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By Myrick N. Bolles

The concentration of gold and silver in mattes low in copper, and the subsequent separation and recovery of either or both of these metals, is a question the satisfactory solution of which has long vexed metallurgists. It covers a broad and important department of metallurgical science and brings in its train a series of attendant problems continuing from the initial operations of concentration to the final recovery of " values."

Jan 1, 1905

IN the early period of steelmaking, ingot structure and segregation were of no practical importance. Crucible melting required very small ingots that gave little segregation, and a small inserted hot top prevented pipe. As larger ingots were poured from bessemer converters and open-hearth furnaces, segrega- [ ] tion, piping, and gas evolution became increasingly important. The techniques of making semikilled and rimmed ingots were developed with little knowledge of the actual mechanism of the process. The first studies of solidification were made by the Brearleysl and Gathmann,2 who used stearine to show the effects of shrinkage and mold shape. Fig 11-1 is a picture of a series of stearine ingots at various stages of solidification. These studies showed that the liquid solidifies at a nearly uniform rate from the sides and bottom of the mold and demonstrated the formation of

Jan 1, 1951

By H. M. Day

THE constitution of the system silver-mercury has attracted the attention of many investigators during the last two decades, but since their results are for the most part in poor agreement, there is little need for a review of their individual contributions. It remained for the very careful thermal and microscopic investigation of Murphy1 in 1931 to give the constitutional diagram in its present and unquestioned form, which is shown in Fig. 1. He devised methods for taking cooling curves on alloys under high pressures and for the microscopic observation of alloys which contained liquid mercury as a structural constituent at ordinary temperatures. The compositions of the intermediate phases were con-firmed and supplemented through X-ray analyses by Preston and Stenbeck.3 According to Murphy, at 276° C. silver is able to dissolve 44 to 45 weight per cent of mercury, which may increase at lower tempera-tures to about 50 per cent. Preston concluded that the saturation boundary occurred at 46 ± 2 per cent at 100° C. From the values reported in the literature, these are the only ones that may be accepted as lying even in the right region.

Jan 1, 1938

By Curtis L. Graversen, J. H. Hamilton, John C. Nixon, John R. Lewis

RECENTLY there has been much speculation concerning the advantages of using oxygen enriched air or pure oxygen in pyrometallurgical processes. The advantage of using oxygen in the iron blast furnace and elsewhere in ferrous production metallurgy has been given careful consideration and, as a result, several experiments have been tried and a number of papers have recently appeared on this subject.1.2 The use of oxygen in nonferrous smelting likewise poses interesting problems, therefore any experimental data obtained in this area should likewise be of general interest.3 Ashcroft4 in 1933 claimed to have obtained improved results when copper concentrates were roasted in pure oxygen. However, his' paper gives neither data nor experimental details. A few years ago a research program was started in this laboratory which had for its objective the determination of the mechanism of oxidation of metallic sulfides under varying conditions. To date we have studied the oxidation of galena, 5 sphalerite, and chalcocite. It is a well known fact that copper sulfide minerals are oxidized slowly by weathering agents, so that the sulfides of copper which find their way into a tailing pond are gradually changed into watersoluble and acid-soluble compounds. Commercially, the oxidation of copper sulfide minerals is accomplished by roasting them at elevated temperatures in air using a suitable (usually multiple-hearth) roaster. Most copper smelters are equipped with such roasters. In this phase of the study we were especially interested in determining the effect of temperature on: (I) the air oxidation of chalcocite and (2) the oxidation of chalcocite using commercial oxygen. The amount of sulphur removed as sulphur dioxide, the percentages of water-soluble copper, and of acid-soluble copper were determined for the air oxidation tests. In the tests using commercial oxygen, the percentages of sulphur dioxide, water-soluble copper, acid-soluble copper, water-soluble sulphur and acid-soluble sulphur were determined. For these experiments the temperature was varied from 250 to 700°°C. EXPERIMENTAL Preparation of Chalcocite (Cu2S) Natural chalcocite is not pure. Minerals such as bornite, covellite, and chalcopyrite may be present. It was decided, therefore, to prepare some chalcocite in our own laboratory. An intimate mixture of sulphur and finely divided metallic copper in the ratio of 4 g of copper to I g of sulphur was prepared. To this was added a slight excess of

Jan 1, 1948

By J. K. Buehler

With the rapid acceleration of the cost of shovel dippers and major standard shovel clipper rebuild components, maintenance management at Kennecott Copper Corp.'s Bingham Canyon mine initiated a dipper maintenance and rebuild program. The program focused on extending the service life of the shovel dipper, reducing field labor in maintaining dippers, and lowering shovel dipper rebuild costs. While comprehensive evaluation of the program is still underway, preliminary benefits of the program indicate: •Reduced field ,gelding for shovel dipper field maintenance, •Fewer dipper rebuild units entering the shop, and •Reduced dipper rebuild costs per unit.

Jan 1, 1979

By F. N. Rhines, A. H. Grobe

At elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing. When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible1 and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver. Norbury2 and Leroux and Raub3 have reported internal oxidation (subscaleiormation) in alloys of silver with 2, 7.5, and 30 per cent of copper. The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver.4 Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation. Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detai1.5,6 The present research confirms this anticipation. The oxidation of a series of 20 dilute alloys of silver has been studied metallographically; some types of subscale not encountered among the copper alloys have been found. Instances of internal oxidation in alloys of most of the metals of the 1-6 and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking. A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation; i.e., they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them. In a study of 40 alloys of these white metals only a few cases of internal oxidation have been found. The probable reasons for this difference in behavior will be discussed presently. Experimental Procedure Silver.—The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99.993 per cent Ag)* and the purest avail-

Jan 1, 1942

By A. H. Grobe, F. N. Rhines

At elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing. When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible1 and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver. Norbury2 and Leroux and Raub3 have reported internal oxidation (subscaleiormation) in alloys of silver with 2, 7.5, and 30 per cent of copper. The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver.4 Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation. Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detai1.5,6 The present research confirms this anticipation. The oxidation of a series of 20 dilute alloys of silver has been studied metallographically; some types of subscale not encountered among the copper alloys have been found. Instances of internal oxidation in alloys of most of the metals of the 1-6 and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking. A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation; i.e., they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them. In a study of 40 alloys of these white metals only a few cases of internal oxidation have been found. The probable reasons for this difference in behavior will be discussed presently. Experimental Procedure Silver.—The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99.993 per cent Ag)* and the purest avail-

Jan 1, 1942

By H. G. Moulton

THE INCREASING scale of mining operations over the past decade, particularly in connection with the exploitation of large bodies of comparatively low-grade copper ores, has made necessary the study of the behavior of rock under failure. When extractions of as high as 40,000 tons a day are reached in steam-shovel operations and as high as 20,000 tons per day in underground mining operations, it is evident that excavations soon become of such size that the behavior of the rock will often be dependent on fundamental principles applicable to more or less homogeneous materials under stress, rather than on weathering or local planes of weakness. In the ordinary rock excavations encountered in civil-engineering practice, such as excavations for subways, highways, railroads, etc., rock faces are not carried to depths sufficient to develop any pressures, or consequently any failures, except those due to loose masses resulting from local planes of weakness. When, however, orebodies whose tonnage is measured by hundreds of thousands are to be extracted by steam-shovel operations in open pits, it is necessary to determine if possible in advance the slopes that the sides of the pits will assume, for these slopes influence the shape of the excavations and thereby the amount of ore that may be extracted by the open-pit method. When large orebodies are mined underground at depths of 300 to 500 ft. (91 to 152 m.) by caving methods, the surface subsiding as the ore is withdrawn, it is necessary to determine in advance the outermost limits of fracture in the subsiding surface, for on the delineation of these limits depends the location of surface improvements, mills, smelters, etc. and also the location of development work, such as hoisting shafts, main haulage levels, and all other underground openings that must remain undisturbed during the period of ore extraction. Heretofore, in civil-engineering practice, it has been assumed that earth and rock behave differently in failure. For the calculation of earth

Jan 2, 1920

By R. W. Hyde, B. S. Old, S. E. Eaton

INTRODUCTION ONE of the most important problems facing the steel industry at the present time is that of maintaining at a minimum the sulphur content of many grades of steel where sulphur is known to have harmful effects on both quality and yield. The present outlook in this struggle to reduce the amount of sulphur in steel is rather gloomy since the sulphur content of the raw materials available in the United States is gradually rising, with little relief in sight. A flow sheet of sulphur in the steel process is shown in Fig I. The values used here were obtained by averaging coke oven and blast furnace data at No. 5 furnace in Cleveland and are considered typical for high top pressure practice. The sulphur evolved in the blast furnace top gas was obtained by difference and since the amount is relatively small, little significance should be attached to this particular value. From Fig I it is apparent, however, that coals used in the production of metallurgical coke represent by far the largest single source of sulphur in steelmaking. As an indication of the decrease in quality of these coals as regards sulphur content the weighed average annual sulphur analysis of the coals supplied to two different steel plants, since 1925, is plotted in Fig 2.1 The sharp rise since 1940 is strikingly apparent. Another indication of this trend is found in estimates of coking coal reserves. Thus in the case of Pittsburgh seam coals available in Allegheny, Fayette, Greene, Washington, and Westmoreland Counties in Pa. as of Jan. 1937 only 25 pct of the coal reserves would contain less than 1.50 pct sulphur after washing.2,3 Many of these lower sulphur reserves have been seriously depleted in recent years because of accelerated war demands. Still another demonstration of the increasing sulphur content of coals on a country-wide basis is found in a report by the Bureau of Mines4 which shows a steady increase in the sulphur content of coke made in the United States, It should be noted that this increase continues in spite of the wider use of coal washing in recent years. Sulphur occurs in coal in three forms, pyritic (FeS2), organic sulphur, and a small amount of sulphate sulphur (CaSO4), The sulphur is subsequently found in the coke in combination with carbonaceous material of unknown composition and as calcium and iron sulphides: In considering the general problem of sulphur elimination, the Republic Steel Corp. was interested in determining which, if either, of the two major forms of sulphur in coal contributes the greater portion of sulphur to the coke, Since the ratio of pyritic to organic sulphur varies widely in different coals, it was thought that if it could be shown definitely that the major part of the sulphur occurring in coke originates from one of the two major forms of sulphur in the coal, it would then be possible to select with confidence coal which, although high in total sulphur, would yield coke of fairly low sulphur content, Using the new

Jan 1, 1948

By I. Iwasaki, K. Adam

During wet grinding the electrochemical interactions between grinding media and pyrrhotite not only accelerate media wear but also adversely affect the suede mineral's flotation response. A possible remedy of the adverse effects on floatability by applying electric potentials to grinding media was examined. Flotation tests, Auger electron spectroscopy, and X-ray photoelectron spectroscopy were used to study pyrrhotite surface properties. Although anodic polarization of the steels increased metal loss by corrosion, pyrrhotite flotation recovery was increased. In the case of cathodic polarization, flotation recovery improved somewhat in a narrow range of overpotentials. At higher cathodic overpotentials, however, mineral floatability was progressively lowered although the corrosive wear of grinding media might be reduced.

Jan 1, 1985

By Bernard H. Coyle, Robert N. Anderson, Judith A. Koperski

Between 6 and 8 million cars are shredded annually in the U.S. This shredded material is magnetically separated leaving a mixture of nonmetallics and nonferrous metals which can be further separated into its metallic and nonmetallic constituents. The metallic portion is a mixture of metalr; and alloys containing predominately zinc, and some aluminum, copper, and residual iron. Hydrometallurgical strategies are proposed for recovering the aluminum, copper, and zinc. The thermodynamic and kinetic behavior of the most promising alternatives to separation are discussed.

Jan 1, 1978

By A. G. McGregor

IN THE Southwest a number of large steel chimneys discharge the gases from the copper smelting furnaces. Some of these chimneys show no deterioration after twenty years, others show serious deterioration after tour years service. A steel stack 20 ft. 7 ½ in. (6.3 m.) in diameter by 279 ft. (85 m.) high, Fig. 1, used for roaster gases only at the Calumet & Arizona Mining Co.'s plant at Douglas, Ariz., was lined to the top of the bell, 40 ft. (12 m.) from the base, with common brick placed on end, lime and cement mortar being used. Above the bell, the stack was lined with 4 by 4 by 8 in. (10 by 10 by 20 cm.) building tile, placed on end, making a lining 4 in. thick. The tiles were supported on angle-iron rings, riveted to the inside of the chimney shell about 15 ft. apart. The chimney was put into use in the latter part of 1913. Four years later, considerable of the tile lining had fallen out of place and mixed with the flue dust at the bottom of the chimney. About a year later, several . flattened and distorted sheets were noticed about 70 ft. below the top. An investigation showed that the thickness of these distorted sheets, which was originally ¼ in., had been reduced one half. One year later, or six years after the chimney went into use, several holes, a square foot and smaller in area, appeared near the flat spots mentioned. Soon afterwards, when the chimney was shut down for repairs, it was found that most of the tile lining for 125 ft. from the top had fallen out and that the steel shell was badly corroded; but where the lining remained in place the shell was undamaged. Many of the tile which had fallen out of place had become soft or flaky and crumbling, others were as hard as when placed. An analysis of the hard and soft tile is shown on p. 2. These tile were of a fireclay mixture, and were used instead of common brick on account of lower cost. The steel forming the upper 125 ft. (38 m.) was replaced, and a 4 ¼ -in. (11-cm.) lining of firebrick was laid from the bell to the top of the chimney. The brick were placed on end, wedges and keys being used. After each 8-in. course was set, keyed, and wedged tight, thin mortar -water, sodium silicate, and finely ground silica-was worked into the joints. The brick are supported on angle-iron rings, every 15 ft., in the same way as the tile.

Jan 1, 1921

By M. C. Fuerstenau, J. D. Miller

The response of calcite to flotation with saturated fatty acids and alkyl sulfonates of various chain lengths is presented. The amount of collector re-quired for flotation is shown to decrease systemati-cally with increasing carbon content from 8 to 12-carbon atoms per molecule. This systematic flotation response is correlated with the solubilities of the calcium-collector salts, which were established with a nephelometer. The 14-carbon collectors deviate from this systematic behavior, and no flotation is possible with the 16-carbon homologs. As determined by infrared analysis, the mechanism of collector adsorption involves a specific chemical reaction be-tween the collector and the surface. A reaction of the form CaCO3(s)+ 2 RCOO"=*=Ca(RCOO)2(s) + C03= is suggested. The pH of the system is also shown to be a most important parameter as it controls the carbonate, calcium, and collector ion concentrations in solution and thus controls flotation response. The importance of hydrocarbon chain length of collectors was recognized early, and various studies have been made on this aspect of flotation. Wilkinson, ' for example, noted that as the chain length of alkyl xanthates is increased, the amount of collector required for flotation of sphalerite is decreased. The same effect has been shown in the flotation of galena.2 Similar results were obtained when malachite3 and calcite4 were floated with various fatty acids. DeBruyn5 has shown that a similar phenomenon occurs when quartz is floated with amines at constant pH. Recently, Fuerstenau, Healy, and Somasundaran6 correlated this phenomenon with the van der Waals cohesive free energy of association of the hydrocarbon chains. It seems unlikely, however, that chain association could be involved in the sulfide and carbonate systems with the collector additions employed, especially with the short-chain xanthates. Rather, it would seem that the decrease in collector concentration with increase in chain length noted for flotation is related to the solubility of the metal-collector salt. The purpose of this investigation is to verify this premise and also quantify this phenomenon if possible. Calcite was selected for study with both alkyl sulfonates and saturated fatty acids as collectors. EXPERIMENTAL MATERIALS AND METHODS The collectors used in this investigation ranged from 8 through 14 carbon atoms per molecule. The fatty acids had a reported purity of greater than 99%. The sodium alkyl sulfonates were provided by the Marathon Oil Cot, Littleton, Colorado, and had the

Jan 1, 1968

By C. O. Brawner

FACTORS THAT INFLUENCE STABILITY AND STABILIZATION METHOD The most effective stabilization method and design can only be developed if the cause(s) and mechanics of the slide are known. Therefore, it is important that the stability be evaluated by an engineer who has had extensive rock stability experience. The most important factors that influence stability are structural geology, ground water, blasting and the mining method or methods. Structural Geology - The majority of failures in rock slopes occur along discontinuities in the rock (joints, bedding planes, shear or fault zones, etc.). Therefore, on all surface mining projects, the development and maintenance of a comprehensive structural geologic mapping program should be a first priority program that is considered a part of the operations function. This program should include mapping all major features - faults, shear zones and through going joints. All structural features which could influence stability should be mapped and presented in a structural domain format for the entire mine (Canmet, 1977). Where planes, wedges or blocks will be undercut by the mining excavation, shear strength and strain to failure tests should be performed on the joints, fault gouge and gouge-rock contact surfaces. These tests must be performed on the samples in the direction of potential slide movement and must determine the range of peak and residual shear strength values. A preliminary assessment of friction angle can be obtained from measurements of failed surfaces in the field (Figure 1) or from core sliding tests (Barton, 1981). An assessment must be made of the past geologic history of

Jan 1, 1983

By K. Osseo-Asare

The presence of carbonaceous matter in gold ores presents a two-fold problem: (1) The poor release of gold from the carbonaceous matrix and (2) the uptake of dissolved gold by the carbonaceous leach residues. A critical review is presented of the published information from various parts of the world pertaining to the nature of the carbon-containing components of these ores and their different roles in the gold extraction process. Included in this paper are new results based on the authors' research on carbonaceous ores from the Prestea goldfields of Ghana. Methods for isolating and characterizing the carbon-containing materials are given and a discussion is presented of the interaction of the carbonaceous ores as well as the fractionated components with aurocyanide solutions. Emphasis is on basic physico-chemical phenomena, investigated with the aid of X-ray diffraction, infrared spectroscopy, adsorption, and electrophoretic mobility studies.

Jan 1, 1984

By J. E. Fox Jr., J. L. Lummus, J. P. Gallus

Fresh water or brine drilling fluids may be kept free of suspended drilled solids by the addition of a water soluble acrylamide-carboxylic acid copolymer at the flowline. Addition of from .01 to 0.2 lblbbl of the polymer solution to drilling fluids containing less than 5 per cent clay solids by weight causes the solids to flocculate and settle rapidly to the bottom of the pits. Solutions of the polymer injected at the pump suction reduce the loss of water to permeable formations without impairing the permeability to oil. The use of drill-itlg fluids clarified with the polymer has resulted in increased drilling rates, extended bit life, and lower drilling fluid costs. INTRODUCTION Field experience and the results of a number of investigations have established that the accumulation of solids in drilling fluid reduces drilling rate.'-' Drilling with water makes possible higher drilling rates than can be achieved with mud but in many areas drilling with water may not be feasible because of the possibility of encountering high formation pressures or by-dratable formations. To combat these conditions, the drilling fluid must possess certain physical properties such as viscosity, density, fluid loss, etc., which require the presence of solids. The current trend in drilling fluid treatment is to maintain as low a percentage of solids as is possible without harmfully affecting the mud properties needed for drilling. Mechanical separating devices such as wet cyclones and decanting-type centrifuges are proving to be an economical means of controlling the percentage of solids and thereby maintaining low solids muds. Also: special muds have been developed for the purpose of retarding the hydration of drilled solids so that they may be more easily removed by shale shakers or settling pits. In some areas, such as West Texas, the characteristics of some formations will permit drilling with water. However, because of the dispersion of drilled solids, it is usually not possible to maintain clear water even with the aid of mechanical separators, or by utilizing large settling pits. For this reason the commonly used term "water drilling" is a misnomer since the water usually contains some solids. Because of the improved drilling rates and other benefits which might be effected, a laboratory and field study was made of the use of flocculating agents for maintaining clear water for drilling. PROCEDURE Laboratory—Solids Settling Two techniques were employed to determine the effectiveness of flocculating agents in settling solids from drilling mud. First, the rate of fall of solids was measured in graduated beakers containing mud treated with various flocculating agents. Natural gum, oil-in-water emulsions prepared with ethoxylated nonyl phenols and diesel oil. and a powdered synthetic acrylamide-carboxylic acid copolymer* (hereinafter referred to as "polymer") were tested as flocculating agents in both fresh water and salt saturated muds containing 4 per cent solids. The polymer was not added in the powder form directly to the muds but was first dissolved in water in a concentration of 3.5 lb/bbl. The polymer solution was then added directly to the mud. The concentration of the flocculating agents, including the polymer, was varied. High rates of fall of the solids indicated high flocculating efficiency. A second technique consisted of measuring the time in minutes required to obtain clear water at the pump suction after addition of the various flocculating agents at the flowline. These tests were made using a model mud circulating system having a total volume of approximately 10 gal. The natural fresh water and brine muds used contained 4 per cent solids. A sketch of the circulating system appears in Fig. 1. The circulating rate

By M. S. Seltzer

High temperature steady-state creep rates have been determined jor lead sulfide single crystals whose defect concentrations were fixed by equilibration under controlled sulfur pressure. The activation energy of creep, Qc , for undoped lead sulfide, is a function 01 composilion, decreasing from 2.9 to 2.2 ev as the carrier concentration increases from 9 x 1016 to 8 1018 electrons cm-3 for lead excess crystals, and increasing from 1.7 to 2.3 ev as the concentration of holes increases from 4 x 1017 to 1 x 1018 cm-3 in sulfur excess material. For five different composilions, Qc for undoped and bismuth-doped crystals has been found to be equal to Qpb + Qs, the self-diffusion activation energies for lead and sulfur in PbS. It is well-established1 that high-temperature steady-state creep of pure metals is a diffusion-controlled process, where the activation energy of creep is equal, within experimental error, to the activation energy of self-diffusion. The relationship between the activation energy for steady-state creep and those for self-diffusion in binary compounds is more complicated, however, because two different diffusing species must be considered, and becayse the activation energies may be influenced by compositional variations and by foreign atom additions.2-4 In some cases experimentally determined creep activation energies are correlated with those for self-diffusion of the slower-moving species, but such agreement is by no means universal. Interpretation of experimental results is difficult because few investigations include measurements of creep rates and self-diffusion coefficients of both diffusing species on single crystals of similar composition and foreign atom concentration. The objective of this investigation, therefore, is to determine the influence of stoichiometric defects and foreign atoms on steady-state creep and self-diffusion for a well-characterized binary compound. Lead sulfide, a compound semiconductor which crystallizes in the NaC1-type structure, and whose homogeneity range includes compositions on either side of the 1:l atom ratio, was chosen for study in this investigation. The pressure-temperature-composition relations for PbS are available,5,3 and deviations from stoichiometry may be monitored by electrical measurements.7 Single-crystal specimens are available to allow observation of effects due to bulk phenomena without interference from grain-boundary effects. These crystals have been employed to determine steady-state creep rates under compressive stress for "pure" and bismuth-doped PbS as a function of sulfur pressure and temperature as well as crystal orientation and applied stress in order to establish the relationships between defect concentrations and creep rates. EXPERIMENTAL PROCEDURES Crystal Growth. Lead sulfide crystals, prepared by the Bridgman method, are grown in evacuated quartz crucibles, filled with almost equal atomic proportions of high-purity (99.999 pct) lead and sulfur, and heated to a temperature above the melting point of PbS (about 1127°C) so that the lead and sulfur react to form molten PbS. The crucible and melt are dropped through the hot zone of the crystal-growing furnace at the rate of 1 cm per hr. The maximum melting point of PbS is slightly on the lead-rich side of the 50:50 composition; hence crystals grown from a near stoichiometric melt are usually n-type semiconductors containing excess lead atoms. Typically the lead excess concentration in solid solution with the PbS is 3 x 1018 atoms cm-3. Crystals containing either 1/20 or 1/2 mole pct Bi2S3 were prepared by addition of the foreign atoms prior to crystal synthesis. Preparation of Specimens of Controlled Stoichiom-etry. Since it is difficult to grow crystals of desired composition, the process of crystal growth and control of stoichiometry are separated into two distinct operations. Equilibration of as-grown PbS to a desired composition is most easily accomplished by first annealing the n-type crystals under high sulfur pressure (about 1 atm) at temperatures above 700°C. This process serves to put excess lead precipitates into solution, yielding 0 -type crystals upon quenching to room temperature. Inter diffusion occurs readily in crystals so treated, and the methods described by Bloem may then be employed to obtain crystals of controlled stoi-chiometry. For the creep measurements made in this study, this involves heating crystals in mixtures of H2 and H2S The equilibrium constant for H2S is given by: Thus the sulfur partial pressure is obtained from knowledge of the H2/H2S ratio and Kh2S for the temperature in question. Fig. 1 shows the p-T-x diagram for PbS. It can be seen that, within the stability limits for single-phase lead sulfide, desired compositions may be obtained by equilibrating under a specified sulfur pressure and temperature. Characterization of Crystals. The principal methods for evaluating PbS crystals include measurement of electrical properties and mass-spectrographic analysis. The measured electrical parameters include Hall coefficient, conductivity type, and electrical resistivity Bloem7 has shown that there is a 1:l relation between the defect concentration and carrier concentration obtained. Hence, if the contribution to the carrier con-

Jan 1, 1968

By H. S. Drinker

THE first discovery of zinc 011 the property now worked by this company was made by the celebrated mineralogist, Prof. William Theodore Rapper, in 1845. Different claimants kept the property in continual litigation till 1861, when everything was satisfactorily settled by the purchase of the land by the company, who have worked it ever since. The mines are situated in a valley, four miles south of Bethlehem, Pa., in Lehigh County. The valley is from two to three miles broad, and is bounded 011 the north and south by syenitic hills. Syenite underlies the valley, and upon this is deposited the Potsdam sandstone, then a layer of slate, and, finally, a dolomitic limestone, belonging to the Chazy or Black River formation, in which the zinc deposits are inclosed. The rocks occur in folds, and have evidently been subjected to tremendous pressure from below, the zinc deposit being found in an anticlinal axis, in nearly vertical veins. I t is supposed that the zinc was originally disseminated through the

By B. C. Craft

The principal events in the oil and gas operations for Louisiana during 1933 have been the rapid development of the Converse field in Sabine Parish, the discovery of three new salt domes, one in North Louisiana and two in South Louisiana, increased development in the Iowa field on the Calcasieu-Jefferson Davis Parish line, and extensive geophysical operations over a wide territory. Other miscellaneous events worthy of mention are the continued leasing of prospective oil lands over a wide area, extension of production at the East Hackberry field, Cameron Parish, discovery of deep sands at Caillou Island, Terrebonne Parish, and the completion of several important wildcats. Despite proration, oil production showed a substantial increase during 1933. The total output for this area was 25,599,802 bbl. as compared with 22,507,387 bbl. during 1932. North Louisiana There were 111 oil wells and 47 gas wells completed in North Louisiana during 1933 as compared with 109 oil wells and 33 gas wells during 1932. North Louisiana oil production decreased approximately 692,625 bbl. in 1933 from its 1932 figure. The normal decline in the old fields was partly offset by increased production at the Zwolle and Converse fields in Sabine Parish. Acid treatment of wells in the Zwolle, Converse and Monroe fields was highly successful. The method of application has been described by H. K. Shearer, Geologist, Pelican Natural Gas Co., as fo1lows:l With tubing in the hole and standing valve removed, the casing is filled with oil to the surface. The limestone solvent is pumped in through the tubing, at the same time bleeding off enough oil from the casinghead to equal the volume contained in the tubing plus the volume of open hole to be treated. The amount of solvent used in most of the wells treated was 1000 gal., which is enough to dissolve about 11 cu. ft. of chalk or limestone. After the computed amount of oil is bled off, the casinghead is closed and the remainder of the solvent is pumped in at whatever pressure is necessary to force it into the oil-producing horizon. The solvent is followed up with enough oil to

Jan 1, 1934

CONTENTS PAGE SOUTHWARD, GLENN B.-Coal Mining by the V System. Discussed by Glenn B. Southward, Howard N. Eavenson, Edward B. Raiguel, Thomas de Venny, J.. J. Rutledge, Graham Bright 1 ARMS, RAY W.-Dry Cleaning of Coal. Discussed by Ray W. Arms, S. A. Taylor, Howard N. Eavenson, W. R. Crane, F. F. Jorgenson, G. R. Delamater. 6 EAVENSON, HOWARD N.-Data About Labor Employed in Various Bituminous Coal Mines. Discussed by Howard N. Eavenson, George H. Ashley, E. A. Holbrook, S. A. Taylor, R. V. Norris 14 Coal Mining by the V System Discussion of the paper of GLENN B. SOUTHWARD presented at the New York Meeting, February, 1924, and issued as Paper No. 1300-C, with MINING AND METALLURGY, February, 1924. MEMBER.-How do you pay your men for loading? GLENN B. SOUTHWARD.-Everything is on time basis. MEMBER.-How many men do you have loading across one of the diagonal faces? GLENN B. SOUTHWARD.-From four to five, depending on the length of the face. Our loaders are so arranged that each will give about twenty-five tons per loader a day. MEMBER.-How much timber do you use? GLENN B. SOUTHWARD.-A little more than will be used in room-and-pillar work, but not a great deal more. We have not attempted to recover much of our timber. MEMBER.-IS the mine union or non-union? GLENN B. SOUTHWARD.-Non-union. HOWARD N. EAVENSON, Pittsburgh, Pa.-I went .through that mine some weeks ago, and think that the author has been very conservative in his statements about the amount of loadings, etc. EDWARD B. RAIGUEL, Huntington, W. Va. (written discussion).¬Page 7 shows 60 men employed in day and night shifts, inside the mine, producing 750 tons per day. Let us reduce these figures to a man-hour basis, for comparison with Mr. Eavenson's figures on West Virginia mines, as follows:

Jan 6, 1924