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By A. R. Calawa, T. C. Harman, M. Finn, P. Youtz

A study has been made of the growing, annealing, and diffusion parameters in PbSe, Pb1-ySnySe, and Pb1-xSnxTe. Single crystals of these materials have been grown using the Bridgman technique. For all of the above materials the as-grown crystals are p type with high carrier densities. To reduce the carrier concentration and increase the carrier mobility, the samples are annealed either isothermally or by a two-zone method. From isothermal anneals, the liquidus-solidus boundary on the metal-rich side of the stoichiometric composition has been obtained for some alloys of Pb1-xSnxTe and on both the metal- and seleniunz-rich sides for PbSe and alloys of Pbl-ySnySe. In Pbo.935 Sno.065 Se carrier concentrations as low as 5 x1016 Cm-3 and mobilities as high as 44,000 sq cm v-1 sec-1 at 77°K have been obtained. Inter diffusion parameters mere also studied. The ddiffusion experiments mere identical to the isothermal or two-zone annealing experiments except that the samples were removed prior to complete equilibration. The resulting p-n junction depths were determined by sectioning and thermal probing. Inter diffusion coefficients for various temperatures were calculated for both PbSe and Pb0.93Sn0.0,Se. RECENTLY, there has been considerable interest in the PbTe-SnTe and PbSe-SnSe alloys with the rock salt crystal structure. The unusual feature of these systems is the variation of energy gap EG with composition. Several investigations1-3 have shown that EG for the lead chalcogenides decreases as the tin content increases, goes through zero, and then increases again with further increase in tin content. The possibility of obtaining an arbitrary energy gap by selecting the composition is an especially attractive feature of these alloys for applications involving long-wavelength infrared detectors and lasers. In addition, some unusual magneto-optical, galvanomagnetic, and thermomag-netic effects should occur for alloys with low band gaps. If uncompensated low carrier density crystals can be obtained, then a small carrier effective mass, a large dielectric constant, and the resultant high carrier mobility should yield enormous effects at low temperature in a magnetic field. The relative variation of the energy gap with pressure should also be very large for these low gap materials. The primary purpose of this paper is to provide some information concerning the preparation of low carrier concentra- tion, high carrier mobility, and homogeneous single crystals with a predetermined alloy composition. I) DETERMINATION OF ALLOY COMPOSITIONS In all of the work described in this paper, the composition of lead and tin chalcogenides in the alloys was determined by electron microprobe analysis. Separate X-ray spectrometers are used to make simultaneous intensity measurements of the Pb La1 and Sn La1 lines emitted by the sample under excitation by a beam of 25 kev electrons focused to a spot about 2 µm in diam. These intensities are compared to the intensities of the same lines emitted by standards under the same conditions. The standards used are the terminal compounds of each pseudobinary system, i.e., PbTe and SnTe for Pbl-xSnxTe alloys, PbSe and SnSe for Pbl-ySnySe alloys. The composition of the sample is then obtained from theoretical calibration curves which relate the weight fractions of lead and tin in the alloy to the measured ratios of X-ray intensities for the sample and the standards. The lead and tin calibration curves for each alloy system were calculated by using corrections for backscattered electrons,4 ionization,5 and absorption,6 and assuming that the atom fraction of tellurium or selenium in the sample and standards is exactly +. Results obtained by using the microprobe are in good agreement with those obtained by wet chemical analysis. II) CRYSTAL GROWTH FROM THE VAPOR Early work on the vapor growth of PbSe was carried out by Prior.7 He used small chips of Bridgman-grown single crystals as the source material and frequently converted the whole charge of a few grams into one crystal. In the present work, vapor growth occurred using a metal-rich or chalcogenide-rich two-phased alloy powder as the source material. Small, nearly stoichiometric crystals are formed on the walls of the quartz tube. The procedure will now be described in detail. Initially, a 100-g charge containing (metal)o.51(chalco-genide)o 49 proportions or (metal)o.49(chalcogenide)o. 51 proportions of the as-received elements in chunk form are placed in a fused silica ampoule. After the ampoule is loaded, it is evacuated with a diffusion pump and sealed. The sealed ampoule is placed in the center of a vertical resistance furnace. The region containing the ampoule is heated to about 50°C above the liquidus temper-ature for the particular composition used. After about one-half hour at temperature, the elements are reacted and the molten material homogenized. The ampoule is quenched in water. The quenched ingot is crushed to a coarse powder for vapor growth experiments and to a fine powder for the isothermal annealing experiments which are discussed in a later section. Vapor growth experiments were carried out using the powdered, metal-rich or chalcogenide-rich alloys

Jan 1, 1969

By G. R. Belton, Y. K. Rao

A galvanic cell, using liquid MgCl2 or MgC12-CaC12 mixtures as the electrolyte, has been used to determine activities in Mg-A1 liquid alloys between 700' and 880°C. The incovporation of a chlorine electrode in the cell also allowed measurements to be made of the standard free energy of formation of MgCl2(l). The results are shown to be in good agreement with thermo-chetrlical values from the literature, and this is taken as evidence that the small, known solubility of magnesium in iMgCl2 introduces no significant error in galcanic cell measurements. Within experimental error, the activity coefficients and relative partial molar enthalpies at 800°C are shown to be represented by the following "subregular" solution equations: logy~~ =-0.68(1 -xMgj3 log yAL =-1.02(1 - XMf + 0.68(1 - XMf H.M = -4400(1 - %)3 / cal Mg 7Ag' HZ =-6600(1 - xA1)' + 4400(1 - XMf cal SCHNEIDER and toll' have used a transpiration technique to measure the vapor pressures of magnesium over Mg-A1 alloys between 544" and 594°C. amsstad,' however, has since suggested that the extrapolation to zero flow rate, used by these authors in interpreting their apparent pressure vs flow rate data, gives unreliable results. Rogers, Tomlinson, and Richardson,3 in interpreting the results of solution equilibria between Mg-A1 alloys and liquid MgC12, also considered the measurements of Schneider and Stoll to be unreliable and preferred to derive activities for the alloys from the earlier boiling point determinations of ~eit~ebel~ and the partial molar heats recommended by Kubaschewski and ~atterall.~ These latter heats were based substantially on the early calorimetric work of Kawa-kami but, unfortunately, his work on other systems has sometimes been found to be inaccurate.7 Rogers et al., in the above-mentioned paper,3 tentatively concluded that the most likely species responsible for the limited solubility (0.3 mole pct at 800°C) of magnesium in MgC12 were Mg° (neutral) and Mg2++. Two more recent studies8,9 have supported Mg2++ as the soluble species. In the present study, activities in Mg-A1 alloys have been determined by means of a galvanic cell involving liquid MgCl2 or MgC12CaCl, mixtures as the electrolyte. Since the reactive nature of magnesium precluded simple Faraday yield experiments, a chlorine electrode was incorporated in the cell in order that the performance of the cell could be checked by measurements of the heat and free energy of formation of MgC12. This procedure was considered necessary since it has been suggested1' that the solubility of a metal in a molten salt might introduce electronic conductivity; also, previous determinations of the standard electrode potential for MgC12 differed by as much as 70 mv11-13 EXPERIMENTAL Materials. Analyses of the materials used in preparing the alloys and the electrolyte mixtures are presented in Table I. The alloys were prepared by induction melting weighed amounts of the metals in a graphite crucible held under an argon atmosphere. Pure anhydrous magnesium chloride was prepared by heating the mixture MgCl, . 6H20 +NH4C1(1:1) to 650°C, followed by melting under dry argon. The melting point of the dry MgC12 was found by differential thermal analysis to be 714.8oC, which compares well with the accepted value of 714C.14 This agreement was taken to be an indication of the high purity of the dried salt. Table I. Compositions of Materials, wt pn Impurity Mg Al MgCI2 CaCI, Ba - - 0.005 Ca - - 0.010 Cu 0.02 0.02 Fe - 0.10 0.001 0.010 Pb 0.01 - 0.001 0.005 Mn 0.15 0.001 Si - 0.10 Sr - - 0.005 MBSO* - 0.040 ARGON TUNGSTEN CHLORINE LEAD—411 11 II ALUMINA 'A I / ave GRAPHITE on irA~_ ( ^"l ROD MAGNESIUM S>ILICA~^ /, OR ALLOY-. I /A] ___________ -«^- _ ELECTROLYTE I y FRITTED DISCS Fig. l—Arrangement of chlorine and metal electrodes in electrolytic cell.

Jan 1, 1970

By C. W. Parmalee

The ideal fuel for burning ceramic wares is the one that, among other characteristics, has little or no sulfur. For that reason wood was long considered the most desirable fuel but its high cost has practically eliminated its use except in regions where it is very abundant or other circumstances warrant its choice. The fuels commonly employed are natural and producer gas, oil, and coal. The last named is undoubtedly the most important, not only in this country but abroad. Occasionally anthracite is used but the larger part is bituminous. The quality of the coal used depends on the kind and the value of the products being manufactured. For some materials, such as common brick, hollow block, etc., the quality of the coal is of less importance than in the manufacture of polychrome terra cotta, pottery, porcelain, etc. It is obvious that in burning clays that contain notable amounts of pyrite, marcasite or gypsum, as is the case with many common clays, the sulfur content of the fuel is of much less importance. The permissible amount of sulfur in the coal used will depend on the kind of product being manufactured. "A good sample1 of coal commonly used in pottery ovens has something like this quantity of sulfur: total sulfur, 1.20 per cent.; sulfur in ash, 0.11 per cent.; volatile sulfur, 1.09 per cent." This is based on English pottery practice. Correspondence with a. number of leading manufacturers in this country has produced the following figures: Sanitary Ware.—(a) 1.0 per cent, maximum, (b) 0.5 per cent. Sewer Pipe.—(a) 1.2 per cent., (b) 1.1 per cent, present run, 3.0 per cent, has been used. Terra Cotta.—(a) 0.5 per cent, basis of contract, 1.0 per cent, approximate. Pottery.—1.0 per cent, contract, 1.5 per cent, probable content. Enameled Brick.—1.3 per cent, maximum, (a) and (6) designate different firms giving figures. Since a pottery kiln for sanitary ware will require about 14 tons of coal for a bum, the quantity of SO2 that will be generated from a 1-per

Jan 1, 1920

By J. G. LECKIE

During the first ten months of 1943 copper was produced at a higher rate than in 1947. However, on Oct. 24 one of the large mines was shut down due to a strike. As of Dec. 31 the strike was still in effect and had already resulted in a loss of production of 50,000 tons of copper. The demand for copper was considerably greater throughout the year than the supply. The price of electrolytic copper delivered at the Atlantic Seaboard refineries advanced from 21.20 to 23.20 cents per lb during the year. This sustained demand for copper, together with the increase in price, has had the natural effect of spurring interest in uncovering new deposits, and in re-examination of known low-grade deposits and old tailing clumps. This is in addition to the usual reevaluation activities which normally result from the constant improvements in efficiency of ore concentration.

Jan 1, 1949

T. R. HARRISON, Washington, D. C. (written discussion *).-Ad-vantage will be taken of this occasion to mention briefly a form of double potentiometer which has been used at the Bureau of Standards for about 2 1/2 yr. in calibrating thermocouples. The calibrations referred to are those made by comparison to standard couples. In order to insure equality of temperature between the couples, the junctions are fused together; consideration of fundamental principles will show that this introduces no error. Two separate potentiometers are used, one connected to each thermocouple, and each potentiometer is provided with a reflecting galvanometer. The two spots of light are reflected on to a single scale, the galvanometers being set in such a position that the spots coincide on the scale at a point marked zero when the circuits are open or when the potentiometers are balanced. By setting one potentiometer to a desired value and adjusting the other so that both spots pass across the scale together as the temperature rises or falls, simultaneous readings are obtained. By making observations first with a rising temperature and then with a falling temperature, the rates of rise and fall being approximately equal, and taking the means of the results found, several minor errors such as those clue to differences in the time lags of the two systems, etc., are eliminated or greatly reduced. The differences between the values

Jan 12, 1919

By W. P. Blake

The mining district and the town of Tombstone are situated in Cochise County, Arizona Territory, at the northwest end of the Mule Pass range of mountains, in longitude 110°, and latitude about 31 40' N,, upon the right bank of the San Pedro River, from which the town is distant 9 miles east.. It is also 24 miles south of Benson station on the Southern Pacific Railroad of Arizona, and about 40 miles north of the Mexican line. Its altitude above the sen is 4600 feet. The Dragoon Mountains rise across a valley to the northeast, and the Huachuca Range similarly upon the southwest. The country is open, without timber, and the surface, where the mines are opened, is in general gently rolling, and accessible to wagons by. natural roads. The first locations were made in the pear 1878 by the Scheffelin brothers and Richard Gird, the latter being well known among the pioneers of Arizona as a surveyor and miner, who contributed largely to our knowledge of the geography of the Territory in early days,

Jan 1, 1882

By Henry Faul

MEASUREMENT of radioactivity of rocks and ores has developed into a complete method of geophysical exploration. The problem falls into three natural categories: (I) surface radiation measurement in the field and underground; (2) radioactivity logging of drillholes; and (3) laboratory analysis of samples. Portable counters are used in the field for tracing radioactive formations and for quantitative estimates of radioactive content of surface rock. Wartime advances in battery design make it possible to construct small precision counters that can be carried easily. Even the smallest conventional diamond drillholes can be logged, and actual content of the radioactive element can be measured. The exact grade of very thin active layers or veins can be estimated only approximately. Samples may be analyzed for their alpha, beta or gamma activity, and beta assaying is the best suited to rapid routine operation. Simple calibration with standard samples is sufficient for rough work, but a density correction is necessary when greater precision is required. Samples with high emanating power should be fixed and stored for three weeks to reestablish the radium-radon equilibrium prior to precision assaying. Carnotite can be fixed by sintering or molding with plastics. Among the important new developments, a low-voltage Geiger tube has been designed recently, and crystal scintillation counters hold great promise for high-efficiency gamma-ray measurement.

Jan 1, 1947

By Fred C., Fred C. Bond

Comminution energy is principally energy of deformation before breakage, which appears as heat. An empirical equation is presented which covers the entire comminution range. The new strain-energy theory considers comminution from the known principles of mechanics and the reduction ratio. Energy requirements according to the different theories are compared.

Jan 1, 1950

By Russell Franks

IN recent years a considerable tonnage of the 18 per cent chromium and 8 per cent nickel steels has been used in lightweight high-strength structures that must be resistant to deterioration under atmospheric conditions. These steels are austenitic in character and their strength can best be increased by cold-working. Although a marked increase in tensile strength is obtained, claims have been made that the cold-worked steels do not possess fully satisfactory elastic properties. Under certain conditions, however, this has caused no great concern, because, as explained by Ragsdale,1,2 the cold-rolled steels have been widely applied for construction of lightweight, high-strength trains using spot welding for joining purposes. Ffield3 agrees that the ease with which thin sections of the cold-rolled 18-8 steels can be joined by spot welding is greatly in their favor, but that they would be more satisfactory if higher elastic properties and a higher modulus of elasticity could be obtained. He states that, as far as the mechanical properties are concerned, the straight chromium stainless steel is superior to the cold-worked 18-8 steel, and in order to illustrate, he presented the data of Fig. 1, which also give a stress-strain curve for a low-carbon 13 per cent Cr steel. Ffield? pro-posed that columbium-bearing or titanium-bearing cold-rolled 18-8 steels be given a heat-treatment (preferably for 1 hr.) in the range 400° to 600°C. to precipitate carbides in order to obtain better mechani-cal properties. Discussions by Sutton,4,5 de Ganahl,6,7 8 Krivobok and Lincoln,9 Knerr,10 and Thaden11 have given further information on the properties of the cold-rolled 18-8 steels compared with other materials used in light-weight, high-strength structures. These investigators and others point out that the ultimate tensile strength of the cold-rolled 18-8 steel can be increased to 200,000 lb, per sq. in. or higher; Krivobok et al. indicate that

Jan 1, 1940

By V. J. Driscoll

A method is given for checking pore volume reserve estimates and transient water inflzix factors utilizing early well performance. Principal applications are based on the observation that there is a convenient transient time-range in terms of well spacing in which observed pressure drop will give a good indication of fluid-in-place. Primary quantity determined is a porosity-feet value applicable in the vicinity of an observation well. Checks on porosity or net pay thickness and permeability values also are obtained. These are particularly valuable in improving quality of interpretive factors entering into pore-volume reserve determinations for larger fields. In smaller fields, direct determination of total field reserves and approximate location of boundaries may be made in some cases. Well interference and production data plus a build-up curve on the observation well are needed. The build-up curve may be taken at any time. Field applications are given. The method can be applied with the completion of the second well on a new discovery or to older reservoirs by major changes in withdrawal rates from a local area. Appropriate test length permits results to be obtained with equal accuracy on widely spaced wells. Criteria for optimizing test conditions are given. Provision is made for various boundary and well effects including incomplete observation well build-up. INTRODUCTION Due to low quality data, initial pore volume reserve and water influx estimates may often vary by a factor of two or more from results obtained at a later date. Unfortunately, by conventional methods, more reliable answers from performance usually are not available until after most significant economic decisions have been made. Furthermore, in older reservoirs, uncertainties may still exist as to original oil-in-place, recovery factors and residual oil saturations due to incomplete or inaccurate performance data. This paper outlines situations and appropriate arrangements of basic transient theory whereby well interference data can be utilized to improve the quality of estimates under certain conditions. In addition to production data on offset producers, key information required is a measured pressure drop at an observation well, corrected for any incomplete build-up due to previous production, plus a formation capacity value derived from a conventional pressure build-up plot on the observation well. The method, as outlined, is strictly applicable only to a horizontal single-layered system of uniform rock characteristics containing a homogeneous fluid of low and constant compressibility. However, under the set of test conditions devised, requirements can usually be relaxed so that it should be applicable to most low permeability gas, water and undersaturated oil reservoirs. This is an area where more reliable information is certainly needed. BASIC CONSIDERATIONS A, B, C and F as subscripts or in the text refer to producing Well A, observation Well B, a more remote producing Well C and field boundary F. Combinations such as AB refer to distances and dimensionless times in terms of distances between these points, while single letters refer to distances and dimensionless times in terms of the well-bore or field radius. Equations covering definitions of quantities and complex situations are given in the Appendix. Key equations in practical units are given in Table 2. Transient Pressure Behavior Fig. 1 illustrates pressure drop at Point B with time due to initiation of a constant rate of withdrawal from Point A. This is shown as since a quantitative under-

By T. B. Counselman

C. G. McLachlan—In the foregoing paper the author has presented a very neat method for calculating the solution recovery for a countercurrent flowsheet. He has, however, based his calculations, as he states, on the assumption that "the concentration of dissolved value must be exactly the same in the overflow and underflow of any thickener." This assumption, which is usually made regardless of the type of calculation used, is "not strictly correct because diffusion of the dissolved gold in the solution associated with the solids as it progresses through the countercurrent system is far from being instantaneous, with the result that on a ton for ton basis, the assay of the solution in the thickener underflow is higher than in the corresponding thickener overflow. An agitator introduced into the flowsheet between thickeners will reduce, but not entirely eliminate, this difference. In practice we have found that the best way to take care of this condition— in addition to the use of one or more intermediate agitators—is to circulate 20 pct or 25 pct more solution than called for by the cheoretical calculation. This presents no difficulty provided that adequate thickener capacity is provided in the original design of the countercurrent circuit.

Jan 1, 1951

By T. B. Counselman

C. G. McLachlan—In the foregoing paper the author has presented a very neat method for calculating the solution recovery for a countercurrent flowsheet. He has, however, based his calculations, as he states, on the assumption that "the concentration of dissolved value must be exactly the same in the overflow and underflow of any thickener." This assumption, which is usually made regardless of the type of calculation used, is "not strictly correct because diffusion of the dissolved gold in the solution associated with the solids as it progresses through the countercurrent system is far from being instantaneous, with the result that on a ton for ton basis, the assay of the solution in the thickener underflow is higher than in the corresponding thickener overflow. An agitator introduced into the flowsheet between thickeners will reduce, but not entirely eliminate, this difference. In practice we have found that the best way to take care of this condition— in addition to the use of one or more intermediate agitators—is to circulate 20 pct or 25 pct more solution than called for by the cheoretical calculation. This presents no difficulty provided that adequate thickener capacity is provided in the original design of the countercurrent circuit.

Jan 1, 1951

By Thomas MacFarlane

During the last fifteen years the progress made in the science of lithology has been of a very marked character. From being a miscellaneous collection of facts and observations regarding certain mineral aggregates seemingly incapable of systematic arrangement, it has become a most interesting and orderly department of science. The investigators who have brought about this great change have recorded the results of their labors, and placed at our service an extensive and varied literature on the subject. To this I have paid some attention, and partly from studying it,, partly from my own observations, I have wrought out a classification of original or crystalline rocks, which I venture to bring under the notice of the members of this Institute. The practical importance of the subject will be acknowledged when it is considered that rock species are not without their influence on the contents of the mineral veins which intersect them. Besides, the Institute has been doing good service in defining terms in metallurgy, and no doubt in mining and geology we might

Jan 1, 1880

By J. E. Forciea, O. E. Palasvirta, L. G. Hendrickson

All pilot and commercial plants working with Mesabi Range taconite employ wet magnetic separation. Progress is being made with a dry magnetic process,9-11 but this has not yet been applied to taconite except in the laboratory and pilot plants. Flowsheets in all five plants are similar, including multiple stages of grinding, each followed by magnetic separation, which rejects a finished tailing. The flowsheet in Fig. 1 is used in the preliminary and commercial plants of the Erie and Reserve mining companies and in Unit C of Oliver's Pilotac plant. At Erie the desliming operation is omitted. In the Reserve plants two ball mills are used with each rod mill. Pilotac uses flowsheet 2 in Unit A-B and has also tested flowsheet 3. Principal differences in the three flowsheets are the number of grinding stages and the type of roughing. The terms open- circuit roughing and closed-circuit roughing are best defined by the diagrams.

Jan 12, 1958

By Albert B. Horn, J. J. McKetta, O. L. Culberson

Since water is present in natural gas and petroleum reservoirs, it is of engineering value to have accurate experimental data regarding the behavior of water in hydro-carbon systems. Since experimental data of this nature are so scarce in literature, a program is under way at the University of Texas to obtain experimental data regarding the distribution of water in petroleum hydrocarbons. This initial paper is subdivided into three parts: A. The apparatus and analytical procedure are discussed. B. The equipment has been checked by comparing the experimental data with data of literature on the solubility of methane in water at 77°F and pressures to 10,000 psia. C. Experimental data are presented at 100, 160, 220, 280, and 340°F on the solubility of ethane in water at pressures to 1200 psia. As the temperature is increased the solubility of ethane in water first exhibits a minimum and then a maximum solubility. The range of applicability of Henry's Law is discussed. INTRODUCTION Although considerable experimental data have been published on water-hydrocarbon systems in the hydrate region, the information on these systems in the vapor-liquid and the vapor-liquid- 'References are given at end of paper. Manuscript received at the office of the Petroleum Branch August 31. 1949. liquid regions at elevated pressures is extremely scarce. A survey of the literature on hydrocarbon-water systems at elevated pressures was presented by McKetta and Katz12,13,14 showing the systems and phases investigated. In addition to these existing published data, Poettman and Dean" have reported the water content of propane in the three-phase region (only the propane-rich liquid and the vapor phases were studied) and Michels, et al.15 have reported the solubility of methane in water at pressures to 6800 pounds per square inch at 77°F and at pressures to 1500 psia at temperatures to 300°F. It has been shown12,14 that the presence of water will materially affect the phase equilibrium of hydrocarbon systems. In order to make experimental studies on the quantitative effect of the presence of water in naturally-occurring hydrocarbon systems, it is desirable to have data available on binary hydrocarbon-water systems. A program is underway at this laboratory to determine the phase relations of the hydrocarbon-water systems. Initially the investigation will be limited to binary systems with water as one of the components. Later ternary and complex systems will be investigated and reported. EQUIPMENT AND ANALYTICAL PROCEDURE Apparatus In order to avoid a description of the methods employed in each subsequent paper, a description of the apparatus and the analytical procedure will be given here. The apparatus is shown schematically in Fig. 1. The numbered items in Fig. 1 represent the high pressure valves. The equilibrium cell is of the totally enclosed type, with a volume of 550 cubic centimeters. The cell is mounted in an air bath which in turn is mounted on pillow blocks and connected to a rocking mechanism so that the cell and bath will oscillate approximately 30 degrees above and below the horizontal at 35 oscillations per minute. The air bath is heated by two resistance heaters. The first or primary heater is 250 watts and is controlled by a thermoregulator; the second heater is of 500-watt size and is manually controlled to aid in bringing the cell to equilibrium temperature. Air circulation in the bath is accomplished by means of a fan. the shaft of which is concentric to the heaters. The walls of the bath are insulated with 2-in. thick blocks of 85 per cent magnesia. Temperature observations are made with three calibrated thermocouples. One couple is sealed in a well provided within the equilibrium cell, and is used as the criterion of the cell being at the equilibrium temperature. The other two thermocouples are located on opposite sides of the cell to indicate temperature uniformity within the air bath. The thermoregulator, used in conjunction with a relay, gives a variation in the temperature of the air in the bath of plus or minus one degree Fahrenheit. However, since the equilibrium cell weighs approximately 55 pounds, the

Jan 1, 1950

By Robert I. Jaffee, Bruce W. Gonser, Eugene M. Smith

THERE has been little investigation of the gold-germanium binary alloys. Haughton1 does not mention any work on the system. In a review article commemorating the fiftieth anniversary of the discovery of germanium, E. Einecke2 mentioned a gold germanium eutectic at 24 atomic per cent Ge (10.4 weight per cent) melting at 359°C., but did not give the source of his information. From measurements of electrical conductivity, J. 0. Linde3 estimated that at least o.6 weight per cent germanium is soluble in gold. The recent availability of germanium in this country in commercial quantities has led to interest in its properties and its alloys. This study is part of a program of investigation on germanium alloys; work on ternary alloys involving germanium and gold will be reported later. In this investigation, the composition and melting point of the Au-Ge eutectic reported by Einecke has been found to be substantially correct. Eutectic composition has been placed at 12,0 per cent germanium, however. An alloy of 10.4 per cent Ge, Einecke's value, was found to have a few gold dendrites in it. The eutectic temperature has been determined as 356.0 ± 0.5°C., slightly less than the temperature of 359°C reported by Einecke. The liquidus curves and the solid solubility of germanium in gold have been determined, and are shown in Fig. I. MATERIALS AND ALLOYING The germanium used in this investigation was prepared by the Eagle-Picher Lead Co. from pure germanium oxide, by reduction in clay crucibles with sodium cyanide. The regulus is quite pure, assaying over 99.9 per cent Ge. High-purity gold obtained from Handy and Harmon was used. Alloying was carried out in graphite crucibles in an atmosphere of purified hydrogen. The temperature was brought up to 1050° to 1100°C., and the metal was allowed to freeze in the crucible. Prepared in this way, the gold dendrites in hypoeutectic alloys were somewhat segregated at the bottom and sides of the ingot, and on the hypereutectic side the lighter primary germanium tended to gather at the top. Most of the alloys were made from virgin metal. Low-germanium heats were made by alloying pure gold with the eutectic. Melting losses were consistently a few milligrams or less, and the composition could safely be taken from the intended analysis. The 30 per cent and 50 per cent germanium heats for thermal analysis were made in part from remelted higher germanium heats, and they may be off composition as much as one per cent. Because of the high cost of materials, the weight of heats for thermal analysis were 15 to 20 grams and heats for metallographic, X-ray, and hardness specimens were 2 to 4 grams.

Jan 1, 1945

By John R. Eckel

A Iaboratory drilling rig has been devised and placed in operation which permits the application of hydrostatic, terrastatic, and formation pore pressures to a rock sample for drilling under controlled conditions. Calibrated rests of this equipment in-dicate qualitative agreerment with field results on the effect of weight on bit, rotary speed, and rate of circ~~lation on drilling rate. Tests under pressure, using water and air as the drilling fluids, indicate that when drilling saturated limestone samples, a pressure differential between hydrostatic and formation pressure is the only pressure which affects drilling rate. A differential in either direction causes a reduction in rate, but the same diflerential from the wellbore into the formation causes the greater reduction. Also, in lime.stone, air favorably affected drilling rote only when compared to water at high hydrostatic pressurre, all other conditions remaining constant. Large increases in drilling rate with air could be obtained in the laboratory only while drilling a shale, which offered a limited permeability to nitrogen and which could be drilled with a differential from the formation into the wellbore. In general, the magnitude of the changes due to the pressure effect were small compared to changes in drilling rate obtainable by changing either bit weight or rotary speed. INTRODUCTION In the course of Humble's drilling research program, the desirability of investigating several factors which lend themselves to laboratory rather than field study became obvious. Principal reasons for this are the expense involved in field studies and the difficulty of exercising the required degree of control. Of primary importance are investigations of the effect of fluid pressure on rock rate, the effect of pressure on rock drillability, and a study of the fundamental mechanics of rock failure and chip generation. Several years ago some work in the laboratory on the effect of mud properties on drilling rate was re- ported to the API', but the completion of this work and the investigation of the other variables affecting drilling rate required equipment somewhat more elaborate than that used on these earlier tests. This equipment has been assembled to form Humble's Drilling Engineering laboratory. To date only the effect of pressure on rock drillability while using water and air has been investigated, and this work is not yet complete. Facilities are available to investigate the effect of fluid properties on rate of penetration, and information is being assembled on a current basis on the mechanics of drilling. The sequence of presentation in this progress report is somewhat different from that in which the data were obtained since the order of ex-

A. W. TRACY' AND D. H. THOMPSON (presented in written form).-Messrs. Ed¬munds, Anderson and Waring are to be commended for their excellent work in so painstakingly reducing to constants, the variables believed to be associated with these types of stress corrosion. An ammonia stress-cracking apparatus similar in many respects to the one described has been assembled. Certain aspects of its construction may be of interest. Tensile loading of the specimens, which are usually Y8-in. diameter wires, is accomplished by springs acting in compression in compact, portable, tubular assemblies weighing less than 10 lb. The lower end of each assembly contains the test specimen and is passed into the test chamber for exposure to the moist ammoniacal atmosphere. There is considerable convenience in being able to load the specimens in a portable unit, which may be warmed to prevent condensation, and then thrust instantaneously into the test chamber. Spring loading obviates the use of weights, but it has the disadvantage of allowing some relaxation of the load if the specimen elongates during corrosion. The maximum loss in load found so far was 20 per cent. The air supplied to the test chamber is humidified by passing it through thermo¬statically controlled water. The air is dispersed into fine bubbles by being forced through a porous ceramic filter at the bottom of a tank containing about 10 liters of water. The temperature of the water is controlled independently of the tempera¬ture of the test chamber. Thus, with the

Jan 1, 1945

By Russell Franks, W. O. Binder

In recent years a considerable tonnage of the 18 per cent chromium and 8 per cent nickel steels has been used in lightweight high-strength structures that must be resistant to deterioration under atmospheric conditions. These steels are austenitic in character and their strength can best be increased by cold-working. Although a marked increase in tensile strength is obtained, claims have been made that the cold-worked steels do not possess fully satisfactory elastic propertics. Under certain conditions, however, this has caused no great concern, because, as explained by Ragsdale,1,2 he cold-rolled steels have been widely applied for construction of lightweight, high-strength trains using spot welding for joining purposes. Ffield3 agrees that the ease with which thin sections of the cold-rolled 18-8 steels can be joined by spot welding is greatly in their favor, but that they would be more satisfactory if higher elastic properties and a higher modulus of elasticity could be obtained. He states that, as far as the mechanical properties are concerned, the straight chromium stainless steel is superior to the cold-worked 18-8 steel, and in order to illustrate, he prcsented the data of Fig. 1, which also give a stress-strain curve for a low-carbon 13 per cent Cr steel. Ffield† proposed that columbium-bearing or titanium-bearing cold-rolled 18-8 steels be given a heat-treatment (preferably for 1 hr.) in the range 400" to 600°C. to precipitate carbides in order to obtain better mechanical properties. Discussions by Sutton,4,5 de Ganahl,6,7,8 Krivobok and Lincoln,' Knerr,l0 and Thaden11 have given further information on the properties of the cold-rolled 18-8 steels compared with other materials used in lightweight, high-strength structures. These investigators and others point out that the ultimate tensile strength of the cold-rolled 18-8 steel can be increased to 200,000 lb. per sq. in. or higher; Krivobok et al. indicate that

Jan 1, 1940