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C. Q. Payne, New York City: Prof. Blake's inference that magnetic separation may be successfully employed upon smithsonite and iron oxide, after a preliminary roasting, is confirmed by the fact that this separation has been carried on with entire success for over a year at the works of the Wythe Lead and Zinc Mine Co., Austinville, Va. The ore mined on this property is a mixture consisting chiefly of galenite, smithsonite and limonite. The crude material is crushed, screened and washed in log washers for the removal of clay, and then jigged for the separation of the galenite. The zinc-and iron-ores are then roasted in reverberatory furnaces, being turned and moved towards the bridge-end of the hearth by manual labor. The roasted material contains from 20 to 26 per cent. of metallic iron. The slight difference in the specific gravities and the friable condition of the ores after roasting prevent the separation of the oxides by means of jigging. It was therefore the practice, previous to the use of magnetic separation, to charge the roasted material directly into the retorts of the zinc-furnaces. The rapid cutting of the retorts under this practice proved a serious inconvenience and expense. In the spring of 1892, the writer built for the Wythe Lead and Zino Mine Co. a magnetic separator which embodied several novel features and which was designed to treat the roasted zinc- and ironoxides. This separator has proved entirely successful for the purpose for which it was designed. During the first nine months of its operation, 1415 tons of 2240 pounds of roasted material were passed through the separator, producing about 675 tons of heads carrying from 50 to 55 per cent, of metallic iron, which are sold to a neighboring blast-furnace. The tailings, which contain the zinc, carry from 4 to 6 per cent. of metallic iron. For magnetizing the iron-ore previous to separating it from the zinc-ore, no change whatever mas made in the form of the reverberatory furnace previously employed. It was found that, by charging near the bridge-end of the hearth, toward the end of the roast-

Jan 1, 1894

By William L. Boyd, Eugene L. McCarthy, Laurance S. Reid

Proper control of the moisture content of natural gas is essential to reliable operation of gas transmission and distribution facilities serving northern markets. The moisture content of natural gas is usually determined by dew point measurement at the existing pressure. For any gas of constant moistrire content. the dew Point varies with the pressure. A correlation of the data of several investigators is prezented in graphical form by the authors. These data were correlated by the authors and F. M. Townsend, C. C. Tsao. M. I). Rogers. Jr.. and J. A. Porter. graduate students in chemi(.a1 engineering at the University of Oklahoma. Of articular interest are the hitherto unpublished low temperature data observed by Wickliffe Skinner. Jr., which are included in this correlation. PRESENTATION OF DATA The problem of interpreting water dew points, or saturation temperatures. of natural gas in terms of specific moisture con-tent has increased in importance during the past decade bec.arl.;e of extensive development.; in the transmission and petro-chemical phases of the natural gas industry. Virtually all gas transported to northern and eastern markets must be dehydrated to a low water vapor content to prevent hydrate formation in transmission and distribution lines and resultant interruption.; in gas deliveries. Complete dehydration is required in certain phases of tile petro-chemical industry involving low-temperature operations. It is a well-known fact that the water vapor content of pure hydrocarbon vapors and their mixtures at superatmospheric pressures cannot be predicted with accuracy by assuming validity of the ideal gas laws." Earlier interest in the general problem was concentrated on the water vapor content of pure hydrocarhons and hydrocarbon mixtures in the pressure and temperature ranges common to gas and oil producing reservoirs in order to obtain fundamental data for the improvement of production techniques and the furtherance of reservoir studies. Excellent data are published for pressures ranging from atmospheric to 10,000 psig and for temperatures ranging from 100° to 460° F4,9,10,11 and are found to be in close agreement. However, experimental data at high pressures and temperatures below 100°F are comparatively limited in scope. Experimental data in the lower temperature range have been reported by Laulhere and Briscoe.8 Deaton, et al,2,3 Hammerscllmidt,5,6 and wade," In general, the pressures employed in these investigations ranged from atmospheric to 1.000 psig while temperatures ranged from 32° to 120°F; i.e., the usual conditions encountered in gas transmission line operations, Additional data were reported by Russell, et al,12 at pressures as high as 2.000 psig and covering a rather narrow atmospheric temperature range. In 1947, Hammerschmidt published a correlation of all available data,' in which the water vapor content of gases at saturation. under high pressure and low temperature. was predicted by extrapolation. In 1948, Wickliffe Skinner. Jr.. presented data on the moisture content of a low nitrogen content gas at low temperature and at pressures ranging upward to 1.500 psia.1-3 Comparison of Skinner's experimental data with the extrapolated data of Hammerscllmidt revealed an appreciable variation in the lower temperature range. emphasizing the need for a new correlation which would rely on Skinner's data at lower temperatures. Careful scrutiny of available data suggested that presence of an appreciable quantity of nitrogen in a gas mixture may affect its saturated moisture content so that data obtained from gases with more than three per cent nitrogen were not used in this correlation. CORRELATION OF DATA Data employed in this correlation are presented in Table I. The data of Dodson and Standing.4 McKetta and Katz,9 and Olds, Sage and Lacey10 were compared and found to be in close agreement so that the data of Olds. et al, re-plotted in a more convenient form by the Humble Oil and Refining Co.,' were used for temperatures of 100°F and above. Skinner's data were used for temperatures below 40°F. Between these intermediate temperature limits, the data of Hammerschmidt.7 Wade" and extrapolated data of Olds. et al.1 were tabulated

Jan 1, 1950

By Robert L. Frantz

Progress and improvement continue to be the bywords of a dynamic coal industry. The industry continues to gain strength and expand its horizons in the face of competition from atomic energy and the problems of restrictive legislation. The direct contribution of coal mining and transportation to the national economy is about $3 billion a year ac- cording to a study made by the National Coal Policy conference. Coal remains the backbone of the power industry producing almost two-thirds of all the electrical energy generated by fossil fuels and one-quarter of all the energy consumed in the nation. Power supplied by electric utilities increased 6.9% last year. The chairman of the Federal Power Commission predicted a 7.5% growth rate until 1980 for the nation's electric output. Some 80,500 MW of fossil fired power plant capacity are on order or under construction before 1974, compared to a present capacity, all sources, of about 290,000 MW. The comparable new additions of nuclear power plants is expected to total about 51,000 MW.

Jan 2, 1969

By AIME AIME

IN a recent technical paper of the Central Committee of the French Coal Mines (Note technique No. 198, by L. Lahoussay) the author points out that continuous in¬crease in depth of mine shafts makes it more and more necessary to look for appropriate means to reduce the weights and dimensions of the hoisting ropes. Increasing depth demands a larger section and weight for the cable if the useful load is not to be cut down at the same time. This naturally leads to increased cost per ton, and at the same time creates serious mechanical difficulties. The dimensions of the hoisting engine must be increased, acceleration at the start must be decreased so as to avoid periods of excessive peak power loads, and a longer time be allowed to slow down the speed of the hoist when applying brakes. The hoisting rope, upon which depend the dimensions and hence the mass of the hoisting engine, presents the greatest obstacle to the development of hoisting from greater depths. Evidently, for a given depth, the total weight of the rope can be notably reduced by utilizing a wire rope of decreasing section, approaching the theoretical logarithmic form. This is a solution frequently adopted for great depths. Of course, the weight of the rope could be easily' diminished by reducing the useful load, but it is certain that with increasing depth of mining, more effort must be made to confine the hoisting to a small number of shafts, and increase the load hoisted per trip.

Jan 1, 1933

By F. R. Brotzen, L. D. Whitmire

Single crystals of high-purity molybdenum were de-formed at temperatures from 195°to 473°K, and the effect of deformation on the electrical resistivily was deler-mined. To separale the resislivity components of point and line defecls some cryslals were annealed at 473°K. The vale of resislivily increase wilh strain was nearly linear and was strongly dependent upon the deformation temperature. Point dejects are annealed out without any effect on the flow stress. At low temperatures the flow stress is a linear function of the square root of the resistivity increase attributable to dislocations. ELECTRICAL-resistivity measurements have been used successfully to gain information on structural changes in metallic materials. During plastic deformation the electrical resistivity rises because of electron scattering from newly created lattice defects. Such measurements lend themselves, therefore, to corroborating results from direct observation of lattice defects and, to a certain extent, to correlating defect densities and distribution with mechanical properties. Published information on research with single crystals of the bcc metals of Group VI, particularly molybdenum, is still limited. Yet, molybdenum single crystals of relatively high purity can be readily prepared by electron-beam-melting techniques. Furthermore, some valuable information on the defect structure of deformed crystals by direct observation is available. Lawley and Gaigher,1 for example, have examined dislocation configurations in deformed molybdenum crystals by means of transmission electron microscopy. Their results revealed that the dislocation density and distribution were strongly dependent upon the deformation temperature. These findings differed from those by Keh and weissmann,2 who found that the average dislocation density in polycrystalline iron deformed between 138° and 298°K depended only on the degree of strain and not on the deformation temperature. Martin3 and peiffer4 showed that point defects introduced in polycrystalline molybdenum by cold work can be eliminated by annealing at a relatively low tempera-ture. In view of their work it became apparent that resistivity measurements of suitably annealed crystals could disclose changes in their dislocation structure and contribute to the understanding of the work hardening of molybdenum crystals. EXPERIMENTAL PROCEDURE Crystals were grown by electron-beam zone melting5,6 of 0.062-in.-diam molybdenum rods (99.99 pct) supplied by General Electric Lamp and Wire Division, Dover, Ohio. The crystals, about 4 in. long, were prepared by using five zone-refining passes at a speed of about 6 mm per min in a vacuum of about 5 X l0-6 Torr. The resistivity ratio of the crystal, p(4.Z°K)/p(273°K), was generally near 10-3. These crystals were used as tensile specimens of uniform diameter in the "as-grown" condition. They were oriented for maximum shear on the (011)[111] slip system (Schmid factor >0.49). The specimens were held in spherically seated Templin-type grips so as to minimize bending. Samples were deformed on an Instron machine at a strain rate of about 5 X 10-5 sec-1 in an isopentane bath with dry ice at 195°K, in ice water at 273°K, and in a vegetable-oil thermostat at 373° and 473°K. The temperature in the latter was maintained constant within +2°K. Resistance measurements were carried out with a Kelvin double bridge. The resistance of the potential leads was kept low by using large-diameter wires outside the low-temperature bath. Many of the resistance data were checked by measurements made with an ac bridge. Current and potential leads were spot-welded to the specimens. The distance between the potential leads, about 3 in., was also considered to be the gage length for the strain measurements. Diameter and gage length of the samples were measured optically with an error of less than 2 pct. These measurements were used also to insure that the deformation had been uniform over the gage length of the specimen. Resistivity changes were then determined from the resistance measurements at 4.2°K assuming constancy of volume. In the course of a test, the crystal diameter, gage length, and resistance at 4.2°K were determined first in the initial state and subsequently for various amounts of elongation.

Jan 1, 1968

By J. C. M. Li

The steady state shape of a shrinking cylindrical grain boundary of miform boundary energy is shown to be circular. This is based on the principle of either the minimum rate of entropy production or the minimum thermokinetic potential. The circular shape corresponds also to a state of minimum (not maximum) velocity. The steady state shape of a grain boundary moving between two inclined surfaces is a circular cylindrical arc whose position and curvature will be afjected by the nature of the surfaces. The minimum thermokinetic potential is the only valid criterion in this case. THE preceding paper1 reports an interesting experiment in which it is shown that a grain boundary moving between two inclined surfaces assumes a circular cylindrical arc whose axis nearly coincides with the line of intersection of the two surfaces. The driving force is well defined since it is the energy of the grain boundary itself. The velocity of the grain boundary is found not to vary linearly with the driving force. Several interesting questions arise: 1) What principle determines the shape of a moving grain boundary? 2) What is the effect of the inclined surfaces? 3) How do we understand the nonlinear velocity-driving force relationship? It is attempted in this paper to discuss the first two questions based on irreversible thermodynamics and in a following paper to discuss the third question based on dislocation theory. STEADY STATE SHAPE OF A SHRINKING LOOP (A CYLINDRICAL GRAIN BOUNDARY) In irreversible thermodynamics, there are two criteria for the steady state. One is the minimum rate of entropy production2 which is based on the symmetry of phenomenological coefficients and is applicable to linear force-flux relations with constant coefficients. The other is the minimum thermokinetic potential3 which is based on the integrability of a certain Pfaffian differential equation and is applicable to nonlinear systems with variable coefficients. In the case of a shrinking grain boundary loop (a two dimensional version of a cylindrical grain), the flux of atoms across the grain boundary can be taken as the local boundary velocity v measured perpendicular to the boundary (the number of atoms transferred per unit area per second is equal to the product of atom density and the velocity of the boundary). The local thermodynamic driving force can be taken as y/p with y being the grain boundary energy (invariant with respect to the orientation and curvature of the grain boundary) and p being the radius of curvature. Such driving force can be understood by considering the loop as an elastic string with tension y. As shown in Fig. 1, across a length ds along the loop, the direction of y changes by an angle d@ which is ds/p. Because of this change of direction, the tension exerts a force perpendicular to the curve equal to yd@. The force per unit length is then y/p. According to the experimental observation, the velocity v is a power function of y/p, where M is the velocity at unit driving force and 'n is a constant. The rate of entropy production per ds along the loop is vyds/pT, where T is the temperature. For a given length L of the loop, the total rate of entropy production is The thermokinetic ptentia13 has only a differential definition and its existence depends on the integrability of this definition. In this case, Eq. [3] happens to be a total differential and the thermokinetic potential can be defined as which turns out to be the same as the rate of entropy production, Eq. [2], except for a constant factor n + 1. Strictly speaking, since the flux-force relation is not linear, the rate of entropy production may not be a minimum at the steady state. However, because of the proportionality between Eqs. [2] and 141, the state of minimum thermokinetic potential happens to be the same as that of minimum rate of entropy production. The steady state shape thus can be obtained by minimizing either integral [2] or [4] for a given L.

Jan 1, 1970

By J. H. Wiggins

This paper first pictures the economic phase of evaporation losses and the actual evaporative conditions in handling and storing crude and gasoline in the United States; then follows a discussion of some of the theories of physics involved in evaporation loss and lastly an application of these theories to handling oil and gas on producing properties. GRANTING that about 600,000,000 bbl. of light oil will be produced in the United States this year and taking the Bureau of Mines' statement that 7 1/2 per cent. of the total crude production will be lost before the finished gasoline is shipped from the refinery, the volumetric evaporation will be 45,000,000 bbl. of the cream of the gasoline. This is a conservative figure and is equivalent to 1,890,000,000 gal. The real value of this liquid is at least 150 per cent. of the value of an equal volume of motor fuel. At only 10 c. per gal., the value lost is $189,000,000; at 15 c. per gal. the loss is $283,000,000. If 750,000,000 bbl. of light and heavy oil are produced here this year and the average price per barrel is $1.333, the gross return to producers will be $1,000,000,000 and the net returns about $200,000,000, if the cost of production is only $1 per barrel. Thus, the evaporation bill is about 20 per cent. of the gross income and is equal to the net income of the crude-oil producers. Two other comparisons with popular phases of the petroleum industry will help give an adequate conception of the evaporation problem. These are: cost of preventing evaporation compared to cost of cracked gasoline and volume of gasoline evaporated compared to volume of gasoline manufactured from natural gas.

Jan 7, 1924

By Richard E. Chism

If internal commotion can be called life, the Mexicans have certainly lived more in the last seventy-five years than any other people. To the oppression of the Spanish viceroys succeeded the sanguinary tumults of the Revolution of Independence, after which the Supreme Congress bequeathed its heritage of uncertain power to the empire of Iturbide, the only one ever established by Americans upon American soil, with an American at its head. That shortlived reign mas followed by years of ceaseless, bloody, and, to the superficial observer, meaningless revolutions—the deeper political and ecclesiastical significance of which it is beyond the scope of this paper to discuss. Then came foreign intervention, the ill-fated Austrian's brief supremacy, and the final triumph of the patriot cause under rugged old Benito Juarez, who crowned the victory of arms by a series of reforms breaking forever the temporal power of the Church and ushering in the calmer era which has lasted from the first accession of Diaz to the present day. During all those troublous times, the revolutionary ocean, that rolled so deeply over all other relics of Spanish dominion, had left almost unaltered the ancient laws of Spain, still lifting themselves above the tide, like landmarks of a flooded world. Many of these laws were obsolete ; some were absurdly inadequate to the demands

Jan 1, 1886

CONTENTS PAGE ZAPFFE, CARL.-Manganiferous Iron Ores of the Cuyuna District, Minnesota. Discussed by A. K. Knickerbocker 1 MCCORMACK, C. P.-Economics of the Cuyuna Manganiferous Iron Ores. Dis-cussed by T. L. Joseph, J. Wilbur Van Evera, C. P. Perin, T. T. Read, L. E. Ives 4 READ, T. T.-Probable Error in Blast-furnace Records and Calculations Therefrom. Discussed by C. H. Herty, Jr., T. T. Read, T. L. Joseph, Ralph H. Sweetser 8 SCHWARTZ, H. A. and HIRD, (Mrs.) ANNA NICHOLSON.-Chemical Equilibria During Solidification and Cooling of White Cast Iron. Discussed by N. B. Pilling, Ralph H. Sweetser, H. M. Boylston, Albert Sauveur 10 HERTY, C. H., JR., BELYEA, A. R., BURKHART, E. H., and MILLER, C. C.-Some Factors Affecting the Elimination of Sulfur in the Basic Open-hearth Process. Discussed by Henry D. Hibbard, L. F. Reinartz,. C. H. Herty, Jr., Ancel St. John, A. L. Feild, C. R. Hayward, Ralph H. Sweetser, C. D. King, Haakon Styri, George A. Orrok 12 HIBBARD, HENRY D.-Finishing Melting Temperatures of Simple Ingot Steels. Discussed by Haakon Styri, George V. Luerssen, A. G. Zimermann, A. L. Feild, George A. Orrok, Albert Sauveur, R. F. Harrington, Henry D. Hibbard, I. A. Billiar, William J. Priestley, H. W. Gillett, W. P. Barba, Jerome Strauss, Harry H. Smith, H. LeChatelier, L. F. Reinartz 19 HERTY, C. H., JR., and TRUE, O. S.-The Reaction between Manganese and Iron Sulfide. Discussed by A. L. Field, H. S. Rawdon, C. H. Herty, Jr., T. L. Joseph, Haakon Styri 37 KAMURA, HEIHACHi.-Reduction of Iron Ores by Carbon Monoxide. Discussed by T. L. Joseph, R. Franchot, Ralph H. Sweetser, C. H. Herty, Jr 43 JOSEPH, T. L.-Effect of Sulfur on Blast-furnace Process. Discussed by R. Franchot, C. A. Meissner, T. L. Joseph, C. H. Herty, Jr., Ralph H. Sweetser, I. E. Waechter, F. N. Speller, T. T. Read 45 GOOSTRAY, JOB, HARRINGTON, R. F., and HOSMER, M. A.-Brief History of Metallurgical Practice in Cannon-making with Particular Reference to the Cast-iron Gun. Discussed by A. G. Zimermann, Geo. A. Orrok, Chas. Me-Knight, Jr., F. Brauer 51 Manganiferous Iron Ores of the Cuyuna District, Minnesota Discussion of the paper of CARL ZAPFFE, presented at the New York Meeting, February, 1925, and issued, as Paper No. 1390-I, with MINING AND METALLURGY, December, 1924. A. K. KNICKERBOCKER,* Virginia, Minn. (written discussion).¬The author makes a broad distinction between the "black" ores (the

Jan 6, 1925

By Frederick Laist

0. C. RALSTON, Salt Lake City, Utah.-I have merely glanced over this paper, consequently, I am hardly in a position to discuss it intelligently. There is one thing, however, that is of interest, that is, the claim that the oil mixture which they have chosen is the best adapted to the work at hand. I would like to ask Mr. Mathewson if they still feel that that is the case-if that really does give the best grade of concentration and the best extraction for the same money, compared to any particular oil mixture which they could get. E. P. MATHEWSON, Anaconda, Mont.-We are still using that mixture, and we consider it the most economical mixture used. DAVID COLE, El Paso, Texas.-I would like to ask Mr. Ralston if there are some other mixtures that would be better? E. P. MATHEWSON.-We are open to suggestions. 0. C. RALSTON.-My own paper on oils* calls attention to the fact that certain hardwood oils, especially the tars, are now being burned or wasted. A great deal of hardwood tar is available as low as 4 or 5 c. per gallon, that being its value as fuel under the boilers. As a matter of fact, a great deal of testing has been done with only the commercial products that are as a usual ride sold on the market. Very little hardwood tar is sold on the market. In asking a great many people who have tested flotation oils, I have not heard hardwood tar mentioned very often. I think I would add to that that the hardwood tars can probably be bought in quantity comparable with the sludge acid at Anaconda, and. should contain a greater proportion of the frothing constituent, and at a price fairly commensurate with what they pay for the sludge acid. E. P. MATHEWSON.-I would like to make a correction in one statement I made that there has been no change made in the mixture. This change has been made: We found that the amount of wood creosote in treating the sand from tables was extremely small, and we tried some experiments on a large scale, dropping it out and using simply the sludge acid and sulphuric acid. We found that this gave practically as good results as wood creosote. We use wood creosote in treating the slimes. We find it necessary in that operation. DAVID COLE.-I would like to ask, what is sludge acid?

Jan 10, 1916

By Sylvan Z. Beer

Aluminum phosphide was synthesized and grown in solution of excess aluminum using a modified two-temperature technique. An inversion in the density difference between ALP and molten aluminum takes place at about 1100°. Dispersed nuclei can act as sources for further crystal growth in a manner resembling ripening. Advantage was taken of this phenomenon by introducing a stirring motion into the molten liquid. This was done with a split-phase 10-kH2 rotating magnetic field produced by four horizontal coils placed symmetrically about the furnace at the level of the molten metal. The method also prevents the formation of a surface film which would impede the reaction. By this technique vastly improved yields were obtained and flat crystals 5 by 5 by 0.5 mm were grown at lower temperatures and at greater rates than heretofore. THE family of III-V intermetallic compounds has received much attention since the prediction of their semiconducting properties in the early 1950s. Of the family, A1P has perhaps the highest band gap of those compounds normally possessing the zinc-blende structure. But it has been least studied because it is difficult to handle and grow. The handling difficulties have been dealt with elsewhere and it is sufficient to say here that, by various techniques, many of the difficulties can be overcome.' The difficulties encountered in crystal growth can be related to the refractory nature of A1P and in turn to its high band gap. Because of the anticipated high melting point of the material and the accompanying high phosphorus vapor pressure, the reported work on synthesis and growth was done by epitaxial synthesis-growth via chlorine2 and iodine3 transport and from solution of excess aluminum by the two-temperature technique.4'5 The transport-grown crystals take on the dimensions of the substrate but do not grow easily in thickness. In the usual two-temperature technique as applied on the synthesis of Alp, the temperature of the molten aluminum is kept at 1000° to 1250°C while the phosphorus is maintained at 1 to 20 atm. A thin film of aluminum phosphide and oxide form immediately, impeding the reaction and affecting the yield. Attempts to grow the Alp from such solutions by the methods used to grow Gap and InP from excess gallium and indium have not been successful. As discussed in the preceding paper,5 the yield can be greatly increased

Jan 1, 1969

By P. C. Claspy, P. H. Smakula

The electro-optic coefficients of LiNbO, and KTao.,5Nboe3,O3 (KTN) have been experimentally determined at the HeNe laser wavelengths of 0.6328, 1.15, and 3.39 µ. The coefficients were calculated fronz the retardation induced by an applied electric field. The retardations were measured by observing one or move transmission maxima and minima as a function of the applied field, and by measuring the retardation directly with a Babinet-Soleil compensator. The values obtained agree quite well with those previo~lsly reported by others. Extinction ratios as high as 3000:l have been observed. Resistivities and Curie temperatures have also been measured. Light-induced optical inhornogeneities in LiNbO, repovted by others have been observed. CONSIDERABLE interest has recently been shown in the electro-optic properties of LiNb03 (Refs. 1 and 2) and KTN.3, 4 These crystals have a number of advantages over such well-known materials as KDP. These advantages include: 1) the infrared transmission of KTN and LiNb03 extends to 5 p whereas that of KDP cuts off at 1.5 p ; 2) driving voltages required for modulators using these materials are considerably lower than those required for KDP. After first discussing some theoretical considerations of the electro-optic effect, we will report the results of measurements of the dc electro-optic coefficients of these materials at wavelengths of 0.6328, 1.15, and 3.39 p. THEORY The generalized equation for the electro-optic effect can be written: Although lattice polarization is the fundamental variable, rather than the applied electric field, we follow the convention of expressing the linear electro-optic effect in terms of the applied field. For LiNbO the quadratic terms are negligible. Since KTN has a center of symmetry the rijk tensor is 0. After applying the usual symmetry considerations and index contractions,* the rijk and gijkl tensors can be expressed as follows: LiNbOaT If field directions are now chosen, the change in refractive index and the angle between the induced optic axes and the crystallographic axes can be found. The induced rotations of the principal axes of the index ellipsoid for fields in principal crystallographic directions are given in Table I. Since KTN is initially isotropic, the principal axes in the zero-field condition are parallel to the crystallographic axes. The induced retardations are given in Table 11. EXPERIMENTAL We obtained the various electro-optic coefficients by measuring the induced retardation as a function of

Jan 1, 1968

By W. S. Stahmann, F. W. Bowdish

Previously published experimental data showing that both collectable and non-collectable sulfide films may be formed on chrysocolla were analysed, and chemical mechanisms were proposed for the formation of the films. A special technique was developed by which the quantity of sulfur adsorbed was determined for samples sulfidized under different conditions of pH and soluble sulfide concentration. The data on sulfur adsorption were used together with the expression for the equilibrium constant for the proposed reaction to indicate the validity of the chemical mechanism theory. A recent paper 1 about contact angle studies on chrysocolla reported the effects of pH value and sodium sulfide concentration during sulfidization upon the character of the surfaces produced. In each experiment the surface of a specimen of chrysocolla was prepared by grinding it with fine abrasive and washing it in tap water. The specimen was then placed in the sulfidizing solution for 10 min, rinsed in tap water, treated for 15 min in a solution containing 30 mg of potassium amyl xanthate per liter, rinsed in distilled water, and tested for air adhesion in a contact angle apparatus. The results, when plotted as in Fig. 1, showed an island representing conditions giving air adherent or collectable surfaces surrounded by conditions giving non-collectable surfaces. Particular interest may be attached to the region of non-collectability to the right of and above the island in Fig. 1, and to the boundry curve separating these two regions. It is apparent that at any pH from 4.0 to 6.0, where a collectable surface may be produced, a sufficient increase in the sulfide concentration results in a non-collectable surface. Thus it appears that too much soluble sulfide has a depressing effect upon the mineral, just as it has in sulfide flotation. This paper presents some speculations regarding the chemical mechanisms by which the collectable and non-collectable sulfide films may be formed and reports on a physical-chemical study intended to support these speculations. THEORETICAL CONSIDERATIONS The experimental results presented in the previous paper were analysed in several ways in an attempt to understand better the chemical mechanisms involved. For several points on the boundary to the right of the region of contact in Fig. 1, molar concentrations of H+, OH-, HS-, and S= ions, as well as various ion concentration products, were calculated. Following the reasoning of Wark and Cox, 2,3 no single kind of ions may be credited with causing depression of the surface because none of them have a constant con-

Jan 1, 1968

By A. S. Joy

Vacuum flotation tests carried out according to the method of Schuhmann and Prakash1 have shown that the acid limiting edge of the flotation area for a Brazilian hematite, in the presence of dodecylamine, is a straight line of slope approximately unity. The flotation tests and the structure, surface ionization, and electrokinetic properties of this hematite have been fully discussed elsewhere. 2 The numbers of adsorbed H+, and OH- ions and collector molecules have been determined in the range of critical conditions defining the acid limit of the flotation area. The total amine adsorption is shown in Fig. 1 as a set of contours superimposed on the straight part of the flotation area. These were determined by spectro-photometric estimation of the complex formed between residual amine and the anionic dye Orange II.3 The ionic strength of the solutions was kept constant and at a value in sufficient excess of the amine concentration to ensure that the diffuse part of the double layer was populated predominantly by indifferent ions. Adsorption of H+ and OH- in the absence of amine was found by potentiometric acid-base titration in the presence of hematite.4 The form of the adsorption-titration curves suggested that the hematite surface behaves in an amphoteric manner, and that positively charged sites arise through loss of a hydroxyl ion, and negatively charged sites by loss of a hydrogen ion. On this basis, curves 8 and 9, shown in Fig. 2, were calculated from the titration curves. These show the variation of the numbers of positive (s +) and negative (s—) sites with pH. To distinguish between ionic and other modes of adsorption, zeta-potential determinations have also been made using the streaming potential technique. The influence of amine on the zeta-potential of the mineral over a wide pH range is shown in Fig. 3. The change in charge ?s, due to adsorption of amine ions in the Stern layer, was calculated by applying the Gouy-Chapman theory, as modified by Stem, to the results shown in Fig. 3. The validity of this treatment has been shown by Ottewill and Jaycock.5 The three full lines, Nos. (1) through (3), included in Fig. 2 show the relationship between ?s and pH at three amine concentrations. The general conclusion from the zeta-potential curves is that adsorption of amine causes a reduction in the negative charge on the surface. Comparison of the values shown in curves (1) through (3) of Fig. 2 with the - curve shows that the magnitude of the reduction is comparable with that of s - at any given

Jan 1, 1964

By E. A. H. Tays

As I promised, in a former paper on the Bryan Mill,* to give further data regarding the plates from four battery-aprons, I now submit the following: These aprons were 4.5 feet wide by 16 feet long; the first two plates of each apron were 4.5 by 4.5 feet, and the remainder of varying sizes, as can be seen by their relative weights, as shown in the table; but all were 54 inches wide. They were in use 4 years and 9 months, and about 15,265 tons of ore passed over each. The ore was quartz, carrying about the same weight in silver as in gold; showing some copper, and highly impregnated with ferric oxide. The tailings show about 0.6 per cent., and the bullion about 10 per cent., of copper. The silver was present mostly as sulphide; and the copper was also present as sulphide, with some carbonate. The ore treated ill 1898 was a fair average of the whole run; so I take it as an example from which to make a few deductions.

Jan 1, 1901

By A. A. Smith, J. S. Smart

THe elements silver, cadmium, tin, antimony and tellurium either are found as impurities in commercial coppers or are intentionally added to produce coppers for special uses. When present in small quantities, each of these metals exerts a significant effect on the properties of copper, but despite considerable experience and investigation much remains to be learned about their specific behavior. The presence of extraneous elements, particularly oxygen, complicates the study of individual additions of impurities in the range o to 0.05 per cent, and the use of high-purity copper has been found extremely helpful in circumventing these difficulties. It has also been found that individual behavior can be satisfactorilv determined from measurements of two commercially important properties, conductivity and softening temperature, according to methods that have been described previously.1,2 Data of this type, obtained in the course of a general investigation of the effects of impurities on the properties of both oxygen-bearing 2nd oxygen-free copper are presented herewith. All samples except those containing cadmium were prepared as 3/8-in. continuously cast oxygen-free rod from pure copper and weighed amounts of a similarly synthesized master alloy. Composition was checked by chemical methods, which in every case verified the calculated analyses. Test wires were cold-drawn one B, and S. number per pass on a string-up machine using four 30-min. 600°C. anneals at 0.3125, 0.257, 0.204 and 0.162 in. and a final cold reduction of 75 per cent to 0.081 in. Some oxygen-bearing samples were produced directly from the 3/8-in. oxygen-free rods by diffusion from a surface scale at 850°C. and drawn to size as listed above, but most of the alloys were remelted in pure graphite and cast through air into a I-in. round mold. The slugs were then hot-rolled to 5/16 in., drawn to 0.162 in., annealed as listed above, and drawn to 0.081 inch. Conductivity wires were annealed for I hr. at 100°C. intervals between 300' and 800°F., using a hydrogen atmosphere for oxygen-free samples and purified nitrogen for the oxygen-bearing type. All samples were quenched from the annealing temperature in 10 per cent H²S04 and conductivity was measured on a Hoopes bridge that had been checked against a Kelvin bridge. The softening temperatures represent the half-hard stage of the annealing curve as determined by a standard procedure.' Effect of Silver Numerous excellent studies of the argentiferous coppers are found in the literature, and these have been adequately

Jan 1, 1943

By A. A. Smith, J. S. Smart

THe elements silver, cadmium, tin, antimony and tellurium either are found as impurities in commercial coppers or are intentionally added to produce coppers for special uses. When present in small quantities, each of these metals exerts a significant effect on the properties of copper, but despite considerable experience and investigation much remains to be learned about their specific behavior. The presence of extraneous elements, particularly oxygen, complicates the study of individual additions of impurities in the range o to 0.05 per cent, and the use of high-purity copper has been found extremely helpful in circumventing these difficulties. It has also been found that individual behavior can be satisfactorilv determined from measurements of two commercially important properties, conductivity and softening temperature, according to methods that have been described previously.1,2 Data of this type, obtained in the course of a general investigation of the effects of impurities on the properties of both oxygen-bearing 2nd oxygen-free copper are presented herewith. All samples except those containing cadmium were prepared as 3/8-in. continuously cast oxygen-free rod from pure copper and weighed amounts of a similarly synthesized master alloy. Composition was checked by chemical methods, which in every case verified the calculated analyses. Test wires were cold-drawn one B, and S. number per pass on a string-up machine using four 30-min. 600°C. anneals at 0.3125, 0.257, 0.204 and 0.162 in. and a final cold reduction of 75 per cent to 0.081 in. Some oxygen-bearing samples were produced directly from the 3/8-in. oxygen-free rods by diffusion from a surface scale at 850°C. and drawn to size as listed above, but most of the alloys were remelted in pure graphite and cast through air into a I-in. round mold. The slugs were then hot-rolled to 5/16 in., drawn to 0.162 in., annealed as listed above, and drawn to 0.081 inch. Conductivity wires were annealed for I hr. at 100°C. intervals between 300' and 800°F., using a hydrogen atmosphere for oxygen-free samples and purified nitrogen for the oxygen-bearing type. All samples were quenched from the annealing temperature in 10 per cent H²S04 and conductivity was measured on a Hoopes bridge that had been checked against a Kelvin bridge. The softening temperatures represent the half-hard stage of the annealing curve as determined by a standard procedure.' Effect of Silver Numerous excellent studies of the argentiferous coppers are found in the literature, and these have been adequately

Jan 1, 1943

By Stanley Reichert

The manganese deposits of the Embree Iron Co., Embreeville, Tenn., are thought to be fairly typical and representative of the East Tennessee type of deposit, and so to warrent rather detailed description. The methods used by the Embree Iron Co. for prospecting and mining, and to a lesser extent for milling; should therefore be applicable to other East Tennessee manganese deposits, as yet' undeveloped. Early History and Discovery of Manganese Brown iron ore (limonite) was mined by the Embree Iron Co. at various times from 1890 to 1910. The early method was simply pick-and-shovel mining in open pits. Later hydraulic giants were used and sluice lines carried the ore down the mountain slopes to log washers.. During this phase of mining, manganese ore was discovered under the iron ore in some of the pits. In other areas oxidized zinc ore was found under the iron. It thus happened that the valuable zinc deposits were discovered in 1914. During the World War period, from 1914 to 1918, there was sporadic prospecting for manganese ore among the abandoned iron workings, but the main activity then centered around the recently discovered lead and zinc deposits. It was not until 1934 that manganese mining began in earnest, under the supervision of R. D. Pritchett, Mine Superintendent. Geology of the Manganese Deposits United States Geological Survey Folios 151 (Roan Mountain) and 118 (Greeneville show that Bumpass Cove is a synclinal structure thrust faulted along the southeast flank, but with normal sequence of strata along the northwest flank. Fig, l. shows the areal geology of Bumpass Cove as taken from the folios superposed on the U.S.G.S. -T.V.A. 1/24,000 topographic maps of the Erwin and Telford 7 ½ minute sheets. The manganese mines occur near the contact of the unfaulted Shady dolomite and the Erwin quartzite. This contact zone is deeply weathered, with overburden averaging 40 to 60 ft. thick. The material overlying' the bedrock along this normal contact is a very tough, plastic clay, termed "buckfat" or "ocher" by the miners. It is not a true ocher, however, in the sense of having commercial value. The manganese deposits occur along this "ocher" band. Fig. 1 also shows how the manganese deposits occur along the broad topographic terrace between the 2100 and 2200-ft. contour lines. This terrace lies at the foot the Erwin quartz ridge. Apparently it is the topographic is expression of the deeply weathered zone along the Shady-Erwin contact.

Jan 1, 1941

By R. A. Burmeister, G. P. Pighini, P. E. Greene

An open tube vapor phase epitaxial growth system has been used for large area (multiple substrate) growth of GaAs1-xPx on GaAs substrates. The GaCl-GaCl transport reaction is used with either a GaAs or Ga (nonsaturated) source. Selenium and tellurium have been used for donor impurities, and zinc as an acceptor. The useable substrate area in this system is approximately 20 sq cm. The uniformity of thick-ness of the epitaxial layers are typically better than ±5 pct across a given wafer. Electrical and optical measurerments indicute comparable uniformity in electrical and luminescent properties within a wufer. The application of this system to the large scale pro-duction of GaAs1-x Px for display devices, both discrete and arrays, is discussed. Typical electrical and luminescent properties of light emitting diodes fabricated front material produced by this technique are presented. THE most promising materials currently being utilized for visible injection electroluminescence are GaAs1-xPx, Ga1-xAlxAs, and Gap. All have reasonably efficient emissions in the red portion of the visible spectrum at room temperature; Gap also has an efficient green emission.' At present, GaAs1-xPx has a technological advantage over Ga1-xAlxAs and Gap for display applications, since relatively large (several sq cm) areas of GaAs1-xPx suitable for use in electroluminescent devices may be readily grown by vapor phase growth techniques. In contrast, the preparation of Gap and Ga1-xAlxAs for electroluminescent device applications generally employs solution growth techniques which are at present not well suited for the growth of large areas of uniform thickness and doping level. The capability of uniform growth over large substrate areas and the use of multiple substrates is necessary for the practical utilization of electroluminescent devices. This is particularly important when quantity production or monolithic devices are required. Furthermore, in many display applications arrays of light emitting devices are used, the individual elements of which are of a size resolvable by the unaided eye. Thus the overall dimensions of display are substantially larger than those of most semiconductor devices. It is also necessary to achieve a high degree of control over the growth parameters to attain the required degree of reproducibility of materials properties for electroluminescent devices. In the case of GaAs1-xPx it is necessary to accurately and precisely control the phosphorus content of the alloy, both on a macroscopic and microscopic scale, in addition to the parameters generally associated with epitaxial growth such as thickness and doping level. This value is critical, as it has a major effect on the performance of electroluminescent devices. This paper describes the epitaxial growth of GaAsl-xPx suitable for electroluminescent display devices using a system developed specifically for this purpose, and which contains several novel features. The results of studies of selected physical properties of the epitaxial layers are also discussed. Finally, a brief summary is given of the characteristics of display devices fabricated from GaAsl-xPx grown in this system. EXPERIMENTAL A) Reactants. A number of techniques suitable for the vapor phase epitaxial growth of GaAs1-xPx have been reported in the literature.'-' The method selected for this investigation is that in which the Ga is transported by the GaC1-GaCI3 reaction in an open tube process. The results reported here were obtained using either the combination of GaAs, AsC13, and pH3, or Ga, AsH3, pH3, and HC1 as the initial re-actants.* The ASH3 and pH3 were obtained as dilute *Several different sources of supply were used for these reactants, y~elding comparable results._____________________________________________________ mixtures in HZ; the HC1 was obtained from the reduction of AsC13 by Hz at elevated temperatures. Both selenium and tellurium were employed as donor impurities, and zinc as an acceptor impurity. Selenium was introduced in the form of H2Se, tellurium in the form of tellurium-doped GaAs, and zinc in the form of diethy1 zinc. B) Apparatus. The prinicipal difference between the apparatus used in the present study and that of Tietjen and Amick,8 in addition to size and other related design features, is that RE induction heating is utilized in place of resistance heated furnaces. Induction heating was selected for this application because it appears to have several advantages, including: 1) It is possible to keep all fused silica portions of the apparatus at temperatures well below those of the reaction zone, thus minimizing a possible source of contamination. 2) The thermal mass of an induction heated system can be made small, thus reducing the total time required for the growth process. 3) Sharp temperature profiles (desirable for high deposition efficiency) are easily achieved. 4) The volume of the system for a given substrate area can generally be made smaller than a comparable resistance heated unit. This results in shorter time

Jan 1, 1970

Jan 1, 1968