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By W. J. Millard

Owing to a moratorium in the drilling of crown-land leases in Trinidad during the year of 1931, only 40 wells were spudded in during the first eight months as compared with 110 during the same period in 1930. Nevertheless the production will show an increase of about 400,000 bbl. over that of 1930. An estimate is given in Table 1. Since the oil produced in 1930 was 9,418,907 bbl. and that in 1931 probably will be 9,853,976 bbl., the year 1931 probably will see an increase of about 4.6 per cent. The gross production of crude oil in the colony has increased steadily year by year, with the exception of 1919, when there was a slight decline. A tabulated statement was given last year.' The Petroleum Times of March 21, 1931 (p. 413) gives the total production of 1930 as 9,418,000 bbl. and the average monthly production as 784,833 bbl. The same two items for 1931 are estimated at 9,853,976 and 821,165 bbl., respectively.

Jan 1, 1932

By Rip Thompson

ALTHOUGH the metallurgical treatment for the Ophir Hill tailings was developed more than 20 years ago and in the interim a vast amount of experimental work was done with later-developed flotation rea-gents, it was found necessary to revert to the original oil reagents and their combina-tions with specific chemical reagents in order to obtain results of economic value. This is of especial interest because in present ore-treatment investigations later-developed flotation reagents are used almost exclusively and the coal-tar deriva-tives, except in certain patented reagents, are virtually neglected. These coal-tar oils and derivatives still have a definite field of application, especially in the treatment of some oxidized ores when modified sulphidi-zation is desirable. The Ophir Hill tailings deposit is in Ophir Canyon, Tooele County, Utah, about 55 miles southwest of Salt Lake City and 25 miles south of the Tooele smelter of the International Smelting and Refining Co. A road good for trucks leads directly from the Ophir mill to the smelter.

Jan 1, 1940

By Thomas M. Dr. Drown

REMARKABLE as have been the direct results of Danks's puddler, there are some indirect and incidental results, which are well worthy of study for their intrinsic value and suggestiveness. The success of Danks's machine is due mainly to the nature of the lining and the manner in which it is attached to the walls of the revolving chamber. Herein lies Danks's merit and good fortune. Given such a lining, and the success of the machine, as far as puddling iron is concerned, could easily be predicted. Other important results have, however, been obtained with this machine, which, though clearly explicable, were, nevertheless, unanticipated. These are the increased yield of bar-iron over the pig-iron charged, and the elimination of phosphorus, which, though not absolutely complete, is yet more decided than in the case of hand-puddling. As regards the increased yield, this is merely what we have a right to expect if we consider the puddling process to consist in the oxidation of the carbon and silicon of the pig by the oxygen of the oxide of iron. That this result is attained, nearly to the extent that the theory requires, in Danks's puddler, and has never been more than partially attained by the most careful experiments in hand-puddling, points clearly to the fact that the contact of the molten pig-iron with the oxide of iron is much more intimate and complete in the one instance than in the other. The action of puddling in Danks's machine may be considered to be twofold first, the removal of the carbon, silicon, and phosphorus of the pig, which is the primary object, and, second, the production of wrought iron direct from the ore, which is entirely an incidental result. Intelligent metallurgists were not long in recognizing in this latter result a fact of deeper import and greater value than the attainment of a perfect puddling process. A new method

Jan 1, 1874

By E. A. Smith, E. R. Parker

METALLURGISTS and engineers have always been interested in the mechanism of high-speed deformation because metals are rapidly deformed in various applications and manufacturing processes. The deformation of metals by impact loads has recently engaged the attention of a number of investigators. Many of their results have not been disclosed but some of the published investigations1-8 have shown that the tensile strength, yield strength and elongation generally increase with increasing strain rate. The investigation reported herein is an attempt to determine the reason for this increase in strength and elongation. Single-crystal copper specimens were broken in tension at impact velocities up to 100 ft. per sec. The distribution of slip bands in the fractured crystals was found to depend upon the strain rate. In the bars broken at high speeds, the slip bands appear to be more numerous. This might account for the higher strength as well as the greater elongation. EXPERIMENTAL PROCEDURE Single crystals of copper (approximately 99.98 per cent) were made in graphite molds by the conventional method of lowering the mold out of the hot zone of a hydrogen furnace at a rate of one inch per hour. Solidification progressed from the bottom upward, forming a single crystal. The crystals were about 0.30 in. in diameter and 4 in. long. They were made into test bars by sliding threaded steel bushings over each end of a crystal and then flowing silver solder between the crystal and the bushing. The inside diameter of the bushings was slightly greater than the diameter of the crystals, to allow space for the silver solder. The bushings were placed so that the gauge length of the crystals was one inch. The assembly is shown in Fig. I, with two views of a fractured crystal. Annealed polycrystalline copper bars of similar shape were machined from solid stock. X-ray measurements were made on all single crystals to determine their orienta¬tions. The results are shown in Fig. 2, where the location of the axis of each specimen is indicated on a standard projection. The bars were broken in a commercial variable-velocity tension im¬pact machine, which has been described in detail elsewhere.7,8 The stress and strain were recorded by means of wire strain gauges and a special commercial oscillo-raph, also described in detail elsewhere.9,10 The equipment and method can be briefly described as follows. The impact machine consists of a motor-driven flywheel containing a two-pronged hammer. This hammer is held retracted in the flywheel

Jan 1, 1944

As REVISED IN CONFERENCE FEB. 17, 1931 REPORT OF SUBCOMMITTEE ON MINE VENTILATION CODE OF A, I. M. E. COMMITTEE ON VENTILATION ALFRED W. HESSE, Chairman THOMAS G. FEAR GEORGE S. RICE E. A. HOLBROOK WILLIAM A. ROWE HOWARD ECKFELDT R. V. NORRIS CADWALLADER EVANS, JR. H..1. SMITH, Secretary REALIZING, from the safety and health standpoint, the need of furnishing air of good quality to workers underground and of diluting and carrying away dangerous and noxious gases, the following code is offered to unify regulatory measures in coal mine ventilation, so far as is practicable, in the United States of America.

Jan 1, 1931

Discussion of the paper of F. C. LANGENBERG and R. G. WEBBER, presented at the New York meeting, February, 1915, and printed in Bulletin No. 98, February, 1915, pp. 291 to 300. HENRY M. HOWE, Bedford Hills, N. Y.-The results here given are of great interest and are welcome as forming another rivet to increase the stability of our present theories of the constitution and properties of steel. The important discovery is that the hysteresis increases with the fineness of the structure, that is to say with the extent of contact between the particles of ferrite and cementite. All of the specimens except No. 4 consist of ferrite and cementite of different degrees of intimacy of admixture. If hysteresis represents something akin to surface friction, which retards the rotation of the ferrite on the application and release of the magnetizing force, then it is only natural that it should increase as it does with the intimacy of admixture, because it is at the surface of contact of a given particle of ferrite with the neighboring particles of cementite that this friction is to be expected, and of course the extent of surface must in¬crease with the intimacy of admixture. The somewhat greater hardness of specimen 4 than of the others may perhaps he referred to the principle discussed in my paper, Why Does Lag Increase with the Temperature from Which Cooling Starts?' The furnace-cooled specimens were cooled so slowly that the influence of the initial temperature of heating is effaced. But in the air-cooled specimens we have the suggestion that the high temperature, 1,000°, from which the cooling of No. 4 started has prevented the completion of the transformation, with the result that the metal is slightly harder than any of the others. The difference is not to be explained by difference in the fineness of structure, because the whole range of fineness from No. 1 to No. 6 is accompanied by no change in hardness, the only change being an appreciable increase of hardness following the air cooling from 1,000°.

Jan 5, 1915

Albin, B. R Billings, Mont. Amster, Nathan L 25 Broad St., New York, N. Y. Bache, Jules S 42 Broadway, New York, N. Y. Barrett, C. P6338 Harper Ave., Chicago, Ill. Baum, Frank G Hobart Bldg., San Francisco, Cal. Bayless, Hon. William S Russ Bldg., San Francisco, Cal. Bean, Louis H., V.P., Dwight P. Robinson & Co., Inc 125 E. 46th St., New York, N. Y. Beatty, Ross J 1106 First National Bank Bldg., Chicago, Ill. Benwell, Oswald F 205 Colorado National Bank, Denver, Colo. Beymer, Albert S., V.P., Keystone National Bank Pittsburgh, Pa. Bingham, Charles W 1542 Hanna Bldg., Cleveland, Ohio. Blumenthal, Hugo 44 Pine St., New York, N. Y. Boettcher, Charles Ideal Cement Bldg., Denver, Colo. Bowlus, Thomas H Iola, Kans. Bragg, E. B Carmel, Cal.

Jan 1, 1929

Albin, B. R Billings, Mont. '28 Amster, Nathan L 25 Broad St., New York, N. Y. '28 Bache, Jules S 42 Broadway, New York, N. Y. '28 Barrett, C. P 5338 Harper Ave., Chicago, 111. '28 Bayless, William S Russ Bldg., San Francisco, Cal. '28 Bean, Louis, H 60 E. 42nd St., New York, N. Y. '28 Beatty, Ross J Room 604, 6 N. Clark St., Chicago, III. '28 Benwell, Oswald F Hold Mags. '28 Beymer, Albert S., V.P., Keystone National Bank Pittsburgh, Pa. '28 Blumenthal, Hugo 44 Pine St., New York, N. Y. '28 Boettcher. Charles Ideal Cement Bldg., Denver, Colo. '28 Bowlus, Thomas H., Banker, Pres., Allen County State Bank Iola, Ran. '28 Brown, Colvin B Chamber of Commerce, Washington, D. C. '28 Burt, Maxwell Struthers Southern Pines, N. C. '28

Jan 1, 1934

By S. W. Miller

MOST of the steel welding done at the present time is in material containing not over 0.3 per cent. carbon, and the tests here described were in similar material. These tests are not as yet completed but it is hoped that more results and more reasons for the conclusions may be presented at the meeting in February. From the time the author found the peculiar structure in electric welds referred to in a previous paper,1 that is, needles or plates in the grains and similar material, in larger spots, at the grain boundaries, he has felt that these plates which may be iron nitride and probably contain some carbon, were at least partly responsible for the brittleness of electric welds. He has found but few traces of similar lines in oxyacetylene welds until the last 2 mo., when he has found them in large numbers under certain conditions. In the top of these welds, they are quite numerous. In the body of heavy oxyacetylene welds, they appear at times, but not nearly to the extent that they do in electric welds; the author has never seen them in the body of welds in material less than ;3/4 in. (19 mm.) thick. They are shown in Fig. 82. The reason they were not noticed before is undoubtedly due to the fact that in making tests of welded pieces the weld was always ground off level with the plate, and as this structure only appears in the top ;1/16 in. (1.5 mm.) of the weld, they were removed by the grinding or machining; also, welds ¾ in. thick had not been examined. It did not appear, in making bending tests, that this structure had much influence on the strength of oxyacetylene welds; while electric welds are noticeably brittle. Further, oxyacetylene welds made with certain special materials were exceedingly brittle even after the tops of the welds were removed; this was true in cases where there was no sign of the plates whatever and where the welds were remarkably free from oxide and the other usual defects. It appeared, therefore, that this brittleness did not depend on any variable that had been noticed so far, and it was

Jan 2, 1919

Jan 1, 1968

By W. Klement

By quenching liquid alloys, single-phase solid solutions are obtained in the ranges 0 to 42.0 at. pct Co-Au and 0 to 15 and 75 to about 100 at. pet Co-Cu. Metastable solid solutions are also found in multiphase 42.0 to 49.0 and 69. 0 to about 100 at. pet Co-Au alloys. fie inability to achieve complete solid solubiliiies in Au-co and cu-co alloys is rationalized by a conszderation of the rate processes during cooling and solidification. Trends in lattice distortion and shifts in the compositions of the melting-point minima and critical points are discussed for the binary alloys of copper, silver, and gold with some of the transition metals of the first long period. By rapidly cooling alloys from the melt, a continuous series of metastable solid solutions can often be obtained for components of similar crystal structure which normally form eutectic systems.' The eutectic system Au-Co, Fig. 1, and the peritectic system Cu-Co, Fig. 2, were investigated in order to determine the extent of the metastable solid solutions attainable with the present technique.* EXPERIMENTAL PROCEDURES Most of the alloys were prepared by melting weighed quantities of the elements (purity greater than 99.9 pct) under hydrogen in alumina crucibles by means of induction heating. After reweighing, the alloys were cast under argon into 1 mm diam wires. However, it was not possible to prepare some of the Cu-Co alloys with the requisite homogeneity (over about 1 mm3) in this way. For these alloys, reduced powders (purity greater than 99.9 pct) were mixed for 12 to 48 hr, pressed into compacts that were sintered at 1000º to 1050°C for 6 to 48 hr under hydrogen, and then furnace-cooled. Alloy charges of a few mm3, cut from the cast wires or chipped from the sintered compacts, were heated to 1550º to 1600°C in 30 sec in an alumina insert held within a graphite support and then ejected by a pulse of helium onto a lightly polished copper strip on the inner periphery of a rotating wheel. The

Jan 1, 1963

By K. E. Brown, G. H. Fancher

An 8,000-ft experimental field well was utilized to conduct flowing pressure gradient tests under conditions of continuous, multiphase flow through 2 3/8-in. OD tubing. The well was equipped with 10 gas-lift valves and 10 Maihak electronic pressure recorders, as well as instruments to accurately measure the surface pressure, temperature, volume of injected gas and fluid production. These tests were conducted for flow rates ranging from 75 to 936 B/D at various gas-liquid ratios from 105 to 9,433 scf/bbl. An expanding-orifice gas-lift valve allowed each flow rate to be produced with a range of controlled gas-liquid ratios. From these data an accurate pressure traverse has been constructed for various flow rates and for various gas-liquid ratios. A comparison of these tests to Poettmann and Carpenter's correlation indicates that deviations occur for certain ranges of flow rates and gas-liquid ratios. Numerous curves are presented illustrating the comparison of this correlation with the field data. Poettmann and Carpenter's correlation deviates some for low flow rates and, in particular, for gas-liquid ratios in excess of 3,000 scf/bbl. These deviations me believed to be mainly due to the friction-factor correlation. However, Poettmann and Carpenter's correlation gives excellent agreement in those ranges of higher density. This was as expected and predicted by Poettmann. He pointed out that their method was not intended to be extended to those ranges of low densities whereby an extreme reversal in curvature occurs.l As a result of these experimental tests, correlations using Poettmann and Carpenter's method were established between the friction factors and mass flow rates which are applicable for all gas-liquid ratios and flow rates. Definite changing flow patterns do not allow any one correlation to be accurate for all ranges of flow. INTRODUCTION The ability to analytically predict the pressure at any point in a flow string is essential in determining optimum production string dimensions and in the design of gas-lift installations. This information is also invaluable in predicting bottom-hole pressures in flowing wells. Although this problem is not new to industry, it has by no means been solved completely for all types of flow conditions. Versluys,2 Uren, et al, 3 Gosline,4 May,5 and Moore, et al,6,7 were all early investigators of multiphase flow through vertical conduits. However, all of these investigations and proposed methods were very limited as to their range of application. Likewise, many are extremely complicated and therefore not very useful in the field. Only in the last decade have any significant methods been proposed which are generally applicable. The most widely accepted procedure in industry at the present time is a semi-empirical method developed from an energy balance, proposed by Poettmann and Carpenter8 in 1952. Their correlation is based on actual pressure measurements from field wells. Accurate predictions from this correlation are limited to high flow rates and low gas-liquid ratios. Although this method will be discussed in detail later, it should be pointed out that two important parameters, namely the gas-liquid ratio and the viscosity, were omitted in their correlation. The viscosity was justifiably omitted since their data was in the highly turbulent flow region for both phases, and most wells fall in this category. The gas-liquid ratio was incorporated to some extent in the gas-density term. In 1954, Gilbert9 presented numerous pressure gradient curves obtained from field data for various flow rates and gas-liquid ratios for the determination of optimum flow strings. However, no method is presented for predicting pressure gradients except by comparison to these curves. Baxendell, et al,10 proposed a method based on Poettmann and Carpenter's procedure

By W. A. Roper

Since 1950, several papers have been published which have described various methods for studying mobility ratio effects. The methods which have been described for studying mobility ratio effects include X-ray shadowgraph techniques, stepwise potentiometric model procedures, stepwise numerical procedures, gelatin model studies and fluid mapper model studies. The purpose of this paper is to describe a procedure for using a resistance network for studying mobility effects. DESCRIPTION OF APPARATUS The basic unit of the experimental model consisted of a network of 840 resistors fastened to a sheet of black Lucite which was mounted on a wooden frame, Fig. 1. The dimensions of the Lucite sheet were 36 X 36 in. The resistors were fastened to the Lucite sheet at mesh points by means of snaps. The mesh points were arranged in a square pattern, 30 X 30 in., spaced at intervals of l1/2 in. The snap fasteners permitted several resistors to be "stacked" in parallel. By adding additional resistors to the basic unit, the specific resistance on each side of the flood front could be varied. The square network of resistors represented one of four symmetrical elements of a five-spot well pattern. The current input was analogous to an injection well and the current output was analogous to a production well." The power supply was essentially a full wave transformer-rectifier system for converting alternating-current into direct-current. The DC voltage could be varied from 41.43 to 290 v in steps of 41.43 v by selecting the proper outlet jacks. The major components of the power supply were: a Triro power transformer, R 11-A; a dual 5Y3 vacuum tube; two gas filled OD-3 tubes; and a Triplett voltmeter, model 227-1, range 0 to 500 DC v. The voltages at the mesh points were determined with a Keithley electrometer, model 210, No. 185, manufactured by Keithley Instruments, Cleveland, Ohio. A Heathkit vacuum tube volt-

Albin, B. R Billings, Mont. '28 Amster, Nathan L 25 Broad St., New York, N. Y. '28 Bache, Jules S 42 Broadway, New York, N. Y. '28 Barrett, C. P 5338 Harper Ave., Chicago, 111. '28 Bayless, William S Russ Bldg., San Francisco, Cal. '28 Bean, Louis, H 60 E. 42nd St., New York, N. Y. '28 Beatty, Ross J Room 604, 6 N. Clark St., Chicago, III. '28 Benwell, Oswald F Hold Mags. '28 Beymer, Albert S., V.P., Keystone National Bank Pittsburgh, Pa. '28 Blumenthal, Hugo 44 Pine St., New York, N. Y. '28 Boettcher. Charles Ideal Cement Bldg., Denver, Colo. '28 Bowlus, Thomas H., Banker, Pres., Allen County State Bank Iola, Ran. '28 Brown, Colvin B Chamber of Commerce, Washington, D. C. '28 Burt, Maxwell Struthers Southern Pines, N. C. '28

Jan 1, 1936

By G. R. Frank, R. E. Willett, E. H. Hollingsworth

The most generally accepted equilibrium diagram for A1-Fe alloys has a eutectic system on the aluminum side with an essentially insoluble constituent of the formula, FeAl,, as the second phase. In 1938, Bradley and Taylor1 did report a phase change of FeAl,, but this change has never been confirmed. According to them, FeA1, is the stable phase only at higher temperatures; at lower temperatures, it is converted into Fe2Al7 and aluminum. It has now been found that there is, in fact, a phase change of the Al-Fe constituent on the aluminum side of the equilibrium diagram. This change, however, is not the one reported by Bradley and Taylor. The alloys used were cast by continuous processes and had these analyses: Fe - 1.98 to 2.02 pct, Cu-0.01 pct, Si - 0.01 pct, Mn - 0.01 pct, Mg - 0.00 pct, Zn - 0.00 to 0.01 pct, Cr - 0.00 pet, Ti - 0.00 to 0.04 pct. The constituent in these alloys was identified by X-ray analysis with a Guinier camera and by chemical and X-ray powder diffraction analyses. Two procedures were used to separate constituent for the last two analyses. In one procedure, it was separated by treating a sample with a solution of methanol saturated with iodine. And in the other procedure, it was separated by first applying, at 12 amp per sq ft in 15 pct sulfuric acid at 70°F, an oxide coating to a sample, and then dissolving this coating in a solution of 35 ml of 85 pct H3PO4 and 20 g of CrO3 per liter. Several observations directed attention to a phase change of the A1-Fe constituent. Differences that appeared too great to be accounted for by micro-structure alone were found in the voltages required to apply the same thickness of an oxide coating to products from rapidly and slowly chilled ingot. Even more striking was the difference in appearance of the coatings themselves. One applied to a product from a rapidly chilled ingot was dark gray in appearance, in fact, almost black, while one applied to a product from a slowly chilled ingot was essentially white. Also, even a short period of thermal treatment at an elevated temperature of products from rapidly chilled ingot led to the same anodizing behavior as that of products from slowly chilled in-

Jan 1, 1962

By S. W. Miller

MOST of the steel welding done at the present time is in material containing not over 0.3 per cent. carbon, and the tests here described were in similar material. These tests are not as yet completed but it is hoped that more results and more reasons for the conclusions may be presented at the meeting in February. From the time the author found the peculiar structure in electric welds referred to in a previous paper,1 that is, needles or plates in the grains and similar material, in larger spots, at the grain boundaries, he has felt that these plates which may be iron nitride and probably contain some carbon, were at least partly responsible for the brittleness of electric welds. He has found but few traces of similar lines in oxyacetylene welds until the last 2 mo., when he has found them in large numbers under certain conditions. In the top of these welds, they are quite numerous. In the body of heavy oxyacetylene welds, they appear at times, but not nearly to the extent that they do in electric welds; the author has never seen them in the body of welds in material less than ;3/4 in. (19 mm.) thick. They are shown in Fig. 82. The reason they were not noticed before is undoubtedly due to the fact that in making tests of welded pieces the weld was always ground off level with the plate, and as this structure only appears in the top ;1/16 in. (1.5 mm.) of the weld, they were removed by the grinding or machining; also, welds ¾ in. thick had not been examined. It did not appear, in making bending tests, that this structure had much influence on the strength of oxyacetylene welds; while electric welds are noticeably brittle. Further, oxyacetylene welds made with certain special materials were exceedingly brittle even after the tops of the welds were removed; this was true in cases where there was no sign -of the plates whatever and where the welds were remarkably free from oxide and the other usual defects. It appeared, therefore, that this brittleness did not depend on any variable that had been noticed so far, and it was

Jan 2, 1919

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

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

Jan 1, 1967

By E. S. Lenker, H. J. Van Hook

A complete swies of solid solutions has been found between the compounds InAs and GaAs Below the solidus. The melting relations determined by differential thermal and static quenching technzques, indicate that the liquidus and solidus are of the simple ascendant type. No evidence of unmixing of the homogeneous solid solutions was observed at sub-solidus temperatures. A quenching method for locnting the solidus, using X-ray diffraction techniques, is described in some detail. THE semi-conducting properties of compounds formed by various combinations of the less familiar intermetallic elements have created an increasing interest in the phase relations in systems involving these elements. The complete phase diagram of such a system, containing a compound of special interest, will often provide information as to the most favorable conditions for preparing large crystals from a melt, as well as specifying the temperature stability of the crystalline phase or phases produced. In view of the current importance of gallium arsenide in semiconductor research and of the structural similarities of indium arsenide, it was thought that the complete phase relations of the system InAs-GaAs should be investigated. Previous work on the system Ga-As by Koster and homa' and on In-As by Liu and peretti2 has shown that GaAs and InAs are the only compounds formed, having melting points of 1238° and 942°C, respectively. In a survey of various systems of elements from groups IIIb and Vb, spengler3 also re- Mines Ltd., for his continuing encouragement and for permission to publish the results of this work. ports complete miscibility of gallium, indium, and arsenic in the liquid state. In a partial investigation of the InAs-GaAs system, Woolley and smith4 found extensive solid solution throughout the alloy range. Their subsolidus work, however, was inconclusive at temperatures below 900" and they did not determine the liquidus relationships of the system. PRESENT INVESTIGATION The starting materials used were high-purity gallium, indium, and arsenic. The method of preparation of the compounds follows that devised by M. Shafer and is described in detail in a paper by Shafer and eiser.' The end-member compounds, GaAs and InAs, were first prepared by reaction of the elements in the desired proportions in evacuated silica glass vials. The vials were rotated in a furnace as the temperature was slowly raised to insure rapid and complete reaction at low temperatures. Thereafter the starting materials, GaAs and InAs, were melted by heating the sealed vials to 1300" and 1000°C, respectively; the vials in this case were filled as completely as possible to keep the vapor space small and thereby minimize the loss of arsenic to the vapor phase. Ten binary mixtures of these compounds were then prepared by reaction of the powdered material in the solid state just below solidus temperatures. At 900C preparations containing 3, 5, 8, 10, 25, 35, 50, and 75 mol pct GaAs were found to be single homogeneous phases, indicating a complete series of solid solutions between GaAs and InAs. Moreover, it was discovered that the homogeneity of any crystalline binary preparation could be very accurately checked by X-ray diffraction because of the large differences in unit cell dimensions of the end membe5s. The cubic lattice constant ofor GaAs is a = 5.652A and that of InAs is a = 6.061A

Jan 1, 1963

By S. A. Mersol, C. T. Lynch, F. W. Vahldiek

The room-temperature microhardness of as-grown and annealed MoaC single crystals was measured on the (0001), {2110), and1012) planes using Knoop and Vickevs indenters at loads ranging front 25 to 1000 g. The orientatimz dependence of hardness with respect to crystal axes was also studied. The average random hardness of as-grown crystals was determined to be 1520 kg per sq nm. Annealing to 2000°C decreased. the average hardness by 150 units. An increase in hardness after annealing at 2200 ;C was noted. Optical and electron microscopy revealed slip and twin traces on all planes studied, as produced by mi-cvohavdness indentations. Basal (0001)(2i10) slip was determined to be the primary slip system and was substantiated by electron transmission microscopy. A secondary {1010)(2110) slip was produced by mi-crohardness indentations. The lattev also produced twinning- of the {10i2)[0001] type, as proven by electron diffraction. Electrical resistivity and elastic-modulus anisotropy were found and correlated with hardness anisotropy and Mo2C crystal structure. Elastic-modulus values were obtained by microhard-uess and ullrasonic methods. Bonding mechanism of Mo2C is discussed. ROOM-TEMPERATURE microhardness indentations are useful for studying hardness anisotropy, slip, and twinning in brittle materials. Slip has previously been produced in this manner in and WS~~.~ Recently, the authors5 reported slip of the {10i0)(11~0) type produced by high pressure and microhardness indentations on hexagonal TiBz (c/a = 1.066) single and polycrystals. This slip system was also reported by French and ~homas' and Taka-hashi and ~reise~ for hexagonal WC (c/a = 0.976) crystals. These results suggest that prismatic rather than basal slip is favored in hexagonal nonmetallic materials having a c/a ratio considerably less than the ideal (1.633). Buerger precession and cylindrical X-ray rotation patterns were previously' taken on cleaved sections of the Mo2C single crystals studied in this work. Th~y were found to be hexagonal MoaC with a. = 3.0233A, co = 4.7344A, and C/O = 1.5660. The latter ratio is close to that of the beryllium metal (c/a = 1.57), which slips primarily on the (0001) plane: but also slips on the (1010) planes.'0 ~irconium" (c/u = 1.59) and titanium12 (c/o = 1.59) deform mainly by slip on nonbasal planes which contain a close-packed direction. This is due to the fact that for these two metals the initial resolved shear stress for slip on the (10i0) prismatic planes is lower than that on the (0001) plane. The prominence of basal rather than prismatic slip in metals of high c/o ratios is shown by cadmium (c/a = 1.89), zinc (c/a = 1.86), and magnesium (c/a = 1.62) which deform mainly by basal slip. However, in case of the latter, by stressing magnesium crystals in tension or compression parallel to the basal plane, slip on (10i0) planes can also be produced.13 Several hardness values for polycrystalline Mo2C are reported in the literature: Biickle ' and Samsonov'~ give a value of 1800 and 1479 kg per sq mm, respectively, at a 100-g load; and Kieffer and Benesovsk~'~ report a value of 1950 kg per sq mm at a 50-g load. ~ott'~ reports a Vickers hardness value of 2000 kg per sq mm, with the load unspecified. A Rockwell A hardness value of RA = 88 has also been reported.'' In the present work, for comparison with single-crystal Mo2C hardness values, a Khnloo value of 1600 It 150 kg per sq mm was found on 99.6 pct pure and 99 pct dense hot-pressed Mo2C. This work was undertaken partly to explain the considerable differences in hardness values reported for polycrystalline Mo2C. EXPERIMENTAL The Mo2C single crystals investigated were prepared by a Verneuil-type process using an electric arc by the Linde Co. of the Union Carbide Corp.lg The largest specimens grown were boules 7 mm in diam by 40 mm in length. The crystals had an average density of 9.04 g per cu cm, with a Mo + C content of 99.8 wt pct. The major impurities were: 100 ppm each Na, Zr, and Ca; 85 ppm 0, 55 ppm Fe, and 10 ppm each Cr and Ta. The crystals were found to be carbon-poor, the average carbon content being 5.73 wt pct (stoichiometric value is 5.89 pct). The molybdenum content was found to be 94.08 pct, which is nearly stoichiometric. Electron-microprobe traverses of selected specimens were done with a Phillips-AMR microanalyzer. Thin-film and carbon replicas were used to prepare electron micrographs. This work was done with a JEM-6A electron microscope. Prior to optical and electron-optical studies, specimens were mounted in Lucite and polished on a vibratory polisher using diamond-paste grades ranging from 9-1 p and Linde A powder for up to 48 hr. Dilute nitric acid was used for thin-section polishing and chemical etching for 1-15 min. Electrical-resistivity measurements at room temperature were taken with a Rubicon bridge, using gold contacts. For hardness measurements, a Tukon Microhardness Tester Type FB with Knoop and Vickers indenters was used. Measurements were taken at loads ranging from 25 to 1000 g; however, the 100-g load was chosen as the standard load. All measurements were taken at room temperature. Indentations of cracking classes 1 and 2 only were considered for hardness determinations.20)21 (There are six cracking classes, ranging from "class 1" for a perfect inden-

Jan 1, 1967

Members of Fifty Years or More Lawrence Addicks '02 T H Aldrich '98 Walter H Aldridge '89 Eugene Ant. '99 George H Ashley '99 R M Atwater, Jr '97 James B Bailey '00 Samuel Barker, Jr '00 John F Berry '93 Charles A Bohn '93 W S Boyd '02 H C Boynton '01 H A Brassert '99 Arthur C Brinker '01 James F Brophy '01 Davenport Brown '02 Donald C Brown '01 Victor B Buck '98 Frederick Burbidge '87 Frederick P Burrall '97 John Cabot, Jr '99

Jan 1, 1952