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

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

Jan 1, 1969

By H. L. Teicliman, E. M. Sipprelle

ENACTMENT of Public Law 290 by the 78th Congress authorized the U. S. Department of the Interior, Bureau of Mines, to conduct an experimental program to develop the technology for obtaining oil from oil shale. In adopting and later extending this legislation, the Congress recognized the impending necessity of supplementing ground petroleum reserves with synthetic fuels. Under the provisions of this legislation, the Bureau of Mines, among other things, was charged with the responsibility of developing mining techniques, methods, and equipment for mining the oil shales of the Green River formation of Colorado, Utah, and Wyoming.

Jan 1, 1950

Executive ARTHUR S DWIGHT, Chairman B THAYER CHARLES F RAND P MATHEWSON J V W REYNDERS Membership WILLIAM H BASSETT, Chairman W Y WESTERVELT Vice-chairman P MATHEWSON H G MOULTON F T RUBIDGE Finance WALTER H ALDRIDGE, Chairman GEORGE D BARRON GALEN H CLEVENGER

Jan 1, 1923

By H. W. Hindry

This paper presents the ingredients com-~osing a type of oil-base mud that has been successfully used in drilling oil horizons in California, the effect of ingredient concentrations on physical properties, methods of handling at the well and possible advantages of a waterless drilling fluid with excellent plastering properties. Introduction An oil-base mud is a rotary drilling fluid in which oil has been substituted for water as the principal liquid ingredient. In recent years such a mud has been developed and used successfully for drilling the oil horizons of wells in various Calilornia fields. There are several types of oil-base mud, but only the type that is currently used to any appreciable extent will be considered at this time. The oil-base drilling-mud compositions used by Shell Oil Company, Incorporated have been covered by several patent applications on which patents are expected to issue at an early date. The purpose of this paper is to present data on the fundamental design of the mud; the ingredients used and their specifications; the effect of ingredient concentration on physical properties; the selection of the proper mud; the facilities needed for handling the mud; and a general discussion on drilling with oil-base mud. In view of the early stage of development of oil-base mud, the great number of vari- ables, and the almost unlimited possible combinations of these. variables, which in turn require extensive laboratory study, there are certain irregularities and omis. sions in the data presented here. However, it is believed that sufficient data are at hand to permit a fairly complete analysis of the characteristics of oil-base muds. In view of the excellent plastering properties of oil-base mud when properly proportioned, its use should: (I) minimize the possibility of impairing the natural flow potentialities of the producing horizon such as that resulting from infiltration of water from water-base muds; (2) permit smaller clearances for setting liners, since the mud sheath has no appreciable thickness; (3) eliminate the possibility of clogging the perforations of the liner with thick mud sheath; (4) facilitate the removal of the mud sheath from the walls of the hole, for its mud sheath has no appreciable strength; (5) assist in drilling through formations, such as "heaving shale," where water wetting appears to be a source of difficulty. (6) permit cores to be obtained without contamination from drilling water. Fundamental Design of an Oil-base Mud In the design of any rotary drilling mud it is necessary to select materials that will fulfill the following requirements: (I) act as the liquid medium and regulate the viscosity; (2) impart initial and final plastering properties; (3) give gel strength and structure in order to prevent settling; (4) serve as a weighting material. The

Jan 1, 1941

By H. W. Hindry

This paper presents the ingredients com-~osing a type of oil-base mud that has been successfully used in drilling oil horizons in California, the effect of ingredient concentrations on physical properties, methods of handling at the well and possible advantages of a waterless drilling fluid with excellent plastering properties. Introduction An oil-base mud is a rotary drilling fluid in which oil has been substituted for water as the principal liquid ingredient. In recent years such a mud has been developed and used successfully for drilling the oil horizons of wells in various Calilornia fields. There are several types of oil-base mud, but only the type that is currently used to any appreciable extent will be considered at this time. The oil-base drilling-mud compositions used by Shell Oil Company, Incorporated have been covered by several patent applications on which patents are expected to issue at an early date. The purpose of this paper is to present data on the fundamental design of the mud; the ingredients used and their specifications; the effect of ingredient concentration on physical properties; the selection of the proper mud; the facilities needed for handling the mud; and a general discussion on drilling with oil-base mud. In view of the early stage of development of oil-base mud, the great number of vari- ables, and the almost unlimited possible combinations of these. variables, which in turn require extensive laboratory study, there are certain irregularities and omis. sions in the data presented here. However, it is believed that sufficient data are at hand to permit a fairly complete analysis of the characteristics of oil-base muds. In view of the excellent plastering properties of oil-base mud when properly proportioned, its use should: (I) minimize the possibility of impairing the natural flow potentialities of the producing horizon such as that resulting from infiltration of water from water-base muds; (2) permit smaller clearances for setting liners, since the mud sheath has no appreciable thickness; (3) eliminate the possibility of clogging the perforations of the liner with thick mud sheath; (4) facilitate the removal of the mud sheath from the walls of the hole, for its mud sheath has no appreciable strength; (5) assist in drilling through formations, such as "heaving shale," where water wetting appears to be a source of difficulty. (6) permit cores to be obtained without contamination from drilling water. Fundamental Design of an Oil-base Mud In the design of any rotary drilling mud it is necessary to select materials that will fulfill the following requirements: (I) act as the liquid medium and regulate the viscosity; (2) impart initial and final plastering properties; (3) give gel strength and structure in order to prevent settling; (4) serve as a weighting material. The

Jan 1, 1941

By John R. Green

ROTARY kilns, varying in construction, are used in a variety of processes. Products differ and operating conditions vary according to economic requirements. All of these variables influence the degree of instrumentation and type of control necessary or profitable to install. Products fired in rotary kilns are the results of combined temperature and time treatment and the interrelation of these two factors should be kept constantly in mind in the perusal of this paper. MEASUREMENTS OF KILN TEMPERATURE The securing of proper temperatures within the rotary kiln, either of the charge or of the kiln lining in the high fire zone, are basic objectives of kiln operation; therefore the measurement of these high-temperature conditions merits first consideration.. For these measurements, radiation pyrometers, properly designed and protected, have proved adequate, particularly where records or automatic control are desired, while optical pyrometers may serve as portable indicators. Light-sensitive devices or photoelectric cells in this service are capable of producing records as well as certain forms of automatic control. High-temperature measuring devices for rotary-kiln work should have the measuring unit protected from dust, as a continued accumulation of deposit would lower the readings. Fig. I shows a typical application of radiation equipment to a rotary kiln, mounted far enough away from the sighting hole through the kiln hood to be protected from puffs or stingouts and with a sighting tube having a series of settling chambers, to prevent dust from reaching the lens. Although dust conditions inside the kiln itself usually fluctuate considerably and have their effect upon the readings at that moment, such effects are not cumulative and show as a continuous fluctuation in the temperature indicated, provided the radiation unit and recorder are responsive to such slight and rapid temperature fluctuations. The ambient temperature to which a measuring unit is subjected fluctuates from possibly o° to over 200°F., therefore these changes should have no effect upon the final reading or upon the life of the measuring unit. A very narrow sighting angle is desirable, so that measurement of temperature may be made as far as possible into the high fire zone without. effect of the flame temperature. There should be some sighting means on the measuring unit, so that the proper field may be viewed. Measurement of wall temperature taken at a point where the charge has just left the wall is less affected by dusting conditions than when taken elsewhere. Factors Influencing Temperature Table I gives an outline of the factors that produce kiln temperatures and com¬ments on the possibility of measurement and control. Of greater number and of varied influ¬ence are the factors that control when, where and how the heat is delivered to the kiln, the type of flame and the rate of

Jan 1, 1941

J. E. Stead, Middlesborough, England (communication to the author): Prof. Howe's valuable paper on cast-iron brings forward most prominently the correct explanation of the part played by combined carbon in pearlite and cementite, in determining the strength and hardness of cast-iron. On a previous occasioil I have shown that castings made by melting a white Cleveland iron and glazed iron, one containing 1.5 and the other from 4 to 5 per cent. of silicon, and each about 3 per cent. of carbon, were stronger than those made of ordinary foundry-iron; the difference in the final castings being a differ-

Jan 1, 1902

By Nicholas J. Grant, Ernest P. Abrahamson

IN recent work, Bloom and Grant' and Stein and IGrant' have indicated that a high temperature chromium phase exists. In the 68 pct Cr-Ni binary they found a eutectoid reaction, P chromium transforming to a chromium plus y nickel at 1215°C. Un-

Jan 1, 1957

By R. A. Oriani

The partial molal volume of hydrogen is one of the parameters that describe the elastic interaction between the solute and the stress fields about inclusions, dislocations, and cracks. As such the partial molal volume is probably of importance in the elucidation of phenomena such as hydrogen embrittlement and hydrogen yield point. A knowledge of this quantity would also be helpful in thinking about the state of dissolved hydrogen in iron. However, because of the very low lattice solubility of hydrogen in iron the usual ways of determining the lattice expansion are not practicable. It is therefore of interest to apply the thermodynamics of stressed bodies to two sets of measurements of the effect of elastic stress upon the permeability of hydrogen in order to deduce a value of the partial molal volume, VH, of hydrogen dissolved in a iron. Beck ..' and previously de Kazinczy, observed that a uniaxial tensile stress increases the permeability of hydrogen in iron and in various steels. Beck et 01. employed Armco iron and A.I.S.I. 4340 steel, whereas de Kazinczy used a steel the composition of which was 0.13 C, 0.23 Si, 0.46 Mn, 0.006 P, and 0.038 S. Upon releasing the stress the permeability increment disappeared if the stress was below the elastic limit. Both investigators employed cathodic charging to introduce the hydrogen. de Kazinczy measured the permeation through a thin-walled tube by collecting the gas, whereas Beck et al. measured the permeation through sheets of various thicknesses by a very sensitive electrochemical technique. Both investigators measured the steady-state permeation at constant rate of hydrogen ion discharge, and Beck measured in addition the hydrogen diffusivity by a time-lag technique which is independent of the boundary conditions. Beck et al. and de Kazinczy found a linear relationship between log (J,/Jo) and the stress, where Ju/Jo is the ratio of the flux of hydrogen when the metal is under uniaxial tensile stress, a, to the flux under zero stress, for the same temperature and charging current. Beck et al. found in addition that the diffusivity of hydrogen is not changed by stress. Both investigators concluded that the observed change in permeability is due to an increase in hydrogen concentration, and furthermore that the increase in concentration is due directly to the thermodynamic effect of stress upon concentration. Accepting this assessment of the situation for reasons given below, one may use the equation3j4 in order to evaluate I/H, the partial molal volume of hydrogen. This equation is valid for the domain of a/E «¦ 1 (where E is the Young's modulus) and under the assumption that hydrogen expands the lattice isotrop-ically. From the data of Beck el al, one calculates V7H - 2.0 cu cm per g-atom, and from those of de Kazinczy one obtains 1.8 cu cm per g-atom. That the increase of concentration with stress is indeed of thermodynamic origin is attested to by the facts that the experimental results conform to the thermodynamic relation, Eq. [I], and that the results are the same whether a pure iron1 or each of two different steels172 is used. Neither of these facts wou1.d necessarily be expected if the effect of stress were, rather, to increase the ratio kn/k, of the kinetic factors of the following competing reactions: H(ads) — H (dissolved) Such a change of kinetics at the surface could be an alternative explanation of the effect of stress on the permeability. Although this writer does not deem this explanation to be the correct one for the reasons given above, it must be admitted that unambiguous proof that the phenomenon has a thermodynamic origin does not yet exist. Two kinds of experiments may be suggested. One is to plate a variety of metals on the input surface of the steel and repeat the stress experiment at a variety of hydrogen charging currents. The other is to employ somewhat thicker specimens in order to be able to apply uniaxial compressive stress. Eq. [I] shows that ln(c,/c,) depends on the sign of the stress, but it is difficult to see a physical basis for which k2/kl would depend on the sign of a. The present value of V^ in a iron agrees with phragmen's5 estimate, which he based on comparisons with the lattice expansion by hydrogen of titanium, zir-

Jan 1, 1967

NEW MEMBERS The following list comprises the names of those persons who became members during the period of May 10, 1918, to June 10, 1918. ABEEL, GEORGE H., JR., Cons. Min. Engr., .4111 Lafayette Ave., St. Louis, Mo. ALLEN, CARL A Metal Min. Engr., U. S. Bureau of Mines, Butte, Mont. BECKER P. FRANK Engr., Lightner Min. Co., 35 Nassau St., New York, N. Y. BOCK, JAMES H., Steam Shovel Foreman, Chino Copper Co., Santa Rita, N. M. CARRON, FRANK X., Civ. and Min. Engr Rock Springs, Wyo. CROWE, THOMAS B., Mill Supt., Portland Mill, Portland Gold Min. Co., Victor, Colo. DOBSON, PERCY GRENSIDE, Min. Engr. and Geol., Crow's Nest Pass Coal Co., Fernie B. C., Canada. ESTABROOK, W. H., Capt., 3d Bat. 20th Engineers, A. E. F., Care postmaster, N.Y. FRASER, 0. B. J., Engr., International Nickel Co. of Canada, Ltd., Port Colborne, Ont., Canada. GARRIDO,. MANUEL F., Min. Engr 109 W. Myrtle St., San Antonio, Tex. GRODSKY, VLADIMIR ALEXANDROVITCH, Cons. Engr., Motor Products Corpn., Detroit, Mich.

Jan 7, 1918

By G. F. Fix

Oil and gas activity reached a higher peak in Indiana during 1940 than for any like period during the past decade. Major activity, as during 1939, was in the southwestern part of the state, the Indiana portion of the Eastern Interior Coal Basin, where most of the increase was due to field drilling in previously proven areas. The amount of wildcat drilling was about the same as for 1939. No new fields of any apparent consequence were discovered during the year, with the possible exception of the College pool, in southwest Posey County. Only one well had been completed in this area at the end of the year. About 10 ft. of saturated Aux Vases sandstone was drilled in this well and the initial production was I00 bbl. of oil a day. Other discoveries during the year 1940 include: St. Thomas, in southwestern Knox County, where four McClosky wells, ranging from I00 to 300 bbl. a day initially, were com-pleted; Buff kin, in central Posey County, with 11 oil wells and 5 gas wells completed; and new developments in two old areas —Randolph County (part of the old Trenton field) and Gentryville, northwestern Spencer County, where some oil was found many years ago. The St. Thomas field proved disappoint-ing, with very spotty production from the McClosky horizon of the St. Genevieve limestone at a depth of about 1875 ft. The discovery well flowed 362 bbl. a day ini-tially. At the end of the year the field was pretty well outlined by dry holes and some inside locations were dry. The Buffkin pool also proved spotty, with production from shallow Pennsylvanian sands and from the Basal Pennsylvanian Mansfield sandstone, the latter at a depth of approximately I175 ft., with small production from the Cypress sandstone of Chester age. Oil wells in this pool are small, ranging from 25 to 75 bbl. a day. The Randolph County area, on the east side of the Trenton gas field, showed some promise for a commercial gas field, with four completed gas wells having cumulative initial flows of about 1,200,ooo cu. ft. a day. The area appar-ently was not depleted during the Trenton boom at the turn of the century, since casing pressures are about as high as the virgin pressure in the old field. Elsewhere the pressure has dropped as low as 5 pounds. The Griffin field received most of the drilling during 1940, with 163 completed oil wells. This field now covers about 3200 acres on the Indiana side of the Wabash River and is not as yet completely delimited. It produced the major part of Indiana's oil during the year—a total of 3,594,000 bbl. At the end of 1940, there were 253 producing wells in Griffin. New Harmony had five completions for a total of 24. The Rockport field, in Spencer County, continued to be actively developed and had a total of 45 gas wells and 9 oil wells at the end of the year. Oil in commercial quantities had not been found in the field previous to 1940. Total gas production for the year was 394,470,000 cubic feet. In all, 521 wells were drilled in the state during 1940, as compared to 377 for 1939. Of this number 248 were oil wells, 77 were gas wells and 196 were dry. Divided into

Jan 1, 1941

By G. F. Fix

Oil and gas activity reached a higher peak in Indiana during 1940 than for any like period during the past decade. Major activity, as during 1939, was in the southwestern part of the state, the Indiana portion of the Eastern Interior Coal Basin, where most of the increase was due to field drilling in previously proven areas. The amount of wildcat drilling was about the same as for 1939. No new fields of any apparent consequence were discovered during the year, with the possible exception of the College pool, in southwest Posey County. Only one well had been completed in this area at the end of the year. About 10 ft. of saturated Aux Vases sandstone was drilled in this well and the initial production was I00 bbl. of oil a day. Other discoveries during the year 1940 include: St. Thomas, in southwestern Knox County, where four McClosky wells, ranging from I00 to 300 bbl. a day initially, were com-pleted; Buff kin, in central Posey County, with 11 oil wells and 5 gas wells completed; and new developments in two old areas —Randolph County (part of the old Trenton field) and Gentryville, northwestern Spencer County, where some oil was found many years ago. The St. Thomas field proved disappoint-ing, with very spotty production from the McClosky horizon of the St. Genevieve limestone at a depth of about 1875 ft. The discovery well flowed 362 bbl. a day ini-tially. At the end of the year the field was pretty well outlined by dry holes and some inside locations were dry. The Buffkin pool also proved spotty, with production from shallow Pennsylvanian sands and from the Basal Pennsylvanian Mansfield sandstone, the latter at a depth of approximately I175 ft., with small production from the Cypress sandstone of Chester age. Oil wells in this pool are small, ranging from 25 to 75 bbl. a day. The Randolph County area, on the east side of the Trenton gas field, showed some promise for a commercial gas field, with four completed gas wells having cumulative initial flows of about 1,200,ooo cu. ft. a day. The area appar-ently was not depleted during the Trenton boom at the turn of the century, since casing pressures are about as high as the virgin pressure in the old field. Elsewhere the pressure has dropped as low as 5 pounds. The Griffin field received most of the drilling during 1940, with 163 completed oil wells. This field now covers about 3200 acres on the Indiana side of the Wabash River and is not as yet completely delimited. It produced the major part of Indiana's oil during the year—a total of 3,594,000 bbl. At the end of 1940, there were 253 producing wells in Griffin. New Harmony had five completions for a total of 24. The Rockport field, in Spencer County, continued to be actively developed and had a total of 45 gas wells and 9 oil wells at the end of the year. Oil in commercial quantities had not been found in the field previous to 1940. Total gas production for the year was 394,470,000 cubic feet. In all, 521 wells were drilled in the state during 1940, as compared to 377 for 1939. Of this number 248 were oil wells, 77 were gas wells and 196 were dry. Divided into

Jan 1, 1941

By ROBERT R. RICHARDS

My. first paper, read at the Cobalt Meeting of the Institute,1 July, 1907, dealt with the behavior of a small Wilfley table when concentrating galena from quartz, the table being fed with natural products, with sized products; and with classified products. Since galena, having a specific gravity of 7.5, is among the heaviest minerals ordinarily concentrated by Wilfley table, it was desirable that a similar set of tests upon a mineral of, lighter weight should be made. Chalcopyrite, of a specific gravity of 4, would have been the best mineral for this purpose, on account of its great importance as an economic mineral, but in carrying out the test, however, I was obliged to content myself with a cupriferous pyrite, the specific gravity of which was 4.68 and the contents in copper 8.80 per cent. Through the kindness of Mr. H. 0. Cummins, this material was obtained from Shasta, Cal.,in very pure, clean, homogeneous condition. It was broken by rolls to 2 mm. in size, taking care to make a minimum of slimes. The quartz used to mix with it was pure, white, New England quartz, broken in the same way to the same size. In studying the accompanying tables, it should be borne in mind that the material concentrated was of low copper-content, and in many cases the quantity fed to the machine was 1 kg: or less.. As a consequence of the smallness of the 'quantity treated it was very difficult to adjust the table and get it in condition to do its best work before the feed became exhausted, and for this reason many results were obtained which appear irregular.

Sep 1, 1908

By Yuri D. Tretyakov, Robert A. Rapp

The stoichiometry ranges ofNiOl+y and LiFe,O,-d were established by high-temperatwe electrochemical meas7rements in a stabilized-zirconia electrolyte cell. The results were consistent with doubly ionized cation vacancies in NiO,+y and interstitial lithium or iron ions in . The defect structure of the ternary ferrite was derived from the consideration of equilibration with respect to oxygen between the solid and the gas phase. The absolute magnitudes of defect concentrations were calculated. Pavtial molar enthalpies of oxygen in the compounds were calculated and interpreted in terms of the enthalpy of defect formation in these crystals. NICKEL oxide (NiO,,?) is a metal-deficient, p-type, extrinsic semiconductor whose properties are consistent with a structural model based on the presence of cation vacancies as the predominant ionic defect at sufficiently high temperatures and oxygen activities. A survey of previously reported conductivity studies and the presentation of some more recent conductivity measurements will be given in a later paper.' The absolute magnitude of the equilibrium vacancy concentration in NiO has been reported from combined conductivity and thermogravimetric data of ' However, disagreement exists concerning the state of ionization of the nickel vacancies in NiO. Some authors3-' have proposed that the predominant defects in NiO are singly ionized nickel vacancies and positive holes (h') formed by the reaction where, accorhng to the notation of Kroger and Vink,6'7 Oq represents an oxygen ion on its normal lattice site. Other authors"27E have proposed that doubly ionized nickel vacancies (V{i ) and positive holes are predominant and are formed by the reaction One purpose of the present investigation was to establish the nature of the predominant defect in NiO,+? as well as its equilibrium concentration and thermo-dynamic properties at elevated temperatures and known oxygen activities. To accomplish this purpose, the coulometric titration of oxygen into and out of NiO was accomplished using a galvanic cell involving the calcia-stabilized zirconia electrolyte. The ternary oxide, lithium ferrite (LiFe50,-6) is ferromagnetic and has the inverse spinel structure LiFe,O,-d Thus, in the ideal stoichiometric XY204 lattice, Fe3 ions occupy one-eighth of the tetrahedral (A) sites, and i' and Fe3' ions share at random one-half of the octahedral (B) sites within the fcc sublattice of oxygen ions.g The structure and thermodynamics of the spinel structures have been comprehensively decribed.'-' A recent compilation of literature for lithium ferrite is also available. 15 Oxygen-excess LiFe50sis not expected to exist because both i' and 17e3& ions are in their highest normal valency states (positive hole formation is not favorable). As will be discussed, equilibration of the ferrite crystal with oxygen of a surrounding gaseous phase will result in the introduction of equilibrium concentrations of ionic and electronic defects. In the Results and Discussion section a defect model for LiFe50,-d is proposed. This defect model is tested by high-temperature coulometric titration experiments. EXPERIMENT The oxygen activities in nonstoichiometric NiOl+, (and also LiFe,O,-d) were measured by means of coulometric titration with the high-temperature galvanic cell The critical characteristic of a suitable experimental cell is the complete isolation of the phase to be investigated in a minimum sized chamber which is free from extraneous sources and sinks for oxygen (leakage). Then oxygen is only admitted to the chamber or removed from it in known amounts by coulometric titration, which involves the passage of oxygen ions through the solid electrolyte with electrochemical oxidation and reduction reactions at the platinum contacts to the electrolyte. The experimental cell is shown in Fig. 1. The cap of the cell was the tip from a closed-end alumina tube, which was found to be leak-free from a helium leak-detector test. This alumina cap was about 1.2 cm OD and about 1.5 cm high. A Zircoa calcia-stabilized zirconia tablet (crucible lid) of 1.5 cm diam and 0.3 cm thickness served as the solid electrolyte. A Pyrex ring of about 0.1 cm thickness was placed between the electrolyte and the cap. The electrolyte tablet was painted with platinum paste on the entire outer face and on that part of the inner face which would be within the enclosure; these electrodes were further prepared by heating in air at 1000°C for 2 hr. Nickel oxide powder, listed as 99.999 pct pure, was purchased from Leico Industries, Inc. Pills of the NiO were cold-pressed and sintered at 1050°C for 3 hr in a platinum crucible. This poorly sintered NiO was crushed, and chunks were wrapped in 52-mesh Pt gauze (to catalyze the solid-gas exchange) for place-

Jan 1, 1970

By R. W. Nash, A. E. Schwaneke, V. R. Miller

The Bureau of Mines developed a detector for controlling sorting devices to separate the copper-bearing fragments from the barren portion of Michigan native copper and western prophyry copper ores. A successful sorter could be used to preconcentrate the ore and eliminate costly hoisting or hauling of waste. An induction balance unit was developed and used in sorting tests on crushed sized - 2.5 + 1. 3-cm (- 1 + 1/2- in.) ores from the Kingston (0.9% Cu) and Centennial (1.6% Cu) mines of Upper Michigan. Concentrates of 4.0% and 7.5% Cu, respectively, were obtained at recoveries of 85 and 80% of

Jan 8, 1978

By W. J. Millard

VAGUE rumors and stories have been heard, from time to time, about the diamond and gold deposits of southern Venezuela. It is perhaps appropriate, at this time of revived interest in gold mining, to publish a few facts in regard to this country, which has been undergoing exploration since the fifteenth century. Gold and diamonds are found principally in the State of Bolivar which lies in southeastern Venezuela and is bounded by British Guiana on the east and Brazil on the south (see Fig. 1). The famous Mt. Roraima is situated at a point where these three countries meet in a common point (see Fig. 2). Some gold is also found in the southern part of the territory of Amacuro. Good oil prospects exist in the northern part of this same territory. Diamonds are found on the Caroni river from Rio Paragua to the village of Guri. Another small district is on the headwaters of the Cuyuni river. Quartz veins containing gold are chiefly exploited in

Jan 1, 1931

By C. K. Leith

THE purpose of these conferences has been to find some basic principles to guide us in the chaos which confronts us, to arrive at elements of a national policy. None such exists, nor, as a matter of fact, have there been any concerted efforts by the public or the mineral industry to evolve one. In the absence of such a policy the administrative agencies of the government can hardly be expected to be consistent or really effective in their handling of mineral problems, domestic or foreign. Basic Facts MINERAL reserves are unequally distributed among the nations. The principal world supplies are grouped around the north Atlantic, and nearly three-fourths of the world's total is controlled politically and commercially by English-speaking people. No one nation has a complete supply of the minerals necessary for modern industry; specialization, reciprocity, and large-scale movements between the nations are inherent in nature's unequal distribution of them. The principal sources of supply are relatively few compared with the nations to be served-a fact which determines broadly certain natural outlines of the world flow. National isolation with regard to minerals can be accomplished only through backward steps in industry and lower standards of living even in the nations possessing the most of the mineral supplies. A certain measure of unified commercial control, international in scope, is a natural consequence of the limited number of the large sources of supply. Mineral supplies for the world as a whole are so large that there is little need for concern about early exhaustion, but every nation has important problems of early exhaustion of particular minerals, which must affect their policies.

Jan 1, 1933

EXECUTIVE COMMITTEE OF THE BOARD OF DIRECTORS CHESTER A. FULTON, Chairman CARROLL A. GARNER H. Y. WALKER WALLACE E. PRATT FELIX E: WORMSER PAUL D. MERICA, Consultant FINANCE COMMITTEE OF THE BOARD OF DIRECTORS ERIE V. DAVELER, Chairman WILBER JUDSON RUSSELL B. PAUL HENRY KRUMB, Consultant

Jan 1, 1944

United Engineering Trustees, Inc. ARTHUR S. DWIGHT GEORGE D BARRON J V. N DORR Engineering Societies Library Board ROBERT PEELE PHILIP W. HENRY GEORGE C STONE JOSEPH E. POGUE The Engineering Foundation H C BELLINGER GALEN H CLEVENGER J V N DORR

Jan 1, 1923

By O. P. Arora, I. L. Caplan, H. von E. Doering

ThE interpretation of X-ray and electron diffraction data obtained in plastic deformation studies of hcp a titanium requires knowledge of angular relationships between crystallographic planes and directions. Rarey el 01.' have calculated both interplanar angles and angles between directions for a number of c/a ratios. This information, although useful for approximate applications, does not provide exact data for specific hcp metals. Recently, Hu2 has tabulated interplanar angles specifically for hcp titanium. The present study augments the existing data on titanium by providing the angles between plane normals and rational crystallographic directions in addition to interplanar and interdirectional angles. These angular relationships were calculated on an IBM 360 Computer using a Fortran IV program.* Cal-

Jan 1, 1969