzed composition of the specimens is given in Table I. The measurements of the X-ray small-angle scattering were carried out with foils of 0.20 mm thick. The change of the scattering intensity was always measured at the fixed scattering angle of 20 = 2/3 deg. This angle exists nearly on the position of the intensity maximum. The value of the interparticle interference function14 which has large effect in this range of angles may not change abruptly in the case of the spherical shape of small zones. Therefore, from the above considerations, it is concluded that an increase of the intensity measured at this constant angle corresponds to an increase of the average radius and volume fraction of G.P. zones. The specimens were homogenized at 500°, 450°, and 300°C for 1 hr in an air furnace. For the study of the formation and growth at low temperatures, the foil

Jan 1, 1970

Some Things We Don't Know about the Creep of Metals. By H. W. Gillett (T.P. 1087) Reduction of Iron Ores under Pressure by Hydrogen. By Michael Tenenbaum and T. L. Joseph (T.P. loll, with discussion) Induction Furnaces for Rotating Liquid Crucibles. By E. P. Barrett, W. F. Hol- bRook and C. E. Wood (T.P. 986, with discussion) Mechanism of Solidification and Segregation in a Low-carbon Rimming-steel Ingot,. By Anson Hayes and John Chipman (T.P. 988, with discussion) Solidification of Rimming-steel Ingots. By A. HultGRen and G. PhRagmen. (Contribution 112) Dendritic Structure of Some Alloy Steels. By Daniel .I. Martin and James L. Martin (T.P. 1066, with discussion) Occlusion and Evolution of Hydrogen by Pure Iron. By George A. Moore and Donald P. Smith (T.P. 1065, with discussion) Structure of Iron after Con~pression. Hy Charles S. Barrett (T.P. 977, with discussion) Structure of Iron after Drawing, Swaging, and Elongating in Tension. Ry Charles S. Barrett and L. H. LevensoN (T.P. 1038, with discussion) Magnetic Torque Studies of the Texture of Cold-rolled and of Recrystallized Iron-silicon Alloys. By Leo P. TaraSovJ(T.P. 1012, with discussion) Influence of Atmosphere and Pressure on Structure of Iron-carbon-silicon Alloys. By Alfred Boyles (T.P. 1046) Kinetics of the Decomposition of Austenite at Constant Temperature. By J. H. Austin and R. L. Rickett (T.P. 964, with discussion) Reaction Kinctics in Processes of Nucleation and Growth. By William A. Johnson and Robert F. Mehl (T.P. 1089, with discussion) Phase Changes in 3.5 Per Cent Nickel Steel in the Acl Region. By I. N. Bavarine (T.P. 1031, with discussion) Chromium in Structural Steel. By Walter Crafts (T.P. 1055) Surface Allotropic Transformation in Stainless Steel Induced by Polishing. By J. T. BuHwell and J. WUlff (T.P. 1032, with discussion) Nature of :Passivity in Stainless Steels and Other Alloys, I and 11. Ry H. H. Uhlig and John WUlff (T.P. 1050, with discussion) Thermal Expansion of Nickel-iron Alloys (Nickel from 30 to 70 Per Cent). Ry J. M. Lohr and Charles H. Hopkins (T.P. 987, with discussion) Low-temperature Transformation in Iron-nickel-cobalt Alloys. By L. L. Wy~Ian (T.P. 1013, with discussion) Fracture of Steels at Elevated Temperatures after Prolonged Loading. By R. H. Thielemann and E. R. Parker (T.P. 1034, with discussion)

Jan 1, 1939

Some Things We Don't Know about the Creep of Metals. By H. W. Gillett (T.P. 1087) Reduction of Iron Ores under Pressure by Hydrogen. By Michael Tenenbaum and T. L. Joseph (T.P. loll, with discussion) Induction Furnaces for Rotating Liquid Crucibles. By E. P. Barrett, W. F. Hol- bRook and C. E. Wood (T.P. 986, with discussion) Mechanism of Solidification and Segregation in a Low-carbon Rimming-steel Ingot,. By Anson Hayes and John Chipman (T.P. 988, with discussion) Solidification of Rimming-steel Ingots. By A. HultGRen and G. PhRagmen. (Contribution 112) Dendritic Structure of Some Alloy Steels. By Daniel .I. Martin and James L. Martin (T.P. 1066, with discussion) Occlusion and Evolution of Hydrogen by Pure Iron. By George A. Moore and Donald P. Smith (T.P. 1065, with discussion) Structure of Iron after Con~pression. Hy Charles S. Barrett (T.P. 977, with discussion) Structure of Iron after Drawing, Swaging, and Elongating in Tension. Ry Charles S. Barrett and L. H. LevensoN (T.P. 1038, with discussion) Magnetic Torque Studies of the Texture of Cold-rolled and of Recrystallized Iron-silicon Alloys. By Leo P. TaraSovJ(T.P. 1012, with discussion) Influence of Atmosphere and Pressure on Structure of Iron-carbon-silicon Alloys. By Alfred Boyles (T.P. 1046) Kinetics of the Decomposition of Austenite at Constant Temperature. By J. H. Austin and R. L. Rickett (T.P. 964, with discussion) Reaction Kinctics in Processes of Nucleation and Growth. By William A. Johnson and Robert F. Mehl (T.P. 1089, with discussion) Phase Changes in 3.5 Per Cent Nickel Steel in the Acl Region. By I. N. Bavarine (T.P. 1031, with discussion) Chromium in Structural Steel. By Walter Crafts (T.P. 1055) Surface Allotropic Transformation in Stainless Steel Induced by Polishing. By J. T. BuHwell and J. WUlff (T.P. 1032, with discussion) Nature of :Passivity in Stainless Steels and Other Alloys, I and 11. Ry H. H. Uhlig and John WUlff (T.P. 1050, with discussion) Thermal Expansion of Nickel-iron Alloys (Nickel from 30 to 70 Per Cent). Ry J. M. Lohr and Charles H. Hopkins (T.P. 987, with discussion) Low-temperature Transformation in Iron-nickel-cobalt Alloys. By L. L. Wy~Ian (T.P. 1013, with discussion) Fracture of Steels at Elevated Temperatures after Prolonged Loading. By R. H. Thielemann and E. R. Parker (T.P. 1034, with discussion)

Jan 1, 1939

By BERNARD PLANNER

PRODUCTION COSTS, profits, and quality are the primary factors in the peacetime production of iron and steel. In a war emergency, as high production rates and as complete utilization of readily available raw materials as possible, consistent with securing passable quality, become the most important factors. In this connection a discussion of some of the recent developments in the German iron and steel industry, where the problem of scarcity has naturally always been more acute than in the U.S.A., maybe of interest. To get more pig iron out of the existing blast furnaces it was necessary to obtain the maximum efficiency from the iron-bearing raw materials. This was achieved by eliminating all "excess baggage," chiefly by beneficiating the ore. The preparatory work for this was done by various methods which are effective when the ore either is too poor or contains too many impurities or too much gangue. Some of the beneficiation methods are well known, some are combinations of wet-mechanical, magnetic, roasting, sintering, and other treatments.

Jan 1, 1942

By AIME AIME

ON March 14, the University of Tulsa was accepted as a member of the North Central Association of Colleges, which ranks Tulsa among the leading universities of the country. A. G. OIiphant recently donated to the new school of petroleum engineering a splendid collection of books on geology, valued at $25,000. Waite Phillips, an oil producer and chairman of directors of The Independent Oil & Gas Co., donated $150,000 for a petroleum engineering building

Jan 1, 1929

By AIME AIME

T HE Mid-Continent Section of the Petroleum Division met on Mar. 11 in the engineer's room of the Tulsa Building, Tulsa, Okla., for the purpose of reviewing the papers presented at the annual meeting in New York. L. G. E. Pignell, chairman and delegate to New York for the Mid-Continent Section, read a brief report giving the outstanding features of the various papers that were presented. He expressed regret that more members of the Division could not be present in New York to hear the interesting papers and discussions. It was his opinion that the various remedies presented for overproduction seemed rather theoretical and impractical and he recommended that the engineers come to the aid of some of the economists in giving more practical consideration to the overproduction problem.

Jan 1, 1929

By Verne D. Johnston

ALTHOUGH the stocks of Lake Superior iron ore on dock or at furnaces at the beginning of the year were about 6,000,000 tons less than at the beginning of 1938, the steel industry was operating at only 52 1/2 per cent of capacity and continued at approximately this rate to about Aug. 1. Consequently the iron mines in the Lake Superior district during the winter and spring period were almost all on a curtailed production basis, governed mostly by the needs of the communities rather than by anticipation of ore demands. Many of these properties gave extra employment by prosecuting heavy strip- ping programs, and the underground mines by shaft sinking and rock development. All underground mines re- turned to full operation in September, mostly two-shift, five days per week. A few operated the sixth day. The ship- ping schedules were increased so that the actual delivery for the year exceeded early expectations by about 20 per cent. Final Lake shipments were slightly in excess of 45,000,000 gross tons.

Jan 1, 1940

By Nathaniel Herz

PARTING of bullion before shipment to the mint had been considered by the Homestake Mining Co. at various times, but had never been attempted before 1933, be- cause the margin of profit appeared to be too small to warrant the complications in refining. When the gold standard was abandoned by the United States in the spring of 1933, however, parting of the bullion was decided upon. The method selected was the Miller or chlorine process, which consists of the passing of gaseous chlorine into a bath of molten bullion, converting all metals other than gold into chlorides, and remov-

Jan 1, 1935

Roof Bolts An expansion shell and plug Westinghouse roof bolting assembly made for use with threaded steel rods and large flat washers or steel channel employs a plug larger in diameter than those for trolley wire service. The notched plug helps prevent shell and plug from turning. The unit is shipped complete. Circle No. 1 Fan The Jeffrey Mfg. Co. Aerodyne Midget fan is a self contained blower or exhauster for auxiliary ventilation through tubing. Operating rating with 5 hp motor is 6.5 in. maximum static pressure, and 6200 cfm free delivery volume. Weight is 340 to 475 lb and it may be furnished in open or permissible form. Circle No. 2 Heavy-Density Initial installation in the Mesabi Range country of the Wilmot-Daniels heavy-density concentrating system was a 175 ton per hour plant at the [ ] Skubic Bros. Virginia, Minn., operation. This Wilmot Engineering Co. unit has a separatory vessel providing unidirectional medium flow and as the only moving part uses a standard drag-line conveyor for lifting sink out of the bath. Circle No. 3 Portable pH Meter A low priced battery-operated portable pH meter of utmost simplicity announced by the Photovolt Corp. uses only 3 ordinary radio batteries which give over 2000 hours of service. Accuracy of 0.03 pH is claimed by the manufacturer for the model 125, and AC power line supply is available. Circle No. 4

Jan 1, 1952

By M. G. Corson

THE theory of hardening by interference with slip which has been so clearly developed by Jeffries and his co-workers requires that an alloy to be amenable to age or heat hardening should contain among its components some that will stay in solid solution at high temperatures and precipitate as a secondary phase on cooling. This secondary phase may be either a more or less pure individual element (chromium in the case of copper, anti-mony in the case of lead), or some intermetallic com-pound. Those cases of hardening which depend on the precipitation of a compound are not only the most frequent, but are also far superior in the efficiency of hardening obtained. However, the slip interference theory as stated in its most general form is not sufficient to foretell new cases of this type of hardening and also will not explain some phenomena of a more intricate nature. It is not sufficient that a secondary phase might be absorbed by the main one at high temperatures and precipitated at the lower ones. The kinetics of this precipitation and the accompanying. physical phenomena of dimensional changes play independent and highly important parts. These kinetics, while not yet sufficiently studied to he formulated in the shape of physicochemical equations, might find their expression-in a qualitative systema-tization of the phenomena of precipitation according to two different viewpoints. To begin with, we encounter the question as to the velocities of the precipitation and of the growth of the phase precipitated. To harden a metal in an efficient manner we must be able to control the precipitation on one hand and also to bring the total of the secondary phase to such a number and size of the particles pre-cipitated as, will produce a desirable hardening effect under commercially feasible conditions of. age or heat hardening. From this viewpoint six different cases may be dis-cerned.

Jan 7, 1928

By AIME AIME

THE annual meeting of the Woman's Auxiliary to the A.I. M.E. is always held in New York, in con- junction with the annual meeting of the Institute in February. Business sessions, teas, dances, a theater party, luncheons, excursions, and many other interesting activities filled the four days to overflowing. In all ,216 women were present, from all parts of the United ,/ mates, and there were several from Canada. On Mon- ' day not only the visitors, but the New York members also, gathered around the registration desks, where Mrs. E. N. Wolfes, Mrs. S. J. Jennings, and Miss Georgene Davis saw that everyone was properly registered and provided with tickets to whatever functions she desired to attend. Greetings were eagerly ex- changed as friends met at the luncheon on the fifth floor, where the hostesses of the day were Mrs. J. D. Handy, Mrs. T. T. Read, Mrs. Sidney Rolle and Mrs. H. J. Wolf. In the afternoon, there were visits to art galleries and other interesting exhibits, arranged by Mrs. Frederick Laist. Mrs. W. H. Bassett was the hostess at a very delightful Thé damant at the Italian Gardens of the Ambassador Hotel. Many of the men attended this function also. In the evening the visiting ladies were entertained at a theater party, with Mrs. Wilbur Judson as hostess. The play that was seen was Gorki's "At. the Bottom."

Jan 1, 1930

By R. W. Raymond

THIS meeting was held in the new home of the Institute, the United Engineering Society Building, 29 West 39th Street, New York City, directly following the Dedication ceremonies. The first session was held in the large Auditorium, Thursday, April 18. The meeting was called to order by Mr. John Hays Hammond, President of the Council, who said Before taking up the reading and discussion of papers, I will call upon Dr. Rossiter W. Raymond, the oldest living past-President of the Institute, who has been in harness almost continuously for thirty-six years, and who has contributed more than any one else to bring this society to its present great success and to establish the reputation of the American mining engineer the world over, for a few words supplementary to those which were uttered to engineers generally, during the sessions of yesterday and the day before. ADDRESS BY R. W. RAYMOND. The generally accepted Darwinian doctrine of the survival of the fittest is sometimes illustrated by persons who are supposed to be the fittest because they have simply survived. I fear that I come under that category. Almost all of my contemporaries in the early history of this Institute have passed away. Only one or two of the original founders remain, and I may fairly say that scarcely any remain who were active at that : time in shaping the organization and the future career of the Institute. In May, 1871, I was thirty-one years old. Next week I shall be sixty-seven years old. All the intervening years have been devoted to the service of this Institute almost continuously, either as President or Vice-President or Secretary. You may easily imagine, therefore, with what pleasure I greet you on this occasion. I am not here to extend to you the welcome of the City - of

May 1, 1907

By Ellsworth Daggett

Jan 1, 1879

By L. D. Jaffe, F. W. Cotter, E. Cordon

The hardenability of titanium-base alloys was studied by metallographic examination and hardness survey of Jominy specimens end-quenched from the B range. Analyses of the data led to the equation log J = -0.57 + 0.25 @ct Fe + pct Mn + pct Mo) + 0.19 @ct Cr) +0.16 @ct V) + 0.03 @ct Zr). Here J is the distance, in sixteenths of an inch, from the quenched end of a Jominy hardenability specimen in the position of peak hardness, for material quenched from the B range. This equation fitted the experimental data with a standard deviation of approximately 0.29. The effects of the elements Al, Sn, W, Cu, Ni, B, C, N, 0, and H, and of pain size, were not statistically significant or not practically significant. A check against hardenability measurements in the literature showed agreement within the stated standard deviation. The equation should be useful in estimating hardenability of new or modified titanium alloys. HARDENABILITY in a titanium-base alloy is the ability of the alloy to retain the B structure on quenching. An alloy with high hardenability will retain the /3 structure even when cooled relatively slowly from a temperature at which B or P plus a is stable. A low hardenability material will retain P only if quenched extremely rapidly from the range of p or 0-plus-a stability, or will not retain it at all, at room temperature. High hardenability is desirable in titanium alloys to be heat-treated to high-strength levels. Its value is by no means limited to large section sizes. With high hardenability, a material can be solution-treated and cooled at a variety of rates, either to give high strength directly or, more generally, to give a soft ductile condition from which high strength can be obtained by subsequent aging. With low hardenability, high strength can be obtained, if at all, only by very rapid quenching, and there will generally be little increase in hardness on subsequent aging; an alloy of this type is limited in its applicability. On the other hand, alloys of very low hardenability have some advantages in weldability; essentially, they are always in the annealed condition, after welding as well as before. For commercial alloys, hardenability data are usually available, in the form either of property data after cooling from the solution temperature at various rates, with or without subsequent aging, or of results of a standard hardenability test, such as that originally developed for steels by Jominy and Boegehold.' When modifications of an available alloy are considered, or preparation of new alloy compositions, it would be Very convenient to be able to estimate the hardenability of the new material without having to make and test it. A method of estimating hardenability of titanium alloys from their composition was suggested by one of the authors some time ago, on a preliminary basis, utilizing scattered data found in the literature.' It seemed worthwhile to carry out a systematic experimental study of the effect of composition upon hardenability. EXPERIMENTAL PROCEDURE Approximately fifty heats of various compositions, weighing 8 to 10 Ib apiece, were melted in a small inert-gas tungsten-arc furnace with water-cooled copper walls. The starting material was 110 Brine11 titanium sponge, with high-purity metals added for alloying. Each heat was bottom-poured under vacuum through a molybdenum burnout strip into a cold graphite mold, to form an ingot approximately 4-1/2 by 3-1/2 by 3 in.* From each ingot were cut *The material was melted and cast by Pitman-Dunn Laboratory, Frankford Arsenal, to whom the authors must express their thanks. two pieces 4-1/2 by 1-1/2 by 1-1/2 in. These were forged, at temperatures adjusted to the composition, into 1-1/4-in. rounds, from which standard 1-in.-diam hardenability specimens3 were machined. A number of small samples were also prepared from forged materials of each heat, annealed, quenched from various temperatures, and examined metallographically. The P-transus temperature was determined by observation of the degree of resolution of primary a in these pieces. samples for chemical analyses were also taken from the forgings. One hardenability specimen of each heat was solution-treated for 1 hr approximately 50°F above the measured transus temperature, and the other for 1 hr approximately 250°F above the transus. (An additional hour was allowed for the specimens to reach furnace temperature.) These are not necessarily the temperatures that would be selected for

Jan 1, 1964

Jan 1, 1908

By T. Yoshioka, Paul A. Beck

SILICON, germanium, and tin occur with both the white tine-type structure and the diamond cubic structure. In the latter form these elements are semiconductors; in the former they are metallic. The metallic form of germanium and silicon is obtained only under high pressure.' For all three elements the transition from the semiconductor to the metallic state is accompanied by a decrease in the atomic volume of somewhat more than 20 pctily2 Table I. At such a large compression the widening of the s and p bands is sufficient to make the energy gap of 1.1 ev, or less, of the semiconductor disappear, giving rise to the metallic state.*

Jan 1, 1965

By M. B. Riordan

A surface indicating pressure, temperature and flow instrument that ernploys variable frequency sensing elements has proved useful in evaluating flow characteristics of wells. Relative productivity of individual oil and gas sands in a given well can be analyzed at several back pressures. The variable frequency sensing elements are an improvement in sensitivity and accuracy and make possible observation of temperature and pressure variations that have not been possible heretofore. The surface indicating featuere results in a more direct approach to solving problems and eliniinate; many assumptions. All three subsurface factors are evaluated, and correlation between them results in a direct means of analyzing reservoir. and well conditions. Surveys have been used to evaluate well performance. locate gas entry In high ratio wells and to investigate gas injection and water flooding conditions. INTRODUCTION In a flowing well that is open to a multiple number of producing sands with varying characteristics. it is valuable to know which sands are producing fluid at a given back pressure and in what relative quantity. Core studies could qualify an interval as productive, and reserves would be computed on this basis. Unless the well is produced so that the interval does contribute. irreparable damage to the interval can occur. It is generally accepted that the optimum condition of pro-

Jan 1, 1951

By M. B. Riordan

A surface indicating pressure, temperature and flow instrument that ernploys variable frequency sensing elements has proved useful in evaluating flow characteristics of wells. Relative productivity of individual oil and gas sands in a given well can be analyzed at several back pressures. The variable frequency sensing elements are an improvement in sensitivity and accuracy and make possible observation of temperature and pressure variations that have not been possible heretofore. The surface indicating featuere results in a more direct approach to solving problems and eliniinate; many assumptions. All three subsurface factors are evaluated, and correlation between them results in a direct means of analyzing reservoir. and well conditions. Surveys have been used to evaluate well performance. locate gas entry In high ratio wells and to investigate gas injection and water flooding conditions. INTRODUCTION In a flowing well that is open to a multiple number of producing sands with varying characteristics. it is valuable to know which sands are producing fluid at a given back pressure and in what relative quantity. Core studies could qualify an interval as productive, and reserves would be computed on this basis. Unless the well is produced so that the interval does contribute. irreparable damage to the interval can occur. It is generally accepted that the optimum condition of pro-

Jan 1, 1951

By Edward J. Ryan, E. A. Peretti

iV preliminary X-ray and metallographic survey of the ternary system Bi-In-Te revealed that the following isopleths could form quasibinary systems: InTe-Bi, InTe-InBi, InTe-BizTe3, and InzTe3-Bi2Te3. The nature of the InTe-Bi phase diagram was established by Bologna and Peretti.' This article presents the results of an investigation of the InTe-InBi system by thermal analysis, X-ray methods, and metallographic examination. The bismuth and tellurium were bought from the American Smelting and Refining Co. The tellurium had the following spectrographic analysis: 0.0001 pct Mg, 0.0001 pct Si, 0.0001 pct Fe, 0.0002 pct Al, and 99.999+ pct Te (by difference). The bismuth assayed: 0.0001 pct Mg, 0.0001 pct Pb, 0.0001 pct Fe, 0.0001 pct Cu, and 99.999+ pct Bi (by difference). The indium was obtained from the Indium Corp. of America and contained 0.002 pct Cu, 0.006 pct Pb, 0.01 pct Sn, 0.01 pct Zn, and 99.97+pct In. The alloys were made by melting the required proPortions of InTe and in evacuated, sealed quartz

Jan 1, 1967

By J. J. Tietien, R. O. Clough

A technique previously used to prepare alloys of InAs1-xPx and GaAsl-x Px, miry: the gaseous hydrides arsine and phosphine, has been extended to grow single -crystalline GaAs 1-x Sb x by replacing the phos-phine with stibine. Procedures were developed for handling and storing stibine which now make this chemical useful for vapor phase growth. This represents the first time that this series of alloys has been grown from the vapor phase. Layers of P -type GaSb and GaSb-rich alloys have been grown with the carrier concentrations comparable to the lowest ever reported. In addition, a p-type alloy containing 4 pct GaSb exhibited a mobility of 400 sq cm per v-sec which is equivalent to the highest reported for GaAs. RECENTLY, interest has been shown in the preparation and properties of GaAs1-xSbx alloys, since it was predicted1 that for compositions in the range of 0.1 < x < 0.5, they might provide improved Gunn devices. However, preparation of these alloys presents fundamental difficulties. In the case of liquid phase growth, the large concentration difference between the liquidus and solidus in the phase diagram, at any given temperature, introduces constitutional supercooling problems. It is likely that, for this reason, virtually no description of the preparation of GaAs1-xSbx by this technique has been reported. In the case of vapor phase growth, problems are presented by the low vapor pressure of antimony, and the low melting point of GaSb and many of these alloys. In previous attempts1 at the vapor phase growth of these materials, using antimony pentachloride as the source of antimony vapor, alloy compositions were limited to those containing less than about 2 pct GaSb. This was in part due to the difficulty of avoiding condensation of antimony on introducing it to the growth zone. A growth technique has recently been described2 for the preparation of III-V compounds in which the hydrides of arsenic and phosphorous (AsH3 and pH3) are used as the source of the group V element. With this method, GaAs1-xPx and InAs1-xPx have been prepared2&apos;3 across both alloy series with very good electrical properties. Since the use of stibine (SbH3) affords the potential for effective introduction of antimony to the growth apparatus, in analogy with the other group V hydrides, this growth method has been explored for the preparation of GaAs1-xSbx alloys. In addition to GaSb, these alloys have now been prepared with values of x as high as 0.8. In the case of GaSb, undoped p-type layers were grown with carrier concentrations equivalent to the lowest reported in the literature. Thus it has been demonstrated that, with this growth technique, all of the alloys in this series can be prepared. EXPERIMENTAL PROCEDURE A) Growth Technique. The growth apparatus, shown schematically in Fig. 1, and procedure are virtually identical to that described2 for the growth of GaAs1-xPx alloys, with the exception that phosphine is replaced by stibine.* HCl is introduced over the gallium boat to *Purchased from Matheson Co., E. Rutherford,N+J. transport the gallium predominantly via its subchlo-ride to the reaction zone, where it reacts with arsenic and antimony on the substrate surface to form an alloy layer. The fundamental limiting factors to the growth of GaAs1-xSbx alloys from the vapor phase, especially GaSb-rich alloys, are the low melting point of GaSb (712°C) and the low vapor pressure of antimony at this temperature (<l mm). Thus, relatively low antimony pressures must be employed, which, however, imply low growth rates. To provide low antimony pressures, very dilute concentrations of arsine and stibine in a hydrogen carrier gas were used. Typical flow rates (referred to stp) were about 4 cm3 per min of HC1 (0.06 mole pct)+ from 0.1 to 1 cm3 per min of ASH, (0.002 to 0.02 mole pct), and from 1 to 10 cn13 per min of SbH3 (0.02 to 0.2 mole pct), with a total hydrogen carrier gas flow rate of about 6000 cm3 per min. Although no precise data on decomposition. kinetics exist, it is known4 that stibine decomposes extremely rapidly at elevated temperatures. However, the high linear velocities attendent with the high total flow rate (about 2000 cm per sec) delays cracking of the stibine until it reaches the reaction zone and prevents condensation of antimony in the system. To improve the growth rates of the GaSb-rich alloys, growth temperatures just below the alloy solidus are main-

Jan 1, 1970