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By Chester T. Sims, Robert I. Jaffee

The thermoelectric behavior of the Pt—Pt-Re thermocouple and the resistance of rhenium to attack by certain molten metals is discussed. In addition, data are presented on the stress-rupture behavior of drawn wire, the tensile characteristics of rolled sheet, the variation of Young's modulus with temperature, and the effect of specimen size and fabrication method on the work harden ability. Mechanical properties of thoriated rhenium are discussed. This includes data on the effect of thoria in rhenium on tensile properties, ductility, work hardening, and recrystallization. RECENT work by the authors', has described methods of fabrication and some of the physical and mechanical properties of rhenium. Rhenium was established as a high melting, dense, refractory-type metal with favorable mechanical properties. In addition, Todd and co-workers' and others" have studied such properties of rhenium as the work function, specific heat, and the resistance of rhenium to the water cycle. Revelation of these and other properties has led to serious consideration for application as electrical contacts, high temperature thermocouples, and wear resistant materials. chanical properties reported previously,' several additional examinations have been conducted. The stress-rupture behavior and the Young's modulus of rhenium have been investigated at elevated temperatures. Tensile data have been obtained for rolled sheet, and a study of the relative work hardening characteristics of rod, wire, and sheet has been conducted. Variation of Modulus of Elasticity With Temperature—The Young's modulus of a % in. diam annealed rhenium rod was determined from room temperature to 880"C (1620OF). The rod, approximately 6 in. in length, was activated in a transverse vibration apparatus suspended in a furnace. The resonance frequencies of the rod were measured and used to calculate the moduli values. The driven frequency was 569 cycles per sec, and a protective helium atmosphere was used. The data, plotted in Fig. 1, show that the modulus decreases in an approximately linear manner with temperature over the range tested.

Jan 1, 1957

By W. M. Pierce

THE present work has been done in an endeavor to correlate and complete the data on the constitution of alloys of zinc with other common, metals, dealing exclusively, however, with the zinc-rich alloys in which the zinc content is between 90 and 100 per cent. This investigation has included the systems lead-zinc, cadmium-zinc, iron-zinc, copper-zinc, aluminum-zinc, nickel-zinc, manganese-zinc, cobalt-zinc, tin-zinc, and magnesium-zinc. The important ternary system zinc-lead-cadmium and the zinc corners of other ternary systems have been investigated in connection with this work but will not be dealt with here. Zinc does not form a single homogenous zinc-rich solid solution over any considerable range of concentration with any of the metals mentioned. A limited range of solid solubility is said,; by previous investigators, to occur in several cases and certain effects on the properties of zinc are attributed (with varying degrees of consistency among different writers) to the presence of certain other metals dissolved in zinc. The increasing use of rolled zinc and the possibilities offered by zinc as a casting alloy in certain fields have it made essential to determine precisely these equilibrium relationships. In carrying out this .investigation reliance was placed chiefly on two methods, conductivity measurements and microscopic analysis. The first method proved valuable in determining the existence and extent of solid solubility. The second method stands alone as a means of determining structural characteristics and supplements the first method in the measurement of solid solubility. The scleroscopic hardness of all conductivity specimens was measured partly for its value from the point of view of mechanical properties and partly; as a check on the conductivity curves in indicating the limits of solid solubility. No hardness curves are included in this paper, for in no case were they important in arriving at the constitution of any system.

Jan 2, 1922

By C. W. Nicolson

THE Tri-State zinc and lead-mining district is in the northeast corner of Oklahoma, the southeast corner of Kansas and the southwest corner of Missouri. The area throughout which active mining has been conducted is about 45 miles long and about 5 miles wide, extending northeasterly from Commerce, Okla., to Alba, Missouri. Although the lead ores were mined on a very small scale in the vicinity of Joplin, Mo., as early as 1848, nothing of any importance was done in the district until 1870, since when both mining and smelting have been prosecuted with considerable vigor. In the beginning the lead ores only were exploited, but within a few years extensive deposits of zinc ores were found and since that time the production of zinc ore has far exceeded that of lead. Both the surface and mineral rights in Missouri and Kansas were under individual ownership by the time ore was discovered. Although some of these rights were purchased by mining companies, most of the mining has been done under leases covering small areas, usually 40 acres, although in the past many leases were given on much smaller tracts. In Oklahoma most of the mineral land had been alloted by the Government to various Indian tribes and although the title to some of these lands had been acquired by various white men before the discovery of the rich Picher field, the title to most of the land has remained with the Indian tribes and the leasing of the mineral rights has been done by the Federal Government for the benefit of the Indians. The Indian allotments were of 200 acres each and some of the mining leases covered entire allotments, although many leases were granted for only 40 acres or even less. Practically all of the leases granted in the past required the erection of a concentrating plant on each lease, a condition that has had a pronounced effect upon the mining and milling methods of the district, since the apparent ore reserves on each tract were too small to justify large

Jan 1, 1938

Society of Chemical Industry (London), American Section. Foster D. Shell, Secretary, 130 Clinton St., Brooklyn, N. Y. Publications of this Society are not of direct interest in this directory but the address of the Society is listed that the reader may have it on record for reference. Subscription to the Journal (A the Society costs £ 2 10s, or $12.50 at the normal rate of exchange. Individual copies are is 9d, postage extra.

Jan 1, 1933

By G. S. Hume

The total production of crude oil in Canada showed only a small improvement in 1936 over 1935, but developments of great importance took place in Alberta on the west flank of the Turner Valley field in the foothills southwest of Calgary. These have led to renewed activity in drilling such as has not been experienced for many years, and undoubtedly this will result in a very considerable increase in the oil production during 1937.

Jan 1, 1937

Report was made by the Committee of National Engineering Societies on the Reserve Corps of Engineers and it was voted that a committee of - three be formed-consisting of the President of the Institute, Dr. Henry -S. Drinker and the Secretary of the Institute-to select members in different parts of the country to-advise with the local U. S. Engineer Officers as to qualifications of applicants for the Reserve Corps of Engineers.

Jan 8, 1916

By D. S. Choi, D. L. McCain

A method of estimating the chain pillar size required to support the wide working faces of longwall or shortwall coal mining is presented. The pillar size is determined through the use of coal strength, entry geometry, panel width, and overburden pressure. Design analysis is focused on a three-entry development system in the Pittsburgh Seam but can be used for other development plans and other seams by substitution of the proper geometric and strength data.

Jan 1, 1981

By William P. Dyrenforth

The principle of electrostatic separation is discussed and elaborated on by dividing into the three main mechanisms of electrification as applied to separation of solid substances, i.e., (1) contact electrification, (2) electrification by conductive induction, (3) electrification by ion bombardment. Types of equipment used for electrostatic processing are described and the effects of humidity mentioned. Processing of iron ore, titanium minerals, rare earths and cassiterite is discussed and some existing plants are described.

Jan 1, 1978

By I. Iwasaki, R. Titi-Manyaka

Chlorination and chloridization behaviors of pyrite, pyrrhotite, marcasite, chalcocite, covellite, galena, sphalerite, heazlewoodite, and elemental sulfur were investigated by thermogravimetric analysis. The possible reaction mechanisms are discussed on the basis of the theoretical weight changes and thermodynamic considerations. Chlorine is a more effective chloridizing agent than hydrogen chloride. In the light of the experimental results, a scheme for producing nonferrous metal chlorides, molten sulfur, and ferric oxide from complex sulfide flotation concentrates is discussed.

Jan 1, 1974

By R. D. Brown

This paper profiles Canada’s current economic, tax, and political environment with respect to its mining industry. Problems that must be overcome if the industry is to attain its full growth potential and are highlighted, some suggestions reflecting the opinion of many in the industry are given. Tables provide some detail on the current Canadian mining tax system, province by province, as well as for the Yukon and Northwest Territories, plus some relevant economic trends.

Jan 1, 1985

By Joseph D. Weeks

The primary problems of civilization are material ones; their answers are writ in fire. When these problems in their higher aspects have pressed for solution, it has been out of the burning bush that the Divine voice has spoken, or in the cloud and smoke that the Divine finger has traced the rules by which these problems shall be solved. It is with the material problems, however, that we, as engineers, have to deal.

Jan 1, 1896

By George A. Komadina

The Pima mine lies 20 miles southwest of Tucson, Ariz., and 45 miles north of the Mexican border. It is located on a hillside overlooking Tucson, which allows for gravity flow generally through the plant. In April 1965, an expansion was authorized by the mine's board of directors. This will triple the mine's output to 18,000 tpd. At this rate, it is estimated that there is sufficient ore to last 20 years.

Jan 6, 1965

By C. G. Fink, G. L. Putnam

The dissolution of gold by cyanide solutions was studied by determining the time required for the solvents to dissolve gold leaf. Minute traces, even 0.5 ppm, of sulphide ion retard the dissolution of gold, and this behavior cannot be accounted for by the presently accepted hypotheses involving oxygen-depletion or thiocyanate formation. On the other hand, traces of the salts of lead, bismuth, mercury, and thallium considerably accelerate the dissolution. The beneficial effect of lead is dependent upon the pH and cyanide ion concentration of the solution. ALTHOUGH cyanide solvents are used very ex-x*. tensively for the recovery of gold from ores and concentrates, the normal rate of solution of the precious metal as determined by Barsky, Swainson, and Hedley,1 and others2 is less than about 3 mg per sq cm of exposed gold surface per hour, corresponding to a corrosion depth of approximately 1.5 microns (0.00006 in.) per hr. Although the slow rate may be increased to some extent in certain cases, as, for example, when the the gold is partially imbedded in iron pyrites,3 the leaching operation is generally the most time-consuming step of the cyanide process. Frequently it is necessary for the leaching solvents to remain in contact with the ores for 50 to 200 hr in order to dissolve all of the gold particles.' Not only does the slow solution rate cause some increase in the capital costs, but the cyanide consumption also may be increased because of vaporization of hydrocyanic acid and secondary reactions with minerals such as malachite (CuCO3 • Cu(OH)2), and pyrrhotite, which often are associated with gold. It is not surprising that numerous attempts have been made to accelerate the dissolution of gold in cyanide solutions. Experimental Gold Leaf Test: The gold leaf test was apparently originated by M. Faraday, who, by means of it, discovered that dilute cyanide solutions would dissolve gold readily in the presence of oxygen. The usefulness and reliability of the test have been discussed elsewhere.5,6 Essentially, the method consists of determining the time required for 5-ml portions of cyanide solvents to dissolve squares of 23 carat gold leaf, 0.5 cm on edge, when shaken in 10-ml test tubes with the solvents. The weight of gold leaf per test was 0.051 mg as determined by the direct weighing of a leaf 8.6x8.6 cm (weight = 15 mg) and measuring the area of the test sample (0.25 sq cm). Gold leaf is of remarkably uniform thickness.6 Since gold leaf, like native gold, contains small amounts of copper and silver, the results are comparable with those one might expect in cyaniding gold ores. As six or more tests can be made simul- taneously, the relative efficiencies of the solvents can be evaluated readily. All dilute solutions of lead, bismuth, thallium and mercury salts were prepared by the ordinary dilution method used by chemists. Our C.P. sodium cyanide and buffering reagents had no detectable amounts of either sulphide ion or heavy metals. Soluble Sulphides in the Cyanide Process: The action of soluble sulphides is of interest in the study of the dissolution of gold in cyanide solutions. That gold ores which contain compounds of arsenic and antimony often are not amenable to direct cyanide treatment is well known, and it said that arsenic and antimony are "cyanicides."7 It is commonly believed that part of the sulphur content of such ores is soluble in alkaline solutions to give sulphide ion, which reacts with the free cyanide content of the leaching solutions to form inert thio-cyanates or reacts with the dissolved oxygen to form sulphites or sulphates.8 A purpose of this paper is to demonstrate that sulphide ion may behave in a manner that cannot be explained by either the oxygen-depletion or thiocyanate formation theories and to prove directly that concentrations of sulphide ion which cannot be detected even by colorimetric methods may retard the dissolution of gold.

Jan 1, 1951

By C. G. Fink, G. L. Putnam

The dissolution of gold by cyanide solutions was studied by determining the time required for the solvents to dissolve gold leaf. Minute traces, even 0.5 ppm, of sulphide ion retard the dissolution of gold, and this behavior cannot be accounted for by the presently accepted hypotheses involving oxygen-depletion or thiocyanate formation. On the other hand, traces of the salts of lead, bismuth, mercury, and thallium considerably accelerate the dissolution. The beneficial effect of lead is dependent upon the pH and cyanide ion concentration of the solution. ALTHOUGH cyanide solvents are used very ex-x*. tensively for the recovery of gold from ores and concentrates, the normal rate of solution of the precious metal as determined by Barsky, Swainson, and Hedley,1 and others2 is less than about 3 mg per sq cm of exposed gold surface per hour, corresponding to a corrosion depth of approximately 1.5 microns (0.00006 in.) per hr. Although the slow rate may be increased to some extent in certain cases, as, for example, when the the gold is partially imbedded in iron pyrites,3 the leaching operation is generally the most time-consuming step of the cyanide process. Frequently it is necessary for the leaching solvents to remain in contact with the ores for 50 to 200 hr in order to dissolve all of the gold particles.' Not only does the slow solution rate cause some increase in the capital costs, but the cyanide consumption also may be increased because of vaporization of hydrocyanic acid and secondary reactions with minerals such as malachite (CuCO3 • Cu(OH)2), and pyrrhotite, which often are associated with gold. It is not surprising that numerous attempts have been made to accelerate the dissolution of gold in cyanide solutions. Experimental Gold Leaf Test: The gold leaf test was apparently originated by M. Faraday, who, by means of it, discovered that dilute cyanide solutions would dissolve gold readily in the presence of oxygen. The usefulness and reliability of the test have been discussed elsewhere.5,6 Essentially, the method consists of determining the time required for 5-ml portions of cyanide solvents to dissolve squares of 23 carat gold leaf, 0.5 cm on edge, when shaken in 10-ml test tubes with the solvents. The weight of gold leaf per test was 0.051 mg as determined by the direct weighing of a leaf 8.6x8.6 cm (weight = 15 mg) and measuring the area of the test sample (0.25 sq cm). Gold leaf is of remarkably uniform thickness.6 Since gold leaf, like native gold, contains small amounts of copper and silver, the results are comparable with those one might expect in cyaniding gold ores. As six or more tests can be made simul- taneously, the relative efficiencies of the solvents can be evaluated readily. All dilute solutions of lead, bismuth, thallium and mercury salts were prepared by the ordinary dilution method used by chemists. Our C.P. sodium cyanide and buffering reagents had no detectable amounts of either sulphide ion or heavy metals. Soluble Sulphides in the Cyanide Process: The action of soluble sulphides is of interest in the study of the dissolution of gold in cyanide solutions. That gold ores which contain compounds of arsenic and antimony often are not amenable to direct cyanide treatment is well known, and it said that arsenic and antimony are "cyanicides."7 It is commonly believed that part of the sulphur content of such ores is soluble in alkaline solutions to give sulphide ion, which reacts with the free cyanide content of the leaching solutions to form inert thio-cyanates or reacts with the dissolved oxygen to form sulphites or sulphates.8 A purpose of this paper is to demonstrate that sulphide ion may behave in a manner that cannot be explained by either the oxygen-depletion or thiocyanate formation theories and to prove directly that concentrations of sulphide ion which cannot be detected even by colorimetric methods may retard the dissolution of gold.

Jan 1, 1951

By K. M. Rolls, J. Wulff, D. A. Colling

Solid-solution alloys of the Ta- Ti system containing up to 70 at. pct Ti were melted and fabricated into wire. Steady magnetic-field measurements of cold-worked wires at 4.2°K indicate that the resistive critical field increases smoothly with increasing titanium, reaching a maximum of 93 kG (J = 1 amp per sq cm) for a composition of about 50 at. pct Ti. The composition dependence of the resistive critical field indicates it is largely paramagnetically limited for alloys containing more than 35 at. pct Ti. For cold-worked wires the value of the critical current density, Jc , was found to be insensitive to composition changes for compositions in excess of 20 at. pct Ti. It was observed that Jc could be increased by final-size heat treatment at 400°C without altering the value of- the resistive critical field. Experimental data are used to calculate the electronic specific-heat coefficient and the "upper critical field" for the alloys studied. THE effect and importance of metallurgical structure on superconducting properties have been summarized by Livingston and Schadler.1 Specific work on solid-solution alloys such as Nb-zr2-7 and Nb-Ti5-7 have shown that critical current density (Jc) and superconducting transition temperature are structure-sensitive. Berlincourt et al.6,8,9 in their studies of transition-metal alloys find that Ta-Ti alloys remain superconducting at fields comparable to Nb-Ti alloys. 6,8 Transverse critical current tests of a Ta-10 at. pct Ti alloy10 and longitudinal critical current tests of a Ta-25 at. pct Ti alloy1' indicate that such alloys are capable of carrying high currents at intermediate fields (-40 kG). The work reported in the present paper was undertaken to explore the superconducting properties of further compositions in the Ta-Ti alloy system as well as the structure sensitivity of the superconducting properties. I) EXPERIMENTAL PROCEDURE Alloys were prepared by melting tantalum (Fansteel Metallurgical Corp., 99.96 pct purity) and iodide, crystal bar titanium (Foote Mineral Co., 99.92 pct purity) mixtures in an arc furnace on a water-cooled copper hearth using a tungsten electrode. Melting was accomplished in a purified, gettered argon atmosphere at pressures from 250 to 400 Torr. Each alloy was turned and remelted fourteen times to assure complete mixing of tantalum and titanium. Ex- cessive coring in the cast samples was, nevertheless, observed. This was somewhat reduced by annealing in vacuo at 1000°C for 13 hr. The ingots were then machined to 0.250 in. diam, jacketed in Type 304 stainless-steel tubing, and swaged to 0.140 in. diam. They were then drawn to 0.010-in.-diam wire. Alloys containing up to 70 at. pct Ti were readily cold-drawn to wire in this manner. Later experiments showed that oxygen additions up to -3000 ppm could also be cold-worked into wire. Test samples for superconductivity measurements in the 2-in, air-core Bitter solenoids of the M.I.T. National Magnet Laboratory were prepared from 10-in. lengths of 0.010-in.-diam wire, cleaned of residual wire-drawing lubricant. Current contacts were made by clamping clean copper tubing over both No. 18 current lead wire and the ultrasonically indium-tinned ends of the specimen wire.12 Potential leads of No. 32 copper wire were connected to the specimen by ultrasonic soldering in an indium bath. The potential lead separation was about 4 cm, corresponding to the circumference of the Bakelite rod to which the wire was affixed with half-mil Teflon tape. The final specimen configuration is shown in Fig. 1. Specimens were lowered into a liquid helium bath (4.2oK) in a double solenoid dewar and positioned so that the maximum magnetic field was oriented transverse to the wire axis of the gage section. Measurements were made by passing a current through the specimen at a preset solenoidal magnetic field. The current was increased until a 1-pv potential difference appeared across the gage section (1/4 µv per cm). At low magnetic fields, however, it was not possible to use this criterion because power-dissipation difficul-

Jan 1, 1967

By J. B. Cheatham, J. G. Yarbrough

Although adequate removal of cuttings from beneath a drill bit is important for efficient drilling operations, very little basic data are available relative to the fundamentals of chip removal by hydraulic jets. A discussion is presented in this paper of an experimental investigation of the jetting action of hydraulic jets in removing loose particles from the bottom of a cylindrical hole. Conditions for which the jet is no longer capable of removing chips from the bottom of the hole are determined. This situation represents equilibrium between the chip removal force and chip Bolddown forces such as gravity and pressure. In most of the tests loose particles were jetted with water or a water-glycerine mixture to determine the dependence of chip removal on hole size, jet size, height of jet off bottom of hole, flow rate, particle density and fluid viscosity. ,A test with a pressurized mud system indicated that relatively low pressures can completely overcome the removal action of a hydraulic jet. Although the system studied herein is not directly applicable to a rotary drill bit, the work with such simplified systems can provide a better understanding of the chip removal action of jets, and with logical extensions it may provide a reasonable basis for the best use of fluid jets in drilling. INTRODUCTION The primary deterrent to maximum drilling rates is the inability of the drilling system to remove rock cuttings efficiently enough to prevent interference with the drilling action.1-2 The objective of chip removal studies is to permit predicting and controlling removal forces under downhole drilling conditions. Conditions at the bottom of a hole during rotary drilling are exceedingly complex and are not likely to be described in a quantitative way by investigations in terms of the total drilling action until a better understanding is developed of the simplified components of the problem.3 The present study is concerned with the elementary condition of removal of chips by a single central jet. Even this relatively simple model provides mathematical difficulties because of the turbulent nature of the flow from the jet and because of the shape of the bottom of the hole beneath the jet. Theoretical and experimental studies have been made of turbulent jets impinging normally on an infinite body and deductions based on analytical solutions to simplified problems can give some insight into the problem of cutting removal by a jet. However, because of the present lack of understanding of the behavior of the interaction between the fluid jet and the chips being removed, an experimental approach was chosen for the present study. Methods have been developed for maximizing hydraulic horsepower, impact force and jet velocity; but whether maximizing these parameters maximizes chip removal with present drilling bits has not been demonstrated. Simplifying the problem of chip removal may make it possible to develop some understanding of the manner in which the jet velocity is dissipated. Better understanding of a simple case should materially assist in extending analysis to more complicated cases. Thus, we are not concerned in the present study with the rock fracturing process itself but only with the removal of the debris from the bottom of the hole. A problem which is quite similar to the chip removal problem is the suspension of solids in stirred vessels. This problem has been studied by the chemical industry and correlations have been obtained by dimensional analysis which permit the design of mixing vats7 An approach similar to that used in the mixing vat problem is used in the analysis of the jetting data in the present paper. EXPERIMENTAL PROCEDURE The test equipment arrangement shown sche-matically in Fig. 1 allows the jetting action to remove particles until an equilibrium height is attained for each combination of hole size, jet size and flow rate.*** Equilibrium conditions require that the removal force is unable to remove additional particles. This balance between holddown and removal forces implies a relationship between the two forces which is constant for the particular system. When the holddown forces are constant,

Jan 1, 1965

By J. F. Smith, J. E. Davison

A value for the enthalpy of formation of z2 of -3.14 i 0.21 kcal per g-atom has been measured by the technique of acid solution calorimetry. This result is in quite good agreement with two earlier determinations by tin solution calorimetry and by direct reaction caloriinetry, and averaging of values determined from the three independent calorimetric techniques gives enhanced precision and accuracy with AHh8 (CaMgZ) = - 3.15 i 0.05 kcal per g-atom. For comparison with experimental data, values for the enthalpies of formation of CaMgz, SrMgz, and BaMgz of -9.8, -7.9, and -2.8 kcal per g-atom were estimated from a calculation based on the LVigizer-Seitz approximation as modified by Raimes for polyvalent elements. While complete quantitative accord between these calculated talues and available experimental data is lacking, nonetheless numerical accord is better than might be expected and, more importantly, parallel numerical trends are observed between experimental and calculated vnlues. WITHIN the past decade the enthalpy of formation of CaMg, has been determined a) from measurement of magnesium vapor pressures over binary Ca-Mg alloys,' b) by solution calorimetry with liquid tin as the solvent,' c) from measurement of hydrogen vapor pressures over ternary alloys of calcium, magnesium, and hydrogen,3 and d) by direct reaction alorimetr. The value from tin solution calorimetry is the most precise and is probably the most reliable, and this value is within the quoted uncertainties of the other three experimental results. The overall agreement among the four independent investigations is quite good, particularly so when the diversity of techniques is noted. On the basis of this agreement, CaMgz was chosen as a test material to evaluate the operation of a newly constructed apparatus for the determination of enthalpies of formation of intermetallic phases by acid solution calorimetry. This was believed to be a severe test because of the high chemical reactivity of both calcium and magnesium which reactivity presumably accounts for the fact that an early determination5 of the enthalpies of formation of Ca-Mg alloys by acid solution calorimetry yielded values significantly more negative than the four recent determinations. EXPERIMENTAL APPARATUS AND MATERIALS Experimental Apparatus. The enthalpy of formation of CaMg, was determined by measuring the difference between the heat evolved when dissolving the metallic compound and the heat evolved when dissolving equivalent amounts of unreacted metallic elements in hydro- chloric acid. This was done differentially with an apparatus consisting of twin calorimeters which were constructed to be as nearly identical as possible. The advantage of differential calorimetry is that systematic errors arising from the individual calorimeter design tend to cancel. A schematic representation of the apparatus is shown in Fig. 1. A dead air space around both calorimeters was provided by a large, thermally insulated jacket. Each calorimeter consisted of a 2-liter Dewar flask which was completely enclosed in a copper container. Each Dewar contained 1600 g of 2.5hr HCl to act as the solvent, and thermal effects resulting from solvent evaporation were minimized by covering the acid with 50 g of mineral oil. There was no detectable reaction between the acid and the mineral oil. Equivalent amounts of mechanical energy were added to the calorimeters through twin stirring rods which were driven at the same rpm by a single motor with the intent of the stirring being to maintain thermal equilibrium throughout the solvent. To calibrate the heat capacities of the calorimeters, known amounts of electrical energy could be added by passing measured voltages and currents for known times through submerged heaters, approximately 20 ohms, which were wound noninductively from Manganin wire. A 6-v storage battery was used as a power source, and a dummy heater was used as an exercise circuit to allow the battery to stabilize at a constant electromotive force before energizing one or the other of the calorimetric heaters. A type K-2 potentiometer was used to measure the potential drop across an energized heater while the current was determined from the potential drop across an external standard resistor. Times of energization were measured with an electric timer, and the electrical energy supplied to a heater

Jan 1, 1969

By E. F. Johnson, F. H. Brinkman, H. J. Welge, S. P. Ewing

This paper presents a method for predicting the manrler in which oil will be displaced from a porous body by enriched gas. The calculations apply to a gas rich enough to give a partially, but not a completely, misci-ble displacement. The method — a three-component, two-phase analysis — takes into account condensation of some of the intermediate hydrocarbons from the injected gas into the oil, as well as enhanced volatility of heavier hydrocarbons at elevated pressures and temperatures. The condensation swells the oil and decreases its viscosity, thus aiding in its recovery. The calculations have been extended to apply to actual crude oil-natural gas systems by arranging the components into three groups according to their volatility. As an approximation, each group is then treated as a single component in the analysis. The influence of an angle of dip for an inclined displacement is also taken into account. The recovery predictions are corroborated by experiments which used both consolidated sand cores and un-consolidated glass beads. In some of these tests, actual live crude oil was displaced by a multicomponent gas typical of enriched gases used in oil fields. INTRODUCTION This paper presents a method for predicting the amount of oil that can be displaced from a homogeneous, linear, porous body at various stages during the injection of enriched, or "wet", gas. The porous body can be in either a horizontal or an inclined position. 'This type of displacement is sometimes known as condensing gas drive The method is developed especially for the case in which the injected gas is enriched enough to be partially, but not completely, miscible with the reservoir oil. The need for a calcula-tive procedure for this type of operation is emphasized by the number of field projects where completely miscible drives are not practical, but where near-miscible conditions are feasible. The factors taken into account in the predictive calculations include: (1) the condensation of gas components into the oil, with a resulting increase in oil volume; (2) the lowering of oil viscosity by the addition of lighter ends from the gas; (3) the increase in oil volatility at high temperatures and pressures; and (4) the physical displacement of the oil by the gas. The techniques developed in the paper can be extended to other nonequilibrium displacement processes. Other such processes that we have analyzed include a displacement by lean gas which stripped intermediates from the oil, and a water flood in which the water con. tained in solution a substance somewhat soluble in the oil. ANALYSIS OF ENRICHED-GAS DRIVE GENERAL PRINCIPLES Our method for predicting the amount of oil that can be displaced by an enriched gas uses an analogy between a three-component and a multicomponent system.' The predictive method is based on these assumptions: (1) constant, or nearly constant, pressure; (2) complete equilibrium by diffusion perpendicular to the main direction of flow, but no significant mixing along the direction of flow; (3) constant injection velocity; and (4) flow in a linear porous body. The composition of a liquid or a vapor with respect to three components can be plotted on a three-component, or ternary, diagram like that in Fig. 1. Let Point A represent the composition of the oil originally in place. In this case, Oil A is undersaturated with gas. If Point A lay on the equilibrium Curve BF, the oil would be saturated. In the extreme case where the original oil contained no intermediates or dissolved gas, Point A would lie at the lower left-hand corner of the ternary diagram. In a displacement of Oil A by Gas D, there will be a progressive change in the composition of the oil phase as more and more gas is brought into equilibrium with the oil. The end result of this progressive change is an oil having the composition represented by Point F. This oil is richer in intermediate hydrocarbon and methane than the original oil and, therefore, has a greater forma-

By John W. Wagner, Robert K. Willardson

Single crystals of Pbl-xSnxTe have been grown from nonstoichiometric, cation-rich melts with the objective of producing as-grown, bulk material containing carrier concentrations ranging from 1016 per cu cm to 1018 per cu cm. Three specific crystal composi-tions were investigated in detail; x = 0.00, 0.10, and 0.17. Pull rates of from I to 3 mm per hr were used. Single crystals were successfully pulled from melts containing as little as 30 at. pct Te. Hall coefficients, resistivities, and carrier mobilities of these materials were determined. The relationship between the composition of the melt and the carrier concentration in the as-grown crystal has been studied for the three crystal compositions of interest. BULK single crystals of Pb,-,Sn,Te have previously been grown from stoichiometric melts.1,2 Such crystals are p-type and have relatively high carrier concentrations ranging from -9 x 1018 per cu cm for PbTe to -8 x l020 per cu cm for SnTe at 77°K. These carrier concentrations result from deviations from stoichiometry (lead vacancies) in the as-grown crystals. Since lower carrier concentrations are desirable for electrooptic device applications, these crystals are usually subjected to long-term, isothermal anneals.' This paper reports on the growth of Pbl-xSnxTe single crystals from nonstoichiometric melts with the primary objective of producing as-grown material containing relatively low (1016 to 1018 per cu cm) carrier concentrations and also reports on the general characteristics of these crystals. The phase relationships in the Pbl-xSnxTe systems are such that materials solidifying from nonstoichiometric, cation-rich melts will have smaller deviations from stoichiometry than materials grown from stoichiometric melts. Fig. 1 is the T-x phase diagram for PbTe in the vicinity of the stoichiometric composition.3 A crystal grown from a stoichiometric melt will solidify at a melting point maximum at which the solid will contain -0.5002 atom fraction of tellurium. PbTe single crystals grown in our laboratories from stoichiometric melts have carrier concentrations of 9 x 10" per cu cm, indicating that the excess tellurium in the crystals is as expected from this phase diagram. However, growth of PbTe from a lead-rich melt will result in material having a more nearly stoichiometric composition. Although the addition of Sn to the melt shifts the solidus curve further toward the tellurium-rich side,4 the general discussion given for PbTe applies to the Pbl-xSnxTe systems as well. EXPERIMENTAL Single crystals of Pb1-xSnxTe have been grown in our laboratories from nonstoichiometric, cation-rich melts using the Czochralski technique and boric oxide liquid encapsulation. The details of the growth apparatus and growth technique have been reported in a previous paper on growth of these alloys from stoichiometric melts.2 In the present study, three specific crystal compositions were investigated in detail; x = 0.00, 0.10, and 0.17. Growth of alloy crystals from nonstoichiometric melts requires considerable care, and good quality single crystals were obtained in this study only by optimizing the mechanical and thermal stability of the growth system and by using pull rates of from 1 to 3 mm per hr (Pbl-xSnxTe crystals are easily pulled from stoichiometric melts at rates of from 5 to 10 mm per hr). The liquid encapsulation technique was found to yield near-ideal conditions, since the B2O3 layer increased the thermal stability at the growth interface, permitted easy attainment of near-ideal thermal gradients, and dampened vibrations at the melt surface. The hygroscopic character of the B2O3 was a slight problem and vacuum heat treating was necessary to completely remove the water from the boric oxide. During initial growth, the seed diameter was reduced and a narrow neck (1 to 2 mm diam) of several millimeters length was grown. The latter steps were found to be necessary for the growth of single crystals, i.e., if either of these two requirements were

Jan 1, 1970

By R. Q. Shotts

Nitric acid oxidation rate analyses of three coals, previously studied microscopically by the Bureau of Mines, revealed three components. Relative quantities agree with those found for the four components given by the Bureau and results are consistent with current ideas of coal constitution. Possible multi-component composition for bright coal and a reactivity-rank relation are suggested. THE physically dissimilar components of bituminous coals often are easily recognized mega-scopically. Under the microscope, reflected light or light transmitted through thin sections reveals the presence of the different components, even when these are intimately mixed. Optical methods for the quantitative estimation of the relative abundance of the various components, both by means of thin sections and by particle count, have been fully described.'. ' It has long been recognized that there are chemical and physical differences between the various petro-graphic components of bituminous coals, although analytical differences usually are small.:'. ' Only in the case of fusain have chemical differences been used for quantitative determination of a component. C. C. Hsiao and associates, at the Mineral Industries Experiment Station of the Pennsylvania State College, have described a method of analysis which is based upon the differences in the rate of nitric acid (8N) oxidation, fusain, and the other components of coal."," The reproducibility of their method and its applicability in checking microscopic determinations of fusain content have been supported by several independent investigations.'. " The writer has proposed the use of differences in oxidizability for the estimation of other components." "' The results of the oxidation of whole coals and of float-and-sink fractions of coals were reported. In most cases the plots of the logarithms of the percent dry, non-fusain, organic residue from oxidation, against time, revealed the presence of at least two distinct components. Both components appeared to oxidize according to a first order law, but the reaction constants for the components were distinctly different. One or more of the dull density fractions were found to contain but one component, and some of the lower rank coals oxidized in such a way as to suggest the presence of three components. A suitable way to check the identity and significance of the components delineated by oxidation would be to analyze a sample of coal both by the nitric acid oxidation procedure and by a microscopic method. The writer was wholly unfamiliar with either of the microscopic techniques commonly used, and to make such a comparison it was necessary to rely upon microscopic analyses made by someone else. It is hoped that some laboratory which is equipped to make both types of analyses will some day make them upon identical samples. During the past 20 years, four Alabama coals have been analyzed petrographically and the results published by the United States Bureau of Mines. They are: 1—Flat Top mine, Mary Lee bed; 2—Empire mine, Black Creek bed; 3—Wylam No. 8 mine, Pratt bed, all in the Warrior field; and 4—Soot Creek mine, Fairview bed, in the Coosa field."-" Of these, only the Flat Top mine is still operating. Because of the closing of these mines, it first appeared necessary to rely upon the indirect and unsatisfactory procedure of sampling the beds in other mines located as near to the closed mines as possible. Upon investigation, however, it was found that the Bureau of Mines still had, in storage, the very same samples which had been used in the published petrographic studies. The Bureau very generously furnished about 2000 g each of the Pratt, Mary Lee, and Fairview bed coals, largely lumps but with some fines. The blocks of coal, when received, still were covered by the paraffin coating which had been placed on the polished surface, in the case of the Mary Lee coal almost twenty years ago. Procedure The procedure for oxidizing the coal sample and removing the alkali-soluble humic acid has been described. In the present study, oxidation periods of 1/6, 1/3, 1/2, 3/4, 1, 2, 3, and 4 hr were used. All oxidations were made in triplicate. After the paraffin had been removed in boiling water and the coal washed carefully with cold benzene, the entire sample of approximately 2000 g, obtained from the Bureau of Mines, was crushed to pass a No. 4 sieve. About 200 g of this material was pulverized to pass

Jan 1, 1954