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By J. David Lowell

For the first time in several years, Chile is again opening its doors to foreign investment. In its new investment code, the Chilean government has announced its willingness to become a partner in joint Chilean-foreign projects for a number of government-controlled porphyry copper deposits at the developed, semi-developed, or prospect stage; and, that it will allow privately owned deposits or deposits discovered by new exploration to be developed with up to 100% foreign ownership. Three deposits of particular interest are: El Abra, with at least 300 million mt of +100% Cu; Los Pelambres, with at least 428 million mt of 0.78% Cu and 0.03% Mo; and Andacollo, with 350 million mt of 0.70% Cu and 0.015% Mo. (El Abra is almost entirely government- controlled; but both Los Pelambres and Andacollo are mostly under private ownership.)

Jan 11, 1974

By L. C. Uren, E. J. Bradshaw

This paper presents the results of a group effort by a number of University of California students and faculty members, and the authors attach their names primarily in the capacity of editors and interpreters of the data thus assembled. In addition to the writers, the following individuals have made substantial contributions in time and effort in the conduct of this research: Dr. A. J. Carlson, Associate Professor of Petroleum Engineering; J. E. Gosline, University Research Assistant; C. F. Bedford, G. W. Mikulasek and H. S. Conder, senior and graduate petroleum engineering students; H. Bachman, G. Spencer and G. W. Gard, mechanicians in the Department of Mining and Metallurgy. Acknowledgment is also due the Research Board of the University, the Department of Mining and Metallurgy, and Prof. F. H. Probert, Dean of the College of Mining, for continued cooperation in securing mechanical assistance and funds for the purchase and assembly of apparatus. Significance of the Pressure Gradient The expulsion of petroleum from its reservoir sand doubtless is due to expanding natural gas intimately associated with the oil, to the hydrostatic pressure of encroaching edge waters, and to gravitational influences. These forces may operate independently or collectively. In any case they subject the fluids stored within the reservoir sands to elevated pressures, thus causing movement of oil and gas through the productive formations toward the lower pressure of the well outlets. This movement is opposed by pore friction, capillarity and adhesion: resisting influences brought to bear by the reservoir sand on the moving fluids. The magnitude of the resisting force is influenced directly by the viscosity, surface tension and density of the oil, as well as by the properties of the gas. The more rapid the rate of flow, the greater will be the resistance offered, and the greater will be the energy consumed.

Jan 1, 1932

By John Chipman, A. M. Samarin

It has been long known that the gas evolved during the boil in the open-hearth furnace is mainly carbon monoxide associated with smaller quantities of other gases. A number of attempts have been made to determine the precise effects of carbon and oxygen content of the bath, and of other factors, such as temperature, upon the evolution of carbon monoxide. In his investigation of the carbon-iron oxide product in liquid steel, Hertyl showed that the value of this product at equilibrium could be approximated by plotting the value of the product observed in open-hearth reactions against rate of carbon elimination, and extrapolating to zero rate. The results of this study showed a slight but definite effect of temperature upon the carbon-iron oxide reaction. Experimental studies of the evolution of gases from rimming-steel ingots have not yet attained the degree of precision necessary for an exact understanding of the effects of pouring temperature, carbon content, and iron oxide in the metal upon the composition of these gases. Klinger2 showed that the gas consists mainly of carbon monoxide, and that considerable variation in its composition occurs during the solidification of the ingot. In order that these variations may be understood in their proper relationship to the progress of solidification of the ingot and the segregation that accompanies solidification, it is essential to have a knowledge of the condition of equilibrium in the several chemical reactions by which the gases are being formed. It is also necessary to understand the effects of temperature upon the equilibria, and further, to know the manner in which the temperature of the liquid metal within the ingot changes as the skin of the ingot is being built up. The reactions in which we will be chiefly interested are those involving in the one case the oxides of carbon, and in the other case steam and

Jan 1, 1937

By John F. Elliott, John R. Rawling

The rate of reduction of silica to silicon by carbon at 1550° to 1700°C in iron blast-furnace type slag-metal systems has been investigated. In the tower portion of the temperature range oxygen transport in the metal boundary layer at the slag-tal interface is probably rate limiting. A second step, which apparently involves a chemical process in the slag at the slag-metal interface, appears to be rate limiting when the oxygen-transport limitation is avoided. Above 1650°C rate control of the reduction by carbon probably is mixed between the two steps. INVESTIGATIONS1.2 into the equilibrium distribution of silicon between graphite-saturated slags and metals typical of iron blast-furnace practice show that, under the experimental conditions specified, the reduction of silica to silicon is relatively slow compared with the rates of other slag-metal reactions under similar conditions. For this reason, the reduction of silica in blast-furnace slag-metal systems was considered to be an interesting subject for further study. Investigations of the kinetics of the reaction3-5 suggest that several possible steps may be rate controlling, and that the rate-controlling step depends not only on the physical state of the systems but also on the configuration of the apparatus. The main objects of the investigation reported here were to sug- gest plausible reaction paths for the reduction of silica under the experimental conditions chosen and to determine the step or steps which control the rate of reduction of silica. EXPERIMENTAL Two types of experiments involving the reduction of silica from the slag were carried out. In the first, the only reducing agent present was carbon (graphite), for which the over-all reaction is (SiO2) +2C(gr) —Si + 2Co(g) [l] The second type was a graphite-saturated ferro-silicon-iron concentration cell. In it silica in the slag could be reduced either by carbon according to Eq. [I], or by a reaction of electrochemical nature in which silicon was oxidized at the ferrosilicon-slag interface and silica was reduced at the slag-iron interface without the formation of CO. The two types of experiment are described below. Reduction of Silica with Carbon as the Only Available Reducing Agent. The reduction of silica was accomplished by allowing a liquid lime-alumina-silica slag and graphite-saturated iron to react in an induction-heated graphite crucible. The crucible was 2.25 in. diameter and 5 in. deep; it was fitted with a graphite stirrer which penetrated through the slag and into the metal, Fig. 1. The slag and metal charges weighed 350 g each. Pure carbon monoxide at a pressure of 1 atm was maintained above the melt by passing the purified gas through the crucible at a rate of 0.5 liter per min. The gas did not stir either the slag or metal. Temperature measurements were made by sighting an optical pyrometer down the hollow stirrer rod into a 1/4-in. hole drilled in the stirrer blade. The crucible temperature was maintained within *15"C of the required value by manual control of the power supply to the

Jan 1, 1965

By Charles Behre

UNDER the caption "fault," geologists intend to include all mass movements of solid rocks over adjacent rock masses. When these are studied long after their origin, however, circumstances make it possible to recognize as "fault" only formations showing clear evidence of actual movement of one side with' respect to the other. Necessarily the chief evidence consists of the offset of a vein, bed, or other key structure. Planes of movement parallel to the bedding; or nearly so, are recognized with difficulty or are overlooked and hence many important faults are wholly unrecorded. Indeed, among standard American references on structural geology, one alone emphasizes the importance of bedding-plane movements and that' one only briefly1. For some time the writer, cognizant of this difficulty, has paid special attention to such movements, both as observed in the field and as recorded in the literature. It is believed that enough data are now at hand to justify a short-discussion. Its purposes are fivefold. It is desired first to briefly classify and describe at least the more common kinds of bedding-plane faults, and second, to examine the causes and manner of their formation, at least in instances where the subject has not yet been well covered by other investigators. Third, certain by-products of bedding-plane movements are of such conspicuous importance to the economic geologist and mining engineer as to merit mention. Fourth, concrete illustrations should be placed before the reader in order to lend reality and to furnish a basis of comparison with his experience; such illustrations will necessarily be scattered through the text of this paper. They' are only in part from the writer's own field observations. The fifth and prime objective of this paper is to direct attention to the great importance of movements on the bedding planes, in the hope that the recognition of such movements and their significance may simplify mining problems.

Jan 1, 1937

By H. Sato, R. J. Lipp, I. Iwasaki, K. A. Smith

Selective desliming holds much promise for upgrading low-grade, finely disseminated iron ores that are not readily amenable to conventional flotation. The process is extremely sensitive to the presence of calcium and magnesium ions that are in process water or are released by constituent minerals. The effects of these two alkaline earth ions on quartz were compared through streaming potential measurements, flocculation and cationic flotation tests, abstraction tests and scanning electron microscope studies. Calcium ion, adsorbed as CaOH+, and magnesium ion, attached by heterocoagulation as Mg(OH)2 precipitate, were responsible for the flocculation of quartz suspension and for the depression in cationic flotation of silica in alkaline pulp solutions. Magnesium hydroxide coating could be removed, similarly to adsorbed calcium ion, by complexation with EDTA and polyphosphates.

Jan 1, 1980

By J. R. Coleman, G. L. Corrigan

FOUR factors that largely determine the end product obtained when cement and water are mixed are the chemical composi-tion of the cement, the fineness to which the cement is ground, the amount of mixing water used, and the procedure used in mixing the slurry. In order to study the effect of two of these factors, the other two, the chemical composition and method of mixing, are kept constant, leaving as variables fineness and water-cement ratio. Through years of experimentation and usage it has been well established that the reduction of cement clinker to a very fine state by grinding improves its cementing value, principally because the reaction between cement and water takes place only at the surface of the cement particle, further action being hindered by the accumulation of reaction products that tend to coat the unreacted material. Therefore, the moE finety-ground %cement, and the greater the surface exposed in propor-tion to its mass, the more rapid is the The work covered by this paper was done by the authors in pursuance of graduate studies in the ~epartment of petroleum Engineering at The University of Texas. The present paper is a condensation of a more detailed DaDer from which, for brevity, information such as the procedure for determining permeability and some of the discussion and procedure relevant to slurry volumes and fineness of cement have bsen deleted. It was felt that this information would not be of interest to most readers and should be outside the scope of this paper. Manuscript received at the office of the Institute Aug. 16, 1940. Issued as T.P. 1266 in Petroleum Technology. January 1941. hydration rate. Similarly, the greater the surface exposed, the greater the proportion of the cement that reacts, and the lower the amount of residue that is unreacted and so remains inert and unable to make any contribution to cementing properties.] Although it is more expensive to manufacture a finely ground cement than a coarser cement, the advantages of fine grinding of construction cements were so marked that the fineness of cement has increased considerably in past years. When the manufacture of special oil-well cements was begun, it was necessary to consider properties of cement that previously were considered of minor importance, foremost of these being pumpability. Since, with the water-cement ratio constant, a finely ground cement will produce a neat slurry of higher consistency and shorter time of pumpability than will a coarser cement, there is a tendency to grind oil-well cements to a lower degree of fineness. Therefore, in order to produce oil-well cements that will make a slurry having a long time of pumpability, cements are manufactured that because of their coarseness generally are Poorer cementing materials than some of the more finely ground construction and on the other hand, often it is necessary to Pump oil-well cements for long periods of time to place them properly behind a string of casing in a deep well, and since high strength is not of foremost importance for such cement, there is room for considerable controversy concening the proper fineness range.

Jan 1, 1941

By G. L. Corrigan, J. R. Coleman

FOUR factors that largely determine the end product obtained when cement and water are mixed are the chemical composi-tion of the cement, the fineness to which the cement is ground, the amount of mixing water used, and the procedure used in mixing the slurry. In order to study the effect of two of these factors, the other two, the chemical composition and method of mixing, are kept constant, leaving as variables fineness and water-cement ratio. Through years of experimentation and usage it has been well established that the reduction of cement clinker to a very fine state by grinding improves its cementing value, principally because the reaction between cement and water takes place only at the surface of the cement particle, further action being hindered by the accumulation of reaction products that tend to coat the unreacted material. Therefore, the moE finety-ground %cement, and the greater the surface exposed in propor-tion to its mass, the more rapid is the The work covered by this paper was done by the authors in pursuance of graduate studies in the ~epartment of petroleum Engineering at The University of Texas. The present paper is a condensation of a more detailed DaDer from which, for brevity, information such as the procedure for determining permeability and some of the discussion and procedure relevant to slurry volumes and fineness of cement have bsen deleted. It was felt that this information would not be of interest to most readers and should be outside the scope of this paper. Manuscript received at the office of the Institute Aug. 16, 1940. Issued as T.P. 1266 in Petroleum Technology. January 1941. hydration rate. Similarly, the greater the surface exposed, the greater the proportion of the cement that reacts, and the lower the amount of residue that is unreacted and so remains inert and unable to make any contribution to cementing properties.] Although it is more expensive to manufacture a finely ground cement than a coarser cement, the advantages of fine grinding of construction cements were so marked that the fineness of cement has increased considerably in past years. When the manufacture of special oil-well cements was begun, it was necessary to consider properties of cement that previously were considered of minor importance, foremost of these being pumpability. Since, with the water-cement ratio constant, a finely ground cement will produce a neat slurry of higher consistency and shorter time of pumpability than will a coarser cement, there is a tendency to grind oil-well cements to a lower degree of fineness. Therefore, in order to produce oil-well cements that will make a slurry having a long time of pumpability, cements are manufactured that because of their coarseness generally are Poorer cementing materials than some of the more finely ground construction and on the other hand, often it is necessary to Pump oil-well cements for long periods of time to place them properly behind a string of casing in a deep well, and since high strength is not of foremost importance for such cement, there is room for considerable controversy concening the proper fineness range.

Jan 1, 1941

By D. C. Ganow, N. J. Grant, I. R. Silver, A. R. Chaudhuri

The structural changes that result when a metal is "cold worked" lead to higher values of yield and tensile strength on subsequent deformation at room temperature. Further it has been shown that the beneficial effects of cold work are, to some extent, maintained even at elevated temperatures. The strength improvements from prior cold work decrease as the temperature is raised and are a function of grain size, amount of cold work, and strain rate (or time of test). If recrystallization occurs during test, the cold-worked material may even show weaker stress-rupture properties than the annealed material. A question that arises is whether there is a significant effect on the subsequent creep behavior if the prior deformation is performed under creep conditions at high temperatures not too different than the test temperature, but at significantly different strain rates and for various amounts of strain. An answer to this question was sought in the work described in the present paper. PROCEDURE Two materials were used in this work, high-purity aluminum and a solid-solution A1 2 pct Mg alloy. The compositions are shown in Table I. The grain size in the two materials was 0.2 to 0.3 mm. The deformation for both the prestraining and for the creep tests was at constant stress. The procedure adopted was to prestrain a specimen to the desired elongation, remove the load, and cool to room temperature rapidly by spraying. the test bar with cold water. The specimen was then placed in a creep machine, held at the test temperature for less than 5 min, and loaded. Less than 15 min was required to bring the specimen to temperature. The creep stress was based on the diameter resulting from the prior strain, and values of elongation at fracture listed in the tables do not include the respective elongations resulting from the prestrain. The choice of the stresses for the prestrain and for the creep tests was made so that the tests could be completed in relatively short times to maximize any effect of prestrain. The specimens had a gage length of 1 in., the pure aluminum specimens having a diameter of 0.150 in. and the alloy specimens a diameter of 0.125 in. For pure aluminum, prestrain was at 400' and 600°F with testing at 500°F; for the alloy, prestraining was at 700°F and testing at 600°F. RESULTS The prestrain conditions for the aluminum and the alloy specimens are shown in Tables I1 and IV. In addition to showing the time required to achieve the desired prestrain, the expected rupture Lives are given which would have resulted had the creep prestrain been continued to fracture. The prestrained and the annealed specimens were then tested in creep to fracture; the temperature and stress for the pure aliminum specimens being 500o F and 1800 psi and for the alloy, 600' F and 3400 psi. The creep curves for the prestrained and the annealed specimens of pure aluminum showed all three stages of creep; hence in addition to the effect of prestraining on the rupture life, it was also possible to determine the effect of prestraining on the minimum creep rate, and on the time and elongation at the end of each of the three creep stages. The results are shown in Fig. 1 and Table 111.

Jan 1, 1960

By B. H. G. Brady, C. M. St. John

Computational schemes for analysis of rock mass response to excavation, loading and other imposed changes, are employed pervasively in rock mechanics practice. Applications range in complexity from determination of stress and displacement distributions around openings, to prediction of the thermo-hydromechanical behaviour of a saturated fissured mass. While this may be taken as apparent sophistication in rock mechanics design activity, the indiscriminate use of computer methods may sometimes conceal inferior and inadequate engineering procedures. These inadequacies may not always be recognized, due to the general uncertainties which are inherent in rock mechanics investigations. This paper seeks to identify some common deficiencies in rock mechanics applications of computational schemes, and to propose ways of eliminating them. It also indicates some specific developments and applications of computational procedures, which are required to address persistent design problems in geomechanics practice.

Jan 1, 1982

SEVERAL distinctions can rightfully be accorded the Bagdad enterprise. For one thing, it has the most romantic name among the Porphyry Coppers and this is said with all due deference to Copper Queen and Inspiration! Bagdad was one of the richest and most magnificent cities of the glamorous world of the Arabian Nights. The record does not say who was responsible for applying the name Bagdad to the company that in 191 1 took over the property of the Arizona-Nevada Copper Company; but whoever it was must have had visions (or at least hopes) of a fabulously profitable mine. So far as I know, Bagdad is the only Porphyry whose owners, or officials, ran afoul of the law because of alleged sins of omission or commission in vending shares of the company's stock. E. B. Bronson, of New York, had been interested in Bagdad since 1909; and, during the lean period of the 1930's he had, as president of the corporation, endeavored to raise needed funds by the sale of 140,000 shares of treasury stock. Some legal questions arose as to the need for registration under the Securities and Exchange Act; but, when Mr. Bronson finally filed a registration statement, the New York office of the Securities and Exchange Commission found 155 "deficiencies" in the document. According to the judge who later heard the criminal case against Bronson, no evidence was introduced to show that he had personally benefited "to the extent of one dollar." However, it was charged that the setup was such that he was in position to profit if he had wanted to! A somewhat quixotic position, it would seem. In any event, he was convicted, on highly technical

Jan 1, 1957

By S. Stutz

Coal, like most other minerals, only exceptionally occurs in a sufficiently pare state to he directly available for general manufacturing purposes. And even where this is the case, the small coal or slack is usually more impure than the lump coal, as the slate, clay, etc., from the roof and bottom of the vein become mixed with it in the handling it undergoes. These impurities often exceed ten or more per cent. in addition to the impurities of the coal itself. The most common impurities of the coal are slate, or shale, clay, and sulphur. The latter occurs in different forms, but moat frequently as bisulphide of iron, or iron pyrites, and as sulphate of lime, or gypum. In both cases the impnrities add greatly to the amount of ash, and where they are present in considerable quantities the raw coal, and still more the coke made from it, is unfit for the manufacture of iron. Coke will coutain on an average at least fifty per cent. more ash and sulphur than the ram coal from which it is made. To the manufacturer of iron every additional per cent. of ash which his coal or coke contains is a source of additional expense, seemingly small, and yet very important in the aggregate. In the blast-furnace, for instance, the ash must be heated up to the melting-point, and, since it is composed largely of refractory substances, the consumption of carbon in melting it will be equal to at least one-half of its weight; that is, a certain part of tile coke is consumed for the melting and fluxing of the ash and is lost. Besides this, it is well enough known to the iron-master that coke containing lees ash makes the &lag or cinder more liquid and less incliner1 to stick to the walls of the furnace. Fuel containing much sulphur produces generally a white iron, poor in carbon, while from the same ore arrd flux, with a pure fuel, a good foundry iron might be obtained. The work of separating slate, sulphur, etd, from the coal has as yet only been successfully accomplished by the washing process. This process depends for its success on the differences in the specific

Jan 1, 1881

By J. Moore Samuel

INTRODUCTORY BEFORE the year 1909, no measurements of dust losses and flue gases had been made at the Copper Queen Reduction Works, at Douglas, Ariz. At that time the "unaccounted" loss of the smelter had reached a figure, that drew attention to the possibility of large stack losses. The measurement of dust losses had not been studied much at that time, and estimates of dust losses, with a few exceptions, were the results of tests by what has been termed "chemical methods," that is, the aspiration and filtration through cotton, wool or some similar medium of a few liters of gas, the dust being weighed on a chemical balance, and the volume of gas computed from the volume of aspirator water. The possible error of this method is enormous, and the probable error much too large for reliable results. Since the object of these tests was to discover not only the extent of the dust losses, but also the possibility of profitably reducing the same, it was decided that the method adopted must have the following characteristics: 1. The sample of gas taken for filtration must be representative of the whole volume of gas, that is to say, it must have the same dust content. This condition will be fulfilled in all cases if the gas sample is drawn off without change of rate of flow. Then it will contain the same proportion of entrained or suspended particles of dust as the original gas. In the case of flue gases which contain only fume, at a temperature above or near the sublimation point, this condition need not be adhered to since the fume will not behave as entrained particles, but more nearly as a true gas. Consequently the gas sample in this case only may be drawn off at any rate of flow. 2. The gas sample taken must be large enough (a) to yield sufficient dust to permit of accurate chemical and physical examination; (b) so that the ratio of the total volume of gas passing through the flue to the volume of gas sample taken shall not be too large.

Jan 6, 1916

By George M. Enos, Robert J. Anderson

This paper gives a summary of tests made on the accelerated electrolytic corrosion of the tin brass, 70:29:1 copper-zinc-tin (admiralty metal), of different grain sixes in various electrolytes. There has been great difference of opinion as to the effect of grain size on the corrosion rate of brass, particularly in condenser-tube practice, but so far as is known no information has been published on the subject. It has been assumed, on the basis of the amorphous-cement theory, that fine-grained brass would corrode more rapidly than coarse-grained because the amorphous phase is more soluble than the crystalline and there is more cement per unit area exposed in the fine-grained material. In previous work on the corrosion of metals and alloys in acid mine waters from coal mines,1,2 it was found that the grain size, within a restricted range, had practically no effect on the corrosion of the brass 70:29:1 copper-zinc-tin: In the tests made, samples of three grain sizes were included; viz., 0.025, 0.035, and 0.075 mm. diameter (1600, 817, and 177 gr. per sq. mm., respectively), and the average losses on exposure to the most acid of three waters were 7.07, 6.80, and 6.72 mg. per sq. cm. per day (24 hr.), respectively. No distinguishing features were observed on microscopic examination of the corroded samples. In two other mine waters, the corrosion losses were substantially the same for the respective samples. These tests were -incidental to other tests and were not sufficiently comprehensive to warrant drawing definite conclusions. In further work with the accelerated electrolytic corrosion test, as developed recently in the Bureau of Mines, tests were made

Jan 1, 1924

By C Gunther

Secondary minerals are the result of a process of concentration and enrichment and are commonly richer than the primary minerals of the same deposit. Secondary ores that contain abundant sulphides are commonly dibtinguishable in the field from primary ores; this distinction is more difficult with ores that carry a small quantity only of sulphide minerals, and microscopical examination of the ore in thin section is advisable in all doubtful cases. It is frequently difficult, and in some cases impossible, to determine the primary or secondary character of quartzose gold ores. The safest guide is the presence or absence of gaseous or fluid inclusions in association with the ore minerals; such primary association coupled with a lack of traces of oxidation is indicative of primary origin. Any ore that carries traces of oxidation, such as iron stains, dendritic oxides of manganese, kaolin and so forth must be considered to have been acted upon by surface agencies, and secondary enrichment must be suspected. Further examination, however, may indicate that the contained value is primary, and, therefore, persistent in its vertical distribution. The manner of occurrence of secondary minerals is frequently characteristic; secondary minerals, being due to the action of surface waters, are commonly found in cracks through earlier minerals, or as crusts lining vugs or surrounding nucleal masses, or in general, in some distribution later than and not conforming to the arrangement of the primary minerals. Secondary sulphides are often found as soft black pulverulent masses or coatings, although they frequently occur well crystallized or as

Jan 1, 1932

By A. G. McGregor

DURING the past 5 years, five new copper-smelting plants have been built and put into operation in the State of Arizona. The monthly copper output from these plants averages from 5,000,000 to 18,000,000 lb. Previously, there never was as much activity in copper-smelting plant construction in the same length of time in all the rest of the world. Naturally, in this amount of work, some new problems were met and new features in plant design and. equipment developed. Some of these features are described in this paper. CONCENTRATE HAULING, UNLOADING AND SAMPLING SYSTEM (a) Concentrate Car The International Smelting Co. has provided at its plant at Miami specially designed cars for hauling the concentrates from the mills of the Inspiration Copper Co. and the Miami Copper Co.. The car has a bottom that is readily made tight to hold flotation concentrates and is quickly and cheaply unloaded. Figs. 1, 2 and 3 show views and details of the car. The main feature of this car is the slot in the bottom throughout its length, which is closed by means of short planks that overlap like ship-lap as shown by Fig. 1. At one end of the car an iron gate operated by a screw and hand wheel is provided, which clamps or presses the planks together, making the bottom tight. A removable tapered plug rests vertically over this gate when the loading of the concentrates at the mill commences.

Jan 8, 1916

By C. J. Frosch, J. A. May, H. G. White, C. D. Thurmond

Gallium phosphide epitaxial layers were grown from the vapor phase on undoped single-crystal galliurn arsenide substrates in silica tubes by an open-tube wet-hydrogen process. The epitaxial layers were grown over a range of water pressures at three substrate temperatures. Excess donor concentrations were determined by surface barvier capacitance measurelrzents without removing the layers from the substrates. The excess dmlor concentration, ND-NA, is fo~ind to vary approxilnately inversely with the pressure of water added to the hydrogen carrier gas. This is the relationship that would be expected for singly ionized silicon donors on gallium sites in extrinsic galliunz phosphide, with the silicon coming from the SiO generated by the reaction of hydrogen with the silica tube. An increase in the partial pressure of water in the hydrogen stream decreases the SiO pressure. The results indicate that ni, the intrinsic hole and electrmt concentration for gallium phosphide at the three substrate temperatures, is smaller than the concentration estimated from available data for the density of states effective masses and the energy gap. Mass-spectrographic measurements confirm that the dono?, introduced into gallium phosphide is silicon. The equilibrium concentrations of silicon in vapor-flown gallium Phosphide have been estimated from available thernzodynamic information that includes the solubility measurements of silicon in gallium phosphide in equilibrium with a gallium-rich liquid phase. Satisfactory agreement with the measured silicon concentrations is obtained. FROSCH1 has described an open-tube process for growing single-crystal Gap from the vapor phase by a GazO transport mechanism. The method depends upon the reaction of H20 in an H2 carrier gas with a heated source of polycrystalline Gap which provides the necessary vapor species. When the temperature of these vapor species is lowered, super saturation occurs and single-crystal Gap will deposit on a suitable substrate. Unintentionally doped single crystals of Gap grown by the wet H2 process in silica tubes are n type. Evidence is presented to show that the donor introduced is silicon, and that a qua si-equilibrium model accounts for the inverse dependence of the donor concentration on the water partial pressure and predicts the magnitude of the donor concentrations. Ainslie et al. experimentally showed a similar inverse relationship between the carrier density and oxygen pressure for GaAs. Emission-spectrographic analyses showed a decrease in the silicon concentration with increasing oxygen overpressure for GaAs. Cochran and Foster suggested the theoretical possibility of suppressing silicon contamination by using Ga20 generated by the reaction of gallium with water vapor. 1) EXPERIMENTAL The apparatus and procedures are essentially the same as those described by Frosch.' The apparatus consists of a 25-mm-ID SiO2 tube extending through a controlled high-temperature flat zone for the location of the polycrystalline Gap source and a downstream temperature gradient falling at a rate of about 14°C per cm. The latter provides the region of super saturation for the location of the single-crystal substrate. The partial pressure of water in the inflowing hydrogen stream, pA2, O was controlled by mixing me-tered proportions of dry H2 with H2 saturated with H2O vapor at 0°C. The total gas flows were about 200 cu cm per min in all experiments. The Gap sources were prepared by pulverizing boat-grown polycrystalline ingots to pass a 20-mesh sieve. The substrates were cut from an undoped single-crystal boat-grown GaAs ingot purchased from Monsanto. This ingot had a carrier concentration of about 1015 atoms per cu cm, a resistivity of about 5 ohm-cm, and a mobility of about 5000 sq cm per v sec at 25°C. Substrates with dimensions of 1 by 1 by 5 x lo-' cm were employed. The growth faces were chemically polished (111) arsenic faces. Epitaxial layers, at least 7.5 x 10-3 cm thick, were grown,. This required from 1 to 24 hr depending upon the Pii2Q values and the temperatures. In all of the runs, the source temperatures were 50°C higher than the substrate temperatures. Samples were prepared

Jan 1, 1968

By C. B. Gillson, Henry Fay

For several years past, investigations on the chemistry of tellurium have been carried on in the laboratory of this institution. The methods of preparation of pure telluriumf and the estimation of tellurium‡ have been studied, and an attempt to determine the atomic weight of tellurium is now in progress. All these problems had been investigated, however, along purely theoretical lines; and it was thought desirable to study the more practical application of the metal, which can now be had in considerable quantities as a waste product in the refining of copper-ores. In its physical and chemical properties tellurium is very similar to antimony, and it was thought

Jan 1, 1902

By C. S. Smith, W. M. Williams

THE quantitative study of grain shape in three dimensions has been a difficult one from the practical standpoint. Experiments on grain shape have usually been based on indirect observations of two-dimensional metallographic samples or on grains separated by intergranular corrosion or fracture. The latter method was used in particular by Deschl in 1919 in observing the shapes of ß-brass grains which had been separated with mercury. The similarity in detail of shape and packing that exists between bubbles in a soap froth and metal grains was noted by Desch who remarks that: "Surface tension has an. important share in determining the form of the crystal grains in a solidifying metal and such grains have a tendency to assume the shape of foam cells." More recently the relation between grain shape and grain growth has been studied by Harker and Parker.' The importance of surface tension forces in determining microstructure has been discussed by Smith," and an analysis of the topologi-cal rules that apply to such structures has been made by the same author.' Biologists have made valuable contributions to the general problem of shape and form in an assembly of space-filling cells subject to surface tension forces. Particular mention must be made of the extensive researches of Lewis5,8 on botanical and anatomical tissues, and Matzke and Nestler,7,8 who have made painstaking studies of bubble shapes in different kinds of foam. The present paper introduces a new method of studying individual grains in particular alloys—a method which may well find use in other metallurgical researches, and which seems also to be applicable in biological problems. Metal Grains in Three Dimensions The individual grains in a piece of metal or the bubbles in a soap froth must satisfy two conditions —they must be in juxtaposition so as to fill space and their interfaces must conform to the laws of surface tension. If a further restriction is imposed, namely, that only one type of polyhedron be used, then the sole possibility is an assembly of "minimal" tetrakaidecahedra," each polyhedron having eight doubly-curved hexagonal faces and six plane quadrilateral faces, the angles between adjacent faces being 120". Such cells could be stacked on a body-centered cubic lattice and would be quite stable. For many years it was believed that soap bubbles actually possessed the shape of this ideal body, and the hypothesis was the starting point for several investigations on the shapes of soap bubbles, biological cells, and metal grains. These investigations have shown, what might have been obvious in the beginning, that if the condition of symmetry is relaxed the tetrakaidecahedron is almost never found. If we retain only the rule that all contacts should be in local surface tension equilibrium and that the assembly should fill space, metal grains may then take a nearly infinite variety of shapes and no single one may be regarded as an archetype. These two conditions, which are fully discussed in one of the previously mentioned papers,' lead us to think of a typical grain in an annealed metal as having the following characteristics: 1—A grain may have any number of faces, but usually between nine and eighteen. The faces (each of which is, of course, shared by two grains in the assembly) may have any number of edges, but usually between four and six. Pentagons are by far the most frequent. 2—In the assembly of grains each edge is shared by three faces and by three grains. Each vertex is a point shared by four grains, six faces, and four

Jan 1, 1953

By Norman B. Pilling, George P. Halliwell

The effects of lead and tin up to maximum contents of about 0.1 per cent. each, in the presence of oxygen between 0.04 and 0.30 per cent., have been studied. Tin is retained efficiently in the oxidized condition, whereas lead is not. An approximate relation between the lead-oxygen and tin-oxygen contents is deduced which, if observed, permits the presence of these elements without detrimental effect. Excess of lead beyond this limit affects ductility and rolling properties adversely and an excess of tin correspondingly diminishes the conductivity. It is shown that copper carrying a combined lead and tin content of several hundredths per cent., yet fully equal in quality to electrolytic wirebar, may be produced under commercial conditions. Tin is not normally found in more than bare traces in current grades of American electrolytic copper, and lead is rarely found to more than a few thousandths per cent. In the electrolytic refining of copper these metals do not present great difficulty in separation and their presence in any considerable amount in copper that has been refined by this method need not be tolerated. On the other hand, the effect of these elements is not entirely academic, as a considerable tonnage of scrap copper liberally contaminated with them has been reclaimed by the fire-refining process into metal with a residual lead and tin content of several hundredths per cent., yet having excellent working properties and fully equal in quality to current grades of electrolytic wirebar. Such copper has been found entirely suitable for use in the manufacture of electrical apparatus. In the absence of oxygen, tin is known to depress the conductivity rapidly, and lead to impair ductility and the rolling properties, yet the effects of these metals on commercial grades of copper—i. e., copper containing from 0.03 to 0.10 per cent. of oxygen—apparently has not received systematic attention. Occasional reference is made to the fact that in the presence of oxygen lead may be tolerated, yet Addicks says,1 in regard to overpoling: "The unstable condition can be controlled by adding certain substances, notably lead, in small quantities, but as mere

Jan 1, 1926