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By S. H. Penn

One of the more challenging aspects of the unfolding age of space travel centers about the opportunity for man to use the natural resources of other worlds. The first of the extraterrestrial worlds to be exploited will be the moon. After only a scant few thousand years of scratching the earth's crust, man will embark upon a venture that for centuries has excited the imagination of many (while staggering that of most) and may become a reality within the next decade. There has never been a time when so much money and effort will have been expended to exploit an area about which so little is known. Paradoxically, this effort combines much of the detached objectivity so typical of our analytical time with the proverbial optimism of the indefatigable prospector. As the earliest manned lunar missions will be brief and exploratory in nature, astronauts will not be expected to attempt to exploit any of the possible lunar natural resources. In later missions, with a more extended period of time available for the astronauts to stay on the moon, it may be desirable or even necessary to "live off the land". The resulting exploitation of lunar resources will be intended primarily to reduce the dependence of manned missions upon terrestrial logistic support and to reduce the cost of maintaining lunar bases.

Jan 3, 1966

By Thomas T. Read

THE fact that certain types of ore-deposits have attained their present condition through the action of descending surface waters was, perhaps, first clearly pointed out by Posepny.1 The oxidizing effects of such waters were discussed by Penrose,2 and many papers dealing with this phase of the subject have subsequently appeared. That secondary enrichment of sulphide ores, however, might be produced by descending surface waters was not clearly understood until after the copper-bearing veins of the Butte district, Mont., had been carefully studied by the geologists of the U. S. Geological Survey, al¬though De Launay3 had suggested that sulphides might be transported from point to point and re-deposited in the zone above the level of ground-water. As a result of the study of the Butte district, two papers by geologists engaged in the work appeared within a short interval. The first by Weed,4 dealing with the enrichment of veins by later metallic sulphides: and the second by Ernmons,5 treating of the secondary enrichment of ore-deposits in general. In the latter paper it was pointed out that a typical vein of sulphide ores which has been subjected to the action of descending surface waters exhibits four zones,-an upper or surface zone, in which the changes have been mainly of removal, the products being typically oxides; a second zone of oxide enrichment, in which the less soluble metals brought from above have been precipitated as carbonates or oxides; a third zone of sulphide enrichment,

Mar 1, 1906

By K. BRUCE DAVIDSON

-The North Central Texas area includes the following counties in Railroad Commission of Texas District 7-B: Brown, Callahan, Coleman, Comanche, Coryell, Eastland, Erath, Fisher, Hamilton, Haskell, Hood, Jones, Lampasas, Mills, Nolan, Palo Pinto, Parker, S

Jan 1, 1946

By E. J. KENNEDY

METHODICAL AND EFFECTIVE: thus may be characterized the fall meeting of the Iron and Steel and Institute of Metals Divisions at the Hotel Statler, Buffalo, N. Y., on Oct. 4 and 5. Approximately 200 registered. Interest centered 1111 the technical papers which were keenly followed, with substantial discussion: During the entire week of the National Metal Congress (Oct. 3 to 'i), there were also other sessions of interest' to metallurgists, directed by the America11 Society for Steel Treating, American Welding Society, Production Division of the Society of Automotive Engineers, the Iron arid Steel and Machine Shop Practice Divisions of the American Society of Mechanical En,' the Wire Association and the American Drop Forging Institute. The National Metals Exposition at the 174th Regiment Armory was well attended.

Jan 1, 1932

By S. R. Rao, J. Leja, K. S. Moon

A prolonged grinding of sulphide ores in steel mills appears harmful to flotation recovery and selectivity whenever xanthates are used as collectors. Particles finer than about 10µm show a pronounced decrease in floatability. A supposition was made that the cause of the reduction in floatability of ground sulphides is the presence of metallic iron abraded during grinding and deposited on the ground particles. Electro- chemical measurements were made of mixed potentials developed by different sulphide-mineral electrodes (galena, chalcopyrite, pyrite, marmatite, pyrrhotite) in xanthate solutions, without a direct con- tact or in contact with a metallic iron electrode. These measurements showed that without a galvanic contact between the sulphide and the iron, the values of mixed potentials were in the vicinity of the xanthate/dixanthogen redox potential. When contact with iron was established, the mixed potentials shifted towards the more negative reducing or cathodic values. The shift was greater the higher was the ratio of the surface areas: iron electrode to sulphide electrode. Further, the shift in mixed potentials was greater the more reducing were the conditions on the sulphide electrode. Chemical analysis of reaction products produced on the surfaces of sulphides and in the bulk solution showed that less thiosulphate was formed in all of the sulphide-xanthate systems and that more elemental sulphur was detectable on the pyrite and marmatite surfaces. Adsorption of xanthate parallels the amount of thiosulphate formed with which xanthate is exchanged by metathesis. If the supply of oxygen is limited, the demand for oxygen by the abraded metallic iron competes with that by the valuable sulphide, resulting ultimately in poorer hydrophobicity. If excessive amounts of pyrite or pyrrhotite are present as well, the conditions are so reducing that there is little adsorption of xanthate ions on the valuable sulphides to make them hydrophobic and floatable. The presence of increased quantities of sulphur on pyrite or marmatite is responsible for a non-selective flotation. Flotation tests on synthetic mixtures with and without metallic iron powder in the feed confirmed the above conclusions from electrochemical and chemical measurements.

Jan 1, 1976

By John D. Sullivan

A DISCUSSION of the developments of the past decade in the field of refractories, and the effect of these developments on the performance and life of open-hearth furnaces, is perhaps best introduced by reference to Fig. 1. This shows the most important types of refractories doing into various parts of the furnace, together with their cost, and remarks on their use. It has been estimated that half of the refractory makers market comes from the iron and steel industry, and something like one-third of all refractory brick used finds its way into open-hearth furnaces. To melt steel, a furnace capable of withstanding temperatures close to 3000 deg. F. is required. The furnace is assembled of various refractory materials selected by experience and economic considerations. Furnace structures today, from a refractory standpoint, are considerably different from a quarter century ago. Furnace operators, interested in the performance of refractories, care little how they are made or where they come from so long as they give reasonable service. But, the entire history of the refractory is important and technical knowledge of the ceramic materials used in making the refractory is necessary to the manufacturers, so that the proper article gets into the hands of the ultimate consumer.

Jan 1, 1936

By F. A. Olson, S. L. Pohlman

A unique method of measuring weight loss as a function 3 of time, with a sensitivity of 10-5 grams, while leaching copper minerals with a flowing acid leach solution has been developed. Kinetic results obtained coupled with visual and microprobe analyses show topochemical reaction for the leaching of chrysocolla with sulfuric acid. The kinetics follow a shrinking core model and show ion diffusion through a product layer, chemical reaction at the unreacted core interface and mass transfer through the boundary layer as being important.

Jan 1, 1974

By J. D. Lubahn

The influence of precipitation from solid solution on the subsequent deformation resistance of alloys is well known. However, the influence of precipitation or aging that occurs simultaneously with deformation may be entirely different and of considerable importance. It is thought1 that the presence or absence of a yield point jog in impure iron at room temperature and the presence or absence of discontinuous flow at higher temperatures may be directly related to aging phenomena, particularly since the yield point jog is absent when the carbon and nitrogen are sufficiently removed.2 As a preliminary attack on the problem of simultaneous aging and deformation, three kinds of tests—constant strain rate tensile tests, constant load creep tests, and variable strain rate tensile tests—were carried out on an age hardenahle aluminum alloy. Constant Strain Rate Tensile Tests Stress-strain curves at a strain rale of about 0.001 min-1 were obtained for specimens of 61S that had been quenched into liquid nitrogen after a one-hour solution treatment at 521°C, then aged at room temperature 10 min., 20 min., 4 hr, and 26.5 hr before testing. Strain-time curves were obtained on the same chart with the stress-strain curve by means of an auxiliary pen, driven parallel to the axis of the chart drum at constant speed by a synchronous motor and gear chain. The angle of rotation of the chart drum was proportional to strain. The strain rates reported are the measured slopes of the strain time curves. Constant strain rate was approximated (within a factor of 2) by manual adjustment of the oil inlet valve of the hydraulic testing machine in such a way that the course of the recorder pen was parallel to pre-drawn strain-time lines of the desired slope. The specimens were machined from 9/16 in. rod. The cylindrical portion was 0.357 in. in diam by 13/4 in. long and

Jan 1, 1950

By W. P. Sykes

In connection with a study of tungsten steels, Honda and Murakamil reported an investigation of the system iron-tungsten. This report included a tentative equilibrium diagram, photomicrographs of various alloys in the series, and qualitative measurements of hardness and magnetic properties. The present investigation originally had as its object the study of the hardness and tensile properties of a series of carbon-free iron-tungsten alloys. But, as the work progressed it became evident that the system possessed other features of interest, so the scope of the investigation was enlarged. Materials The iron powder used in preparing the alloys was obtained as follows : Iron oxalate was precipitated from a ferrous-sulfate solution by the addition of a solution of oxalic acid. This oxalate, after thorough washing, was ignited to iron oxide, which after reduction in hydrogen at about 1000" C. yielded iron powder containing but about 0.2 per cent. iron oxide and about 0.005 per cent. carbon. Tungsten metal in the form of powder, such as is used in the manufacture of filaments for incandescent lamps, was the other constituent. This material analyzed 99.8 per cent. tungsten and contained no carbon. The metal powders, in the desired proportions, were mixed by tumbling and formed, under pressure of 20 tons per sq. in., into rods 3/8 by 3/8 by 10 in. To form the alloys without contamination, sections of the pressed rods were placed on alundum slabs and heated in an alundum tube wound with a tungsten resistor and packed in heat-insulating material. While the resistor was heated, a stream of hydrogen was continually passed through both the tube and the case containing it. The tungsten winding on the tube, as well as the material heated within the tube, was thus protected from oxidation. Such a furnace will operate constantly for several days at temperatures up to 1500' C. and for shorter periods

Jan 1, 1926

By Daryl R. Tweeton, Jerry R. Riding, Grant Buma, Frank J. Rosswog

In situ solution mining of uranium has environmental advantages over conventional mining. The leaching of uranium, however, alters the ground-water quality in the aquifer where the mining occurs. Currently, regulations require that the ground water be restored to approximately its original condition. This paper, a summary of a study funded by the Bureau of Mines, reviews the state of the art in restoring ground-water quality after in situ uranium leaching. Current restoration practices discussed include disposal of liquid wastes in deep disposal wells and evaporation ponds, producing from all wells during restoration, and recirculating water purified in surface plants. Methods for predicting the effectiveness and cost of current techniques are presented. Possible alternative techniques are also described. Two restoration operations are discussed.

Jan 1, 1979

By J. Burns Read, S. Tour

It is the purpose of this paper to summarize, as far as possible, the metallurgical information and experience gained by the Ordnancc Department, during the war, in the manufacture of artillery cartridge cases, to describe the tests to which artillery cartridge cases were put, and to summarize the knowledge and experience gained in this testing. The authors wish to acknowledge the aid given by manufacturers, army officers, and civilian employees of the Department in obtaining data. Artillery cartridge cases are cold drawn from circular disks punched from strips of rolled brass. The rnanufacture involves from 25 to 30 main operations, which are done almost entirely on a punch press. Descriptions of the operations have appeared in various periodical:: and, therefore, will not he given here. After each cupping, or drawing, operation, except the last, the cases are annealed at from 540" to 650" C. (1000" to 1200°F.), to remove all the hardening stresses set up in the metal and to allow complete recrystallization. After each annealing, the cases are pickled in niter cake or sulfuric-acid solution and then washed in water to remove all traces of acid. In some instances, the cases arc then immersed in a cyanide-salt solution, and afterwards rinsed in water, to remove the thin layer of copper that forms on the surface of the cases during the acid pickle. The last cold-drawing operation is followcd by the heading operation which, by flattening the head of the case on the outside, causes the metal to flow on the inside to approximately the proper finished dimensions. The mouth, or open end, is then annealed at 430" to 450" ('. 1800" to 900" F.) by immersion in a salt bath or by gas flames. After being washed, the eases are tapered, when they arc ready for machining, inspection, and testing. Cartridge-case Disks Good disks of proper composition and physical properties are essential to the production of good cartridge cases. The Ordnance Department

Jan 1, 1923

By J. Burns Read, S. Tour

It is the purpose of this paper to summarize, as far as possible, the metallurgical information and experience gained by the Ordnancc Department, during the war, in the manufacture of artillery cartridge cases, to describe the tests to which artillery cartridge cases were put, and to summarize the knowledge and experience gained in this testing. The authors wish to acknowledge the aid given by manufacturers, army officers, and civilian employees of the Department in obtaining data. Artillery cartridge cases are cold drawn from circular disks punched from strips of rolled brass. The rnanufacture involves from 25 to 30 main operations, which are done almost entirely on a punch press. Descriptions of the operations have appeared in various periodical:: and, therefore, will not he given here. After each cupping, or drawing, operation, except the last, the cases are annealed at from 540" to 650" C. (1000" to 1200°F.), to remove all the hardening stresses set up in the metal and to allow complete recrystallization. After each annealing, the cases are pickled in niter cake or sulfuric-acid solution and then washed in water to remove all traces of acid. In some instances, the cases arc then immersed in a cyanide-salt solution, and afterwards rinsed in water, to remove the thin layer of copper that forms on the surface of the cases during the acid pickle. The last cold-drawing operation is followcd by the heading operation which, by flattening the head of the case on the outside, causes the metal to flow on the inside to approximately the proper finished dimensions. The mouth, or open end, is then annealed at 430" to 450" ('. 1800" to 900" F.) by immersion in a salt bath or by gas flames. After being washed, the eases are tapered, when they arc ready for machining, inspection, and testing. Cartridge-case Disks Good disks of proper composition and physical properties are essential to the production of good cartridge cases. The Ordnance Department

Jan 1, 1923

By F. Habashi

Conclusive evidence is given showing that the dissolution of gold in cyanide solution follows mainly the over-all equation A similar equation can also be written for the dissolution of silver. Theoretical derivation of the velocity equation for this reaction has been obtained, which describes quantitatively the experimental facts. The equation is as follows: where [CN-] and [O2] = the concentrations (in moles/ml) of cyanide and dissolved oxygen, respectively. DcN- and Do2 = the diffusion coefficients of cyanide and dissolved oxygen; 1.83 x 10-5 and 2.76 x 10-5 cm2 sec-1, respectively. A = the surface area of the metal in contact with the aqueous phase, in cm S = the thickness of the boundary layer; varies between 2 and 9 x 10-3 cm, depending on the speed and method of agitation. Rate being expressed in g. equiv. sec-1. INTRODUCTION During recent years a number of papers have been published on the kinetics of dissolution of gold and silver in cyanide solution.1,6 The authors agree that the rate of dissolution is diffusion-controlled, but disagree regarding the mechanism of the reaction. Some authors'-3 support the Bodlander equations: The apparently conflicting results, when critically reviewed, are concordant and lead to the conclusion that the proper equation for the dissolution reaction should be only Eq. 1. This conclusion is based on the following facts: 1) For every 2.2 equivalents of metal dissolved one mole O2 was consumed. 2) For every 1 equivalent of metal dissolved, 2 moles of cyanide were consumed.' 3) Hydrogen peroxide is formed during the dissolution of gold or silver, and for every 2.2 equivalents of metal dissolved, one mole H2O2 was produced.1,2 The fact that Kudryk and Kellogg4 did not detect H2O2 during the dissolution of gold should not throw doubt on the many affirmative reports of other investigators. Lund2 has shown that depending on the crystalline nature of the silver surface, (e.g. method of etching the sample) H2O2 may undergo catalytic decomposition heterogeneously according to: Further Kudryk and Kellogg4 carried out their experiments in the presence of 0.5% KC1 to achieve a greater electrolytic conductivity, and Matsudaira7 has shown that H2O2 is catalytically decomposed (homogeneously) in the presence of C1- ion in alkaline solution. 4) Experiments carried out by Boonstra8 and Lund2 showed that the dissolution of gold and silver respectively in KCN + H2O2 in the absence of oxygen was a slow process. Thus the reaction takes place to a minor extent only. Further kinetic studies showed that: 1) The rate of dissolution depends on the surface area of the metal in contact with the liquid phase, thus indicating that the process of dissolution is a heterogeneous process. 2) The rate of dissolution depends on the speed of stirring,5,6 thus indicating that the process is controlled by a physical phenomenon.

Jan 1, 1967

By R. W. Smith. Discussion by D. Watson, R. M. Manser

D. Wotson, R. M. Monser (Watten Spring Laboratory, Stevenage, Herts., U. K.) - This is a valuable and interesting paper and will make an important contribution to the development of a general theory of silicate flotation. In particular the dominance of surface reactions which produce fluosilicic acid and its ions has been convincingly demonstrated. In a paper to be published shortly, however, we offer some evidence which is not consistent with the feldspar activation theory proposed by Prof. Smith. This theory, given in Eqs. 17-20, suggests that activation takes place through the exchange of SiF6 ions for OH- at aluminum sites. This results in a negatively charged site facilitating adsorption of RNH3 Firstly, we have determined the flotation response (using the vacuum flotation technique) and the adsorption of dodecylamine on a natural feldspar (albite) and on the same feldspar after washing with perchloric acid at pH3. This pre-treatment was shown to remove surface adjacent aluminum atoms. It was found that although the acid washed feldspar floated much less easily than the untreated sample, the function of fluoride ion - giving activation over the pH range 4-6.5-was preserved. Moreover, the amount of dodecylamine adsorbed either with or without fluoride present is little affected by acid-washing, despite the depression caused by this treatment. This suggests that surface aluminum atoms can be of little importance in the fluoride activation mechanism. Secondly, we have determined the changes in solution concentration of F- and H+ (or OH-) accompanying reaction of the surface with fluoride ion. The ratio of H+ lost from solution to F- lost is high, ranging from 6.9 at pH4 to 1.0 at pH 7.5. This is consistent with reaction of HF (6 molecules for every Si removed) at the surface, producing SiFi-ions, but not with the re-adsorption of these ions.

Jan 1, 1967

By Arthur Notman

THE raw material men in all industries, and copper is no exception, are accustomed to think of them- selves as the whole show, and not without justice, for if there were no copper mines the world would have no copper. Nevertheless, many different things costing money and resulting in profits must be done to their product before it is ready for the world's use. In other words, they are making the frequent mistake of Chinking in terms of partial costs. Nobody really uses electrolytic copper. Possibly that is why nobody seems willing to pay anything for it. The manufacturers, being canny, do not buy any more electrolytic than they feel that they can work up and sell profitably, although they like to make the raw material men Chink that they will take all that can be produced. This is a state of affairs that has aroused my sympathy and curiosity, and has induced me to study the financial history of the copper wire and brass industry of the country or such portion of it as publishes any records readily available to the curious minded. About 60 per cent of the electrolytic copper used in this country is drawn into wire and consumed by the electrical industries. The remaining 40 per cent is

Jan 1, 1926

By T. R. Graham, R. G. Feustel, J. R. Long, R. S. Dean

The comprehensive study of the copper-manganese-zinc alloy system in the Bureau of Mines Laboratories has so far been principally concerned with alloys that lie within the alpha solid solution field of the system. Two regions, one centering about 65 per cent copper, 10 manganese and 25 zinc, and the other centering about 70 per cent copper, 20 manganese, 10 zinc, have been carefully examined. These have indicated that when the alloys are made with electrolytic manganese considerable amounts may be readily introduced and that the strength and hardness are increased without excessive losses in ductility. In the course of the work of establishing the limits of the alpha solid solution range,3 enough of certain of the alloys was prepared to permit determination of their- physical properties at a future date. The 60 per cent copper alloys concerned here are part of that series. They cross through the alpha field and into the adjacent alpha plus beta and alpha plus X fields, and are of interest because they offer some information on the effects of manganese on alloys lying in these fields. Composition and Fabrication of Alloys The chemical composition of the alloys involved is given in Table I. They were intended to contain 60 per cent copper with manganese increasing from 5 to 25 per cent in 5 per cent steps and zinc decreasing from 35 to 15 per cent. The analyses are so close to the intended composition that the alloys mill be referred to hereafter by their norninal compositions. They were finished into sheet by cold-rolling and intermediate annealing procedurzs calculated to produce sheet $i6 in. thick, cold-reduced by 20, qo, 60, and 80 per cent in thickness. Physical properties were determined on standard flat tensile specimens with 4-in. gauge length, although the test gauge section used was 2 in. The properties were obtained on cold-worked material and on material annealed at temperatures ranging from 700' to r500°F. after 60 per cent cold reduction. Since an annealing temperature of 1200°F.

Jan 1, 1946

By J. R. Long, T. R. Graham, R. G. Feustel, R. S. Dean

The comprehensive study of the copper-manganese-zinc alloy system in the Bureau of Mines Laboratories has so far been principally concerned with alloys that lie within the alpha solid solution field of the system. Two regions, one centering about 65 per cent copper, 10 manganese and 25 zinc, and the other centering about 70 per cent copper, 20 manganese, 10 zinc, have been carefully examined. These have indicated that when the alloys are made with electrolytic manganese considerable amounts may be readily introduced and that the strength and hardness are increased without excessive losses in ductility. In the course of the work of establishing the limits of the alpha solid solution range,3 enough of certain of the alloys was prepared to permit determination of their- physical properties at a future date. The 60 per cent copper alloys concerned here are part of that series. They cross through the alpha field and into the adjacent alpha plus beta and alpha plus X fields, and are of interest because they offer some information on the effects of manganese on alloys lying in these fields. Composition and Fabrication of Alloys The chemical composition of the alloys involved is given in Table I. They were intended to contain 60 per cent copper with manganese increasing from 5 to 25 per cent in 5 per cent steps and zinc decreasing from 35 to 15 per cent. The analyses are so close to the intended composition that the alloys mill be referred to hereafter by their norninal compositions. They were finished into sheet by cold-rolling and intermediate annealing procedurzs calculated to produce sheet $i6 in. thick, cold-reduced by 20, qo, 60, and 80 per cent in thickness. Physical properties were determined on standard flat tensile specimens with 4-in. gauge length, although the test gauge section used was 2 in. The properties were obtained on cold-worked material and on material annealed at temperatures ranging from 700' to r500°F. after 60 per cent cold reduction. Since an annealing temperature of 1200°F.

Jan 1, 1946

By M. F. COOLBAUGH

WHEN I was asked to speak on the subject of leaching, I did not realize that a complete summary of recent progress in leaching had been given by Stuart Croasdale. I shall try to give some other phases of the subject that were not touched by Mr. Croasdale. Not all metallurgists are in harmony as to their methods of treating metals. If they were it would probably mean lack of progress. They can be divided into two classes-the pyrometallurgists, using fire means, and the hydrometallurgists, or those using leaching methods. Conflict is always good for progress; we have it in politics, and in religion there are fundamentalists, and those who are not fundamentalists. As representing pyrometallurgy, may I hope not to be classed among the fundamentalists. The leaching of ores is not new. The leaching of ores for the recovery of metals, however, is quite new. The older leaching was simply to recover the salts. Agricola, back in 1555, I think it was, outlined a great many methods of leaching for the recovery of salts. They called them solid juices at that time. There was no real competition, however, between leaching meth-

Jan 1, 1926

By D. Havlena, A. S. Odeh

The use of the straight-line method of solving the material balance equation is illustrated by means of six field cases. Also, the application of statistical criteria to arrive at the most probable answer is shown. The theory underlying the straight-line method of solution and the applicability of the statistical criteria was presented in a previous paper.' The field cases include saturated and undersaturated oil reservoirs with and without water drive. The aquifers discussed are: limited radial, infinite radial, very small aquifer and infinite linear. The field cases also include a gas reservoir producing under water drive. INTRODUCTION In a previous paper,' the authors presented the theory underlying the solution of the material balance as an equation of a straight line. The appropriate equations for various material balance cases as well as the methods of analysis and interpretation with comments and discussion were also included. To illustrate the various theoretical cases treated previously, five field cases are analyzed in this paper by employing the straight-line method of solving the material balance equation (MBE) and one example previously published is referred to. The use of statistical criteria to arrive at the most probable answer is also shown. All the field examples presented, except Case 2, are excerpts from complete reservoir studies. To illustrate the method, only sections specifically dealing with the material balance principles are included. Additional geologic information and basic data are reported to better acquire an understanding of the cases and thus to better follow the reasoning that suggested the successful application of the straight-line method of solving the MBE. The six cases are: (1) saturated reservoir, small gas cap, limited aquifer; (2) saturated reservoir, very small gas cap, infinite aquifer; (3) undersaturated-saturated reservoir, very small aquifer; (4) highly undersaturated reservoir, no water drive; (5) high undersaturated one-well reservoir, limited aquifer; and (6) gas reservoir, infinite linear aquifer. THE D4 SAND, GUICO FIELD, VENEZUELA The D, sand, which was discovered in 1943, is presently in a depleted state. Since its discovery it has produced under water drive, gas-cap-gas expansion, and solution gas drive. In Nov., 1947, water injection was initiated to arrest further pressure decline. When discovered, the D, sand was a saturated reservoir with a gas cap /oil zone volume ratio m estimated volu-metrically at 0.0731, an average permeability of 500 md, a porosity value of 25 per cent, and an oil viscosity at reservoir conditions of 0.3 cp. The volumetrically determined stock-tank oil initially in place was 23.1 million bbl. The volumetrically weighted physical data and production data available until Nov., 1953 are reported in Table 1. In Ref. 1, the effects on the straight-line plot of various values of ro/r for a constant ?to, or of various dimen-sionless times for a constant r8/r10 were theorized and were illustrated in Fig. 3A of that reference. In this field case, the previously theoretically predicted effects are established. Thus, the MBE calculations using Eq. 3c of Ref. 1 were performed for various r6/r10 and dimension-less time values. Eq. 3c of Ref. 1 is:

Jan 1, 1965

By Jacques Steininger, Robert E. England

Single crystals of ZnTe and ZnTe1-,Sex with x up to 0.13 have been grown from the elements by temperature gradient solution zoning using excess tellurium as a solvent. Best results have been obtained with charges with the compositions 45/55 at. pct Zn, Te, for ZnTe and increasing amounts of selenium for ZnTe1-xSex. The temperature in the molten zone was maintained at about 1070°C with a gradient of about 10°C per cm. Chemical analyses of quenched ZnTe ingots show tellurium concentrations in the molten zone as high as 70 pct with concentration differences across the zone of 1 to 2 at. pct Dark dots which are observed by transmitted light microscopy in as-grown crystals can be removed by annealing in zinc vapor at 900 C. INTEREST in wide band gap semiconductors has led to a new study of ZnTe and ZnTel-xSex crystal growth. ZnTe is the only II-VI compound with a wide band gap (2.3 ev) that can be made p type with low resistivity. Attempts to make it n type with low enough resistivity to be useful for p-n junctions have so far been unsuccessful.1 ZnSe has a band gap of 2.65 ev but can be made n type only. However, ZnTel-xSex solid solutions with x as low as 0.36 have been made both highly n and p type2 with a minimum band gap around 2.12 ev3 at room temperature and appear to hold the best promise for efficient injection electroluminescence in the visible. ZnTe has the lowest melting point of the zinc chal-cogenides (1295°C) and consequently attempts have been made to grow crystals from both the liquid and the vapor phase.4 Complicated apparatus is required for growth from stoichiometric melts because of the high vapor pressures of the elements at the melting point of ZnTe and because of the problem of quartz devitrification. Small crystals have thus been grown in high-pressure equipment by Fischer5 and by Narita et a1.6 with pressures of the order of 50 atm of argon to prevent excessive evaporation from the melt. Large crystals of ZnTe can be obtained by growth from the vapor phase4 but they often present numerous dislocations and inclusions. An improvement in the quality of vapor- grown ZnTe crystals was reported by Albers and Aten7 by equilibration of mixtures of small crystals with compositions lying on either side of the solid single-phase field at fixed temperature. The same technique was later applied by Aten8 to the growth of ZnTe1-xSex crystals with less than 1 pct inhomo-geneity. Because of the higher liquidus temperatures of the solid solutions and the high vapor pressure of selenium, previous attempts to grow ZnTel-xSex from the melt have been limited and unsuccessful.9 The phase diagram of the Zn- Te system is reproduced in Fig. 1, based on data from Kobayashi10 and Kulwicki.11 Carides and Fishher12 have reported lower liquidus temperatures on the tellurium-rich side, but their data would require confirmation. The liquidus temperature on the tellurium-rich side decreases rapidly with increasing tellurium concentration and the Te2 vapor pressure over the liquidus also decreases accordingly.'3 The decrease in liquidus temperature and vapor pressure therefore makes it possible to use conventional apparatus if there is a sufficient excess of tellurium in the melt. Single crystals of ZnTe have thus been grown by Kucza,14 in a modified Bridgman technique, from solutions containing up to 60 at. pct of Te by lowering unsupported quartz ampoules through a temperature gradient at about 1200°C. Under these conditions, the phase diagram indicates that the entire charge is initially molten. Crystal growth can therefore proceed by normal freezing and rejection of excess tellurium into the melt. The modified Bridgman technique has several major limitations. Because of the rejection of excess tellurium into the melt during freezing, the melt composition and the temperature at the growth interface vary continuously. They tend to follow the liquidus until the eutectic which is very close to pure tellurium (447°C, >99 pct Te). Since the solidus composition also varies with temperature,15 crystals grown by this method are inhomogeneous. They present small variations from stoichiometry which may affect their structure and physical properties. The simultaneous increase in tellurium content and decrease in melt temperature also combine to reduce the rate of diffusion of tellurium away from the growth interface, thereby causing constitutional supercooling and possibly dendritic growth. To minimize these effects, the initial melt composition is in practice kept relatively close to stoichiometry (less than 60 pct Te). This however limits the possibilities of operating at low temperatures and pressures. This paper describes a modified method of crystal growth by temperature gradient solution zoning (TGSZ) which is an adaptation of the temperature gradient zone-melting technique developed by pfann16 and of the traveling solvent method of Mlavsky and weinstein.I7 The TGSZ method now applied to the growth of ZnTe and ZnTel-xSex crystals is characterized by its very simple experimental arrangement and sample preparation technique. Unlike the modified Bridgman technique, there is no increase in the tellurium concentration in the melt and therefore it is possible to operate at lower temperatures and pressures. This method is also suitable for maintaining a constant temperature at the growth interface.

Jan 1, 1969