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By R. E. Ogilvie, H. C. Gatos, R. E. Hanneman

The effect of high pressure on the stability of the (any phase transformation in the Fe-V system was studied by experimental and theoretical methods. The maximum solubility limit of the y loop of the atmospheric phase diagram was found to increase by a factor of five at 40 kbars pres-sure. The solubility limits of (Y and y phases are calculated on an approximate thermodynamic basis at pressures of 20, 40, and 50 kbars as a function THE high-pressure behavior of the a =^ y transformation in iron and iron-base alloys has been the subject of considerable interest recently. For those binary or higher-order alloy systems possessing a closed y loop, the effect of pressure is to extend the region of solubility of the more dense y phase. Although quite accurate calculations have been made of the a y temperature-pressure diagram of pure iron,' only very approximate thermodynamic calculations or experimental measurements have been made of the pressure dependence of a ^ y equilibria in binary systems exhibiting a y loop.2"4 of temperature and are found in excellent agreement with experimental results. The experimental high-pressure phase diagrams were determined using binary diffusion couples diffused under simultaneous conditions of high pressure and temperature and analyzed with an electron microbeam probe. Approximate calculations of the stabilizing effect of high pressure on the o phase are qualitatively confirmed by experimental results. These previous calculations have primarily dealt with the slopes of the allotropic a (Y= y phase boundary at terminal solubility. The lack of detailed understanding or accurate experimental results of the pressure dependence of the two-phase a ^ y field has been due, in part, to the types of experimental methods previously employed. The primary purposes of the current paper are twofold: 1) to develop and make use of thermodynamic expressions with the aid of supplementary data, to approximately calculate the pressure dependence of the entire y loop and the two-phase ((Y + y) width in the Fe-V system; and 2) to accurately determine the corresponding experimental high-pressure phase diagrams. The current paper describes the powerful method used which enables the simultaneously measurement of phase equilibria and diffusion under high pressure and temperature. A second paper, part 11, will deal with the effect of high pressure on binary diffusion in the Fe-V system.

Jan 1, 1965

Jan 1, 1967

By Howard Eavenson

THE low-volatile, or smokeless, coal field of southern West Virginia is in Fayette, Raleigh, Wyoming, Mercer, Summers and McDowell counties, in the extreme southern portion of the state, and extends into the adjacent counties of Tazewell and Buchanan in Virginia. McDowell County is the largest producer, with Fayette and Raleigh counties next. The total area of the field (Fig. 1) is approximately 1600 square miles, or 1,024,000 acres. The percentage of volatile matter in the various seams ranges from 15 to 26 per cent. The upper limit of true low-volatile coal is usually considered to be 23 per cent volatile matter; above this point, the coal usually is classed as medium volatile. This limit will be used in this paper.

Jan 1, 1931

By G. S. Cole, G. F. Bolling

A series of Al-Cu alloys has been cast from constant superheat to solidify either with a hot top or with a free liquid/air interface. All the other variables which affect relative fluid motions were kept constant except the imposition of slow rotations m oscillations of the mold. Depending upon the exact circumstances, evi-dence could be found for the nucleation of equiaxed grains from dendrite bits detached from the columnar zone, or from the free surface, or from solid bits induced at pouring; a special experiment showed the solute buildup during ingot solidification and by inference the reality of constitutional supercooling. All methods of grain nucleation are thus supported. When solidification is arranged in a static mold the columnar- to-equiaxed transition occurs by one of these nucleation paths, subject to the natural decay of temperature gradients which promotes nucleation or the survival of nuclei. But when solidification is forced under special fluid flows it may display odd transitions. In one of these the equiaxed zone is synihesized from. dendrite bits detached from the solid/liquid interface. These survive under the concurrent lowering of temperature gradients and eventually cause transition by impeding columnar growth. GRAIN structure control is desired because real experience shows that specific properties are associated with specific cast grain structures. But since control is thus a matter of need and does not require understanding, much of casting remains art. For example, the manipulation of relative fluid motions in simple ingots provides a control of grain structure development,1-4 but theoretical insight is not required in order to broaden its potential applicability. Fortunately, however, once a variable like fluid flow is recognized it can also provide paths toward new insight. New observations using this variable have provided an insight which is curious. All the theories or descriptions of the columnar-to-equiaxed transition (CET) seem to be supported as long as the appropriate experiment is carried out. In order to develop this idea, let us ignore segregation, the chill zone (until a later section of this paper), and the origin and development of the columnar zone.= The details of questioning how equiaxed material forms in a casting may be divided in two. The first part is simply a questioning of the origin for equi-axed grains: are there fresh nuclei from heterogeneous nucleation, or dendrite bits broken off or melted from the columnar zone or elsewhere,6 or other solid bits surviving from the outset of freezing? The second is more complex, a questioning of the CET: does columnar growth slow down and allow the dominance of equiaxed grains, however they are formed, or do equi-axed grains take over and force columnar growth to stop? This "chicken-or-the-egg" second question can be quite useful, especially because it allows us to delineate the ordinary or NATURAL EQUIAXED ZONE and the induced or SYNTHETIC EQUIAXED ZONE. A natural equiaxed zone occurs if solidification proceeds in the absence of disturbances or extraneous forces such as ultrasonics, stirrings, and so forth. Both the CET theory proposed by Winegard and Chal-mers, 7requiring constitutional supercooling, and the CET theory suggested by Chalmers,8 requiring nuclea-tion only on pouring, pertain to the natural equiaxed zone. The best collating evidence to date for both these theories is contained in the work by Biloni and Chal-mers;9,10 the former theory7 is supported by special versions of the unidirectional growth experiment performed by Plaskett and winegardl1 and the latter theory' is supported in detail for the solidification of small ingots. An equiaxed zone can be synthesized when disturbances caused by forced fluid flows2-4 or other artificial means9,10 break off or melt off dendrite tips from an advancing solid/liquid interface,* if (and only if) temperature gradients in the melt are (forcibly) reduced enough to ensure the survival of these bits of dendrites, 2'3 Willful disturbances even so trivial as those produced by rapping a mold might be included here; as will be shown for example, this follows Southin's suggestion that the free liquid/air interface

Jan 1, 1970

CONTENTS PAGE Simons, Theodore.-Basic Principles of Gravity Concentration-A Mathematical Study : :.. 1 Taggart, Arthur F. and Gaudin, A. M.-Surface Tension and Adsorption Phenomena in Flotation 11 Hersam, Ernest A.-Factors Controlling the Capacity of Rock Crushers 12 Shaw, S. F.-The Ore Deposits of Sierra Mojada, Coahuila, Mexico 12 Wilson, Philip D.-The British Columbia Batholith and Related Ore Deposits 26 Greensfelder, N. S.-Shot-firing by Electricity 27 Mitke, Chas. A.-Metal Mine Ventilation in the Southwest 28 Foley, F. B. and Howell, S. P.-Neumann Bands as Evidence of Action of Explosives upon Metals 30 Schwartz, H. A., Payne, H. R., Gorton, A. F., and Austin, M. M.-Conditions of Stable Equilibrium in Iron-carbon Alloys 30

Jan 12, 1922

By L. E. Porter

The demand for crude oil on the Pacific Coast during the year 1945. was so acute that the California crude supply had to be augmented by tank-car imports from the Texas and Rocky Mountain fields. Crude imports reached a high of 64,800 bbl. per day during June, with a total of 14,259,000 bbl. imported during the first 11 .months. The U. S. Navy also implemented the crude output from California pools by drilling and completing approximately 300 wells in the Naval Petroleum Reserve No. 1 (Elk Hills), from which an established production of 65,000. bbl. per day was reached in late February and maintained until Aug. 17, 1945, when it was reduced to its preprogram level of 15,000 bbl. per day. Even with the conclusion of the Pacific war on V-J day (Aug. 14), the military petroleum product requirements have permitted little material reduction in output of California crude to prewar rates. During the year, a total of 327-760,000 bbl. of crude was produced, or 19 per cent of the total crude production within the United States during the same period, as compared with 310,996,000 bbl. or 18.4 per cent of the nation's crude production in 1944.

Jan 1, 1946

By Edwin M. Chance

EDWIN M. CHANCE, Wilkes-Barre, Pa. (communication to the Secretary*).-I have read with great interest Mr.. Liebermann's paper reporting dynamometer tests of mine cars and wish to express my appreciation of this investigation. The coal-mining industry needs just such precise study of the problems with which it is confronted.

Jan 10, 1916

By I. J. Hegyi, J. J. Tietjen, H. Nelson, J. I. Pankove

The fabrication of p-n junctions in GaAsl-,P, alloys by a vapor-phase gowth technique has for the first tirne resulted in room-temperature injection lasers capable of operating over a broad range of wavelengths extending into the visible region of the spectrum. The shortest wavelength achieved to date is 6750A at room tetnperature. In addition, at 78°K the threshold current density values for these lasers are generally the lo~vest reported, and the emitted radiation extends to the lozc,est wavelength ever attained (6350A). With lasers fabricated from material containing 14 pct Gap, quanticm efficiencies of 26 pct and peak power outputs of 25 zu were obtained at room temperature. ALTHOUGH room-temperature operation of GaAs injection lasers has been well-documented,&apos;-5 the operation of GaAsl-,P, (x > 0) laser diodes has been restricted to relatively low temperatures.8-&apos;0 This has been previously attributed5, 7, 10-12 partially to the difficulty of preparing single-crystalline GaAsl-& alloys having a high degree of chemical homogeneity and purity. Also, with these materials it has been difficult to prepare high-quality, abrupt p-12 junctions by diffusion techniques; and, in turn, this has made it difficult to obtain optimum electrical properties for room-temperature operationL3 in the resulting laser diodes. As a result, GaAsl-,P, laser diodes have not been efficient enough to permit operation at room temperature. For example, using diffused structures, only a few diodes were obtained which could be operated even close to room temperature (255K)." Recently, a vapor-phase growth method of preparing epitaxial deposits of GaAsl - .P, alloys has been described,14 and the high-purity and homogeneity of these materials has been previously demonstrated. Of special significance, with this technique, n- or p -type doping can be initiated or discontinued at any time and at almost any rate during the crystal growth so that the donor and the acceptor concentrations can be easily controlled to obtain desired impurity profiles. This permits high-quality, abrupt p-TZ junctions to be vapor-phase grown entirely during the crystal growth process, so that diffusion or other p-n junction fabrication processes are unnecessary. After growth, the device does not have to be heated to elevated temperatures, which avoids the possible unwanted introduction and motion of both impurities and lattice defects. Using the vapor-phase growth method cited above, over 300 room-temperature injection lasers have been prepared from GaAsl-,P, alloys having compositions in the range of 0 5 x 5 0.41. These lasers have emitted cohe~ent radiation in the spectral range of 8350 to 6350A at 78°K or from 9000 to 6750A at room temperature. The threshold current densities of the best lasers are independent of the alloy composition over the range 0 < x < 0.2 and compare favorably with values for good GaAs lasers.&apos; MATERIAL PREPARATION Multilayer, epitaxial deposits of GaAsl-,P, alloys are prepared by a vapor-growth technique described elsewhere.14 With this technique, the individual layers which comprise the multilayer structure are prepared sequentially in the deposition apparatus without interrupting the crystal growth. The epitaxial layers are deposited on GaAs substrate surfaces oriented normal to the ( 100) direction. The substrate wafers employed in this study were usually doped with tellurium to an electron concentration of approximately 2 x 10" per cu cm. To avoid strains, the first 10 to 15 p of the deposited material is uniformly graded from pure GaAs to the specific GaAsl- ,P, alloy composition of interest. The GaAsl - ,P, alloy growth is then continued to form a layer of constant composition having a thickness in the range of 25 to 75 p. Both the graded region and the layer of constant composition are doped with selenium to an electron concentration of about 2 x 10" per cu cm. The p region of the diode is then incorporated in the crystal by abruptly changing the dopant concentrations in the vapor phase to facilitate doping with zinc. This layer has a hole concentration of approximately 3 X 1019 per cu cm and typically is 50 p thick. DEVICE FABRICATION In general, the GaAs substrate and the region of graded composition are removed. Ohmic contacts are made to the n-type side by tin evaporation and to the p-type side by an electrodeless nickel deposition. This is followed by an electrodeless deposition of gold on both sides. The crystal wafer is then cleaved along (110) planes and sawed into rectangular parallelepipeds. Typical dimensions are 100 by 300 for the junction area and 100 µ for the diode height. The diodes are either soldered to a copper stud or pressure-mounted in a copper clip. RESULTS AND DISCUSSION Approximately 400 laser diodes having compositions in the range of 0.41 have been prepared by the method described above. Each laser was routinely tested at liquid-nitrogen temperature. The lasers were operated with l-psec current pulses at a repetition rate of 60 pulses per sec. The parameters of greatest practical interest are the photon energy or wavelength of the laser output and the threshold current density. Fig. 1 shows the variation of photon energy with alloy composition at 78°K. The composition was determined from the lattice constant of the material obtained by X-ray back-reflection measurements. Although there

Jan 1, 1968

The program of &apos;the Chicago meeting, which is to be held Sept. 22-26, is as follows: Monday. Morning-Registration. Afternoon-Technical Session. Evening Smoker. Tuesday. Morning and Afternoon-Excursion by boat to Gary and trip, through United States Steel Co&apos;s. plant. Evening-Technical Session. Wednesday. Morning- Technical Session. Afternoon-Technical Session. Evening-Banquet, Congress Hotel. Thursday. Morning and Afternoon-Special train to La Salle and De Pue, Ill., Inspection of Zinc Smelters, Cement Works, and Coal Mines. Trip to Starved Rock and points of historical interest. Evening-Return by train to Chicago. Friday. Morning-Optional trips. 1. East Chicago Metallurgical Plants and Oil Refineries at Whiting, Ind. 2. North Chicago and Milwaukee. 3. Local Chicago Plants. 4. Coal trip to Franklin and McCoupin Counties.

Jan 6, 1919

By W. E. Field

In the Coast Mountains approximately 110 miles north of Vancouver, the gold mine of Bralorne- Pioneer Mines Ltd. lies at an elevation of 3500 ft. The deepest or 41 level in the mine is at an elevation of 1400 ft below sea level, and the rock temperature on this level is 122.5°F. The thermal gradient is 1 "F increase in temperature for each 67.5 ft increase in depth. The mine produces between 500 and 600 tons per clay, utilizing an adit two internal shafts, and one service shaft from surface. The Queen shaft, extending from the 26 to the 41 level, IS the deepest, and most production now comes from this area. Stoping in by cut and fill using mill tailing hydraulic backfill.

Jan 12, 1963

By R. A. Meussner, C. T. Fujii

Chromium solution in wustite depresses the oxygen activity in a nonideal manner and expands the lattice slightly. Gravimetric measurements of the equilibrium compositions of wustite containing 0.00 to 1.38 wt pct Cr define the oxygen potential (CO2-CO atm) and the limits of the phase field at 1000°C. These data extrapolate to a maximum solubility of 2 wt pct Cr. The lattice parameter data, room-temperature measurements of quenched samples, differ significantly from those in the literature. Both pure and chromium wus-tites contract at uniform and equal rates as the oxygen content (metal deficit) increases. The a. US metal deficit relationships are straight lines showing none of the curvature previously reported. At constant metal deficit, the a. expands by 0.002? on alloying with 0.4 to 0.5 wt pct Cr but is insensitive to further chromium additions: a small expansion rather than a marked contraction. These results require a modification of the accepted alloying mechanism. IN the high-temperature oxidation of Fe-Cr alloys in Ha-H,and CO2-CO atmospheres the vapor transfer of oxygen from the continuous wustite outer scale to the porous inner scale/alloy interface sustains the high oxidation rates.1"3 The driving force for this transport is the difference in the oxygen activity of the outer wustite and that at the inner scale/alloy interface. In pure CO2, as well as in CO2-CO atmospheres, carburization of the alloy accompanies this oxidation. Current efforts to evaluate the parameters controlling this carburization have shown that the process is not simple; i.e., the carbon concentration in the alloy initially increases rapidly, reaches a maximum, and then decreases slowly as the oxidation time is extended. This is the same pattern reported by McCoy for the more complex oxidation-carburization of stainless steels and an Fe-Cr alloy in CO2 at lower temperatures.4 These changes in the carburization process occur while the overall oxidation rate and the lattice parameters of the scale layers remain constant. If this invariance of the lattice parameter is assumed to indicate a constant scale composition and thus a constant oxygen potential, the carburization results are not easily explained. Electron microprobe traces across the thickness of these outer scales, however, have revealed distinct chromium gradients penetrating 10 to 50 µ from the inner surface where the chromium concentrations were estimated at a few tenths percent. The variation of the chromium cmcentration on the inner surface of the scale, and the resulting change of the oxygen activity, during the oxidation process is considered to be important in defining the carburization process. Thus, to gain an understanding of the complex oxidation-carburization proc- ess, it was necessary to measure the properties of wustite containing known amounts of chromium (chromium wustite). Although the general features of the Fe-Cr-0 equilibrium diagram between 900° and 1300°C have been fairly well established by Richards and white: Wood-house and White,6 Seybolt,7 and Katsura and Muan,8 there have been no detailed studies of the limits of the chromium wustite phase field or the properties of these alloyed wustites. The recent results of a limited study of chromium wustite by Levin and wagner9 indicate that more than 0.67 wt pct Cr is soluble in wustite above 850°C and that this alloying is accompanied by a substantial lattice contraction. This change in the lattice parameter was not evident in the X-ray diffraction patterns of wustite layers from the oxidation experiments;1,3 the lines were sharp even though a chromium gradient existed in the scale. The present paper describes gravimetric equilibrium experiments which delineate the boundaries of the chromium wustite single-phase field at 1000°C and define the changes in the oxygen activity and the lattice parameter of wustite as functions of chromium and oxygen contents. The lattice parameter data of chromium wustite obtained from these equilibrium and special quenching experiments differ considerably from those reported.9 Those for pure wustite show significant differences from the widely accepted data of Jette and Foote.10 Since the causes of these differences are not easily assignable, and since the literature contains many sets of data on wustite which if not in conflict are at best not in harmony, the experimental procedures are discussed in the present paper. EXPERIMENTAL Oxide Preparation. The specimens used in these studies were porous pellets compacted from high-purity (Fe,Cr)2O3 or Fe2O3 powders. These powders were prepared from electrolytic chromium (99.8 pct purity) and electrolytic iron purified by consumable-electrode, vacuum arc-melting processing (299.9 pct purity).11 The oxides were produced by standard analytical procedures: solution of the metals in acids (HC1, then HNO3 added), coprecipitation of the hydroxides (NHaOH), and filtering and washing these precipitates. Initial dehydration of the coprecipitated hydroxides was done in a porcelain evaporating dish heated by a Meker-type burner, final dehydration by firing in a recrystallized alumina crucible at 1000" to 1050°C for 20 hr in an electrically heated furnace. Spectrographic analysis detected the following impurities: silicon, 0.01 pct or less; aluminum, 0.001 pct to trace; manganese and copper, 0.0001 pct to none. Each of these levels is at least one order of magnitude lower than in commercially available CP grade ferric and chromic oxides. Fluorescence analy-

Jan 1, 1969

By T. M. Morris

G. L. Simard and D. J. Salley—The authors and ourselves" independently came to similar conclusions both as to the value of tracer methods for the study of flotation and the general nature of collector-mineral interaction. The dodecylamine-quartz system appears to be simpler than the dithiophosphate-galena one, and the results therefore appear clearer. It is evident from a comparison of the two papers, however, that care must be used in extending the results to other more complicated systems. In the case of dodecylamine-quartz, the possible influence of micelle formation is of interest. There is no a priori reason why complete monolayer formation should necessarily occur at the concentration for micelle formation, since sorption depends on the nature of the substrate as well as on the properties of the solute in solution which alone determine micelle formation. Indeed, the fact that the onset of increased adsorption, point B in fig. 2, occurs at a concentration one tenth the critical value for micelles might imply that micelle formation does not have an influence. Interestingly enough, the data may be handled by the methods used for multilayer adsorption of gases on surfaces. Thus, if the amount adsorbed is plotted versus concentration, a sigmoid type curve is obtained, similar in form to a so-called Type I1 isotherm13 generally attributed to multimolecular adsorption. A monolayer value of about 0.12 mg per g may be estimated from the knee of this isotherm. On the other hand, if a plot is made according to the multilayer gas equation for adsorption to an unrestricted number of layers, eq 38,13 assuming the critical micelle concentration as the saturation concentration, the data above 120 mg per liter fall on a straight line from which a monolayer adsorption of 0.3 mg per g results. These considerations suggest that the monolayer may occupy an area somewhat less than the geometric value of 0.4 mg per g, and that micelle formation may indeed be a factor in the adsorption. the angle between the solid-liquid and liquid-gas interfaces, measured through the liquid. The value of the equilibrium contact-angle is uniquely determined by the value of the interfacial energies of the three intersecting interfaces and is independent of other forces in the system. When the liquid-gas interface intersects the solid at an edge—as was the case for all the experiments reported in this paper—the orientation of the solid-liquid interface is indeterminate or varies through 90" for a right-angle edge. Mr. Morris has called the angle between the horizontal and the liquid-gas interface for this edge condition a "static contact-angle." I feel that this term is unnecessarily misleading. In the first place, "static contact-angle" sounds too much like "equilibrium contact-angle." In the second place, the magnitude of the "static contact-angle," which I would prefer to call the "supporting angle," is determined by the forces in the system other than those derived from the interfacial energies, hence "contact angle" is misleading. If Mr. Morris had said that the "supporting-angle" is variable and depends on the weight of the particle and size of the bubble and that it has a maximum possible value equal to the equilibrium contact-angle, his discussion would have been more accurate. T. M. Morris (author&apos;s reply)—Mr. Kellogg puts forth a reasonable criticism of some of the terminology used in the paper. I agree that the term "static contact angle" may be misleading. Substitution of the term "supporting angle" or "vector angle" may be more suitable. F. X. Tartaron—In this paper the author presents a very interesting mathematical development of the forces present when a mineral particle adheres to an air bubble. Excellent concordance is obtained between mathematical formulation and experimental results. It is the writer&apos;s understanding that when the mineral surface presented to an air bubble is greater than the area of contact, the maximum contact angle is obtained. However, this contact angle represents distortion of the bubble, the normal shape of which is spherical or in cross-section, circular. This distortion produces a force that acts in opposition to the force of adhesion between the bubble and particle. Hence, at maximum contact angle, the force of adhesion between bubble and particle is at a minimum for static conditions. However, when the size of bubble is increased, the size of particle remaining the same (and all other conditions remaining the same), the contact angle decreases, the distortion of the bubble decreases and the force in opposition to adherence of bubble and particle also decreases. Thus, there is stronger attachment between bubble and particle. When this situation is applied to actual flotation conditions, it is doubtful that it has any significance. The reason is that the bubbles are normally so much larger than the particles, that in substantially all cases, it is probable that negligible distortion of the bubble takes place. In table IV, the author makes computations for bubbles from 0.50 to 2 mm diam. This is from 0.02 in. to 0.08 in. Certainly the bubbles generated in a flotation machine are far larger than this. The surfaces of the author&apos;s bubbles range from 0.79 to 12.6 sq mm. The area of contact of the glass rod (0.15 mm diam) is 0.017 sq mm. Thus, ratio of bubble surface to mineral area of contact ranges from 47 to 741 in round numbers. If we take a %-in. diam bubble and a 65-mesh (0.208 mm) particle of cubical shape, the ratio of bubble surface to mineral area of contact is 2931. Mineral particles do not readily become attached to air bubbles. Taggart has shown that in pneumatic flotation machines collector-coated particles are only temporarily attached to bubbles. They keep falling off and down in the froth but at a delayed rate as compared with gangue. Spedden and Hannan&apos;s motion pictures confirm the difficulty of attaching particles to air bubbles. In the agitation froth process, according to Taggart, air is precipitated from the water selectively on to the collector-coated particles and these

Jan 1, 1951

By T. M. Morris

G. L. Simard and D. J. Salley—The authors and ourselves" independently came to similar conclusions both as to the value of tracer methods for the study of flotation and the general nature of collector-mineral interaction. The dodecylamine-quartz system appears to be simpler than the dithiophosphate-galena one, and the results therefore appear clearer. It is evident from a comparison of the two papers, however, that care must be used in extending the results to other more complicated systems. In the case of dodecylamine-quartz, the possible influence of micelle formation is of interest. There is no a priori reason why complete monolayer formation should necessarily occur at the concentration for micelle formation, since sorption depends on the nature of the substrate as well as on the properties of the solute in solution which alone determine micelle formation. Indeed, the fact that the onset of increased adsorption, point B in fig. 2, occurs at a concentration one tenth the critical value for micelles might imply that micelle formation does not have an influence. Interestingly enough, the data may be handled by the methods used for multilayer adsorption of gases on surfaces. Thus, if the amount adsorbed is plotted versus concentration, a sigmoid type curve is obtained, similar in form to a so-called Type I1 isotherm13 generally attributed to multimolecular adsorption. A monolayer value of about 0.12 mg per g may be estimated from the knee of this isotherm. On the other hand, if a plot is made according to the multilayer gas equation for adsorption to an unrestricted number of layers, eq 38,13 assuming the critical micelle concentration as the saturation concentration, the data above 120 mg per liter fall on a straight line from which a monolayer adsorption of 0.3 mg per g results. These considerations suggest that the monolayer may occupy an area somewhat less than the geometric value of 0.4 mg per g, and that micelle formation may indeed be a factor in the adsorption. the angle between the solid-liquid and liquid-gas interfaces, measured through the liquid. The value of the equilibrium contact-angle is uniquely determined by the value of the interfacial energies of the three intersecting interfaces and is independent of other forces in the system. When the liquid-gas interface intersects the solid at an edge—as was the case for all the experiments reported in this paper—the orientation of the solid-liquid interface is indeterminate or varies through 90" for a right-angle edge. Mr. Morris has called the angle between the horizontal and the liquid-gas interface for this edge condition a "static contact-angle." I feel that this term is unnecessarily misleading. In the first place, "static contact-angle" sounds too much like "equilibrium contact-angle." In the second place, the magnitude of the "static contact-angle," which I would prefer to call the "supporting angle," is determined by the forces in the system other than those derived from the interfacial energies, hence "contact angle" is misleading. If Mr. Morris had said that the "supporting-angle" is variable and depends on the weight of the particle and size of the bubble and that it has a maximum possible value equal to the equilibrium contact-angle, his discussion would have been more accurate. T. M. Morris (author&apos;s reply)—Mr. Kellogg puts forth a reasonable criticism of some of the terminology used in the paper. I agree that the term "static contact angle" may be misleading. Substitution of the term "supporting angle" or "vector angle" may be more suitable. F. X. Tartaron—In this paper the author presents a very interesting mathematical development of the forces present when a mineral particle adheres to an air bubble. Excellent concordance is obtained between mathematical formulation and experimental results. It is the writer&apos;s understanding that when the mineral surface presented to an air bubble is greater than the area of contact, the maximum contact angle is obtained. However, this contact angle represents distortion of the bubble, the normal shape of which is spherical or in cross-section, circular. This distortion produces a force that acts in opposition to the force of adhesion between the bubble and particle. Hence, at maximum contact angle, the force of adhesion between bubble and particle is at a minimum for static conditions. However, when the size of bubble is increased, the size of particle remaining the same (and all other conditions remaining the same), the contact angle decreases, the distortion of the bubble decreases and the force in opposition to adherence of bubble and particle also decreases. Thus, there is stronger attachment between bubble and particle. When this situation is applied to actual flotation conditions, it is doubtful that it has any significance. The reason is that the bubbles are normally so much larger than the particles, that in substantially all cases, it is probable that negligible distortion of the bubble takes place. In table IV, the author makes computations for bubbles from 0.50 to 2 mm diam. This is from 0.02 in. to 0.08 in. Certainly the bubbles generated in a flotation machine are far larger than this. The surfaces of the author&apos;s bubbles range from 0.79 to 12.6 sq mm. The area of contact of the glass rod (0.15 mm diam) is 0.017 sq mm. Thus, ratio of bubble surface to mineral area of contact ranges from 47 to 741 in round numbers. If we take a %-in. diam bubble and a 65-mesh (0.208 mm) particle of cubical shape, the ratio of bubble surface to mineral area of contact is 2931. Mineral particles do not readily become attached to air bubbles. Taggart has shown that in pneumatic flotation machines collector-coated particles are only temporarily attached to bubbles. They keep falling off and down in the froth but at a delayed rate as compared with gangue. Spedden and Hannan&apos;s motion pictures confirm the difficulty of attaching particles to air bubbles. In the agitation froth process, according to Taggart, air is precipitated from the water selectively on to the collector-coated particles and these

Jan 1, 1951

Frank Clemes Smith, Deadwood, 8. D. (communication to the Secretary): The reading of Mr. Chance&apos;s interesting paper suggests a few ideas relative to his discussion of certain Black Hills gold-ores. Mr. Chance refers to his examination, in 1897, of " the (Carboniferous) limestone plateau-country which encircles the central area of the Black Hills," and says that " it had been generally assumed that the mineralization of this formation was confined to the northern area;" further, that he "found, however, a general mineralization, extending in zones or belts throughout the region," and that the ores, being more or less specially

Jan 1, 1900

By R. F. Yap, N. Arbiter, C. C. Harris

A fully-instrumented driving mechanism has been constructed to study the power, aerating and solid suspension characteristics of several laboratory flotation machines. Machines operating over normal flotation speed ranges give substantially constant power numbers in liquid systems indicating that they operate close to fully baffled turbulent flow conditions. Owing to lack of geometrical scaling, power numbers for different sizes of cells of the same make are different. Even larger differences occur between cells of different manufacturers. For a given impeller, varying the tank size did not significantly affect the power consumption. Tank geometry and baffling has a slight effect on power consumption with shrouded impellers. For a given impeller speed, suspension height decreases while power increases with increasing mass of solids in suspension. While power consumption is hardly affected by particle size and clearance between the impeller and tank bottom, the suspension height significantly increases as clearance increases and as particle size decreases. Aeration was found to affect not only power but also the suspension characteristics of the machine. For closely sized particles, drastic sedimentation occurred when a critical value of the air flow number was exceeded. The critical air flow number decreased with increasing particle size. This effect was less marked with a wide particle size range. The self-aerating capacity of flotation machines increases with cell size at a given speed for the same impeller-shroud system, but decreases in the presence of frother and solids. Equations have been established for correlating all of the studied variables. Data taken from the literature were also correlated with these equations. The modern mechanical flotation machine has, over a period of 60 years, displaced other designs to become the dominant type. Once the correct chemical environmental conditions have been established, the major requirement, selective mineral-air adherence, is essentially a function of two operating variables — impeller speed and air rate. The special nature of this dependence is such that in the same apparatus, but under different operating conditions, adherence can be either prevented or destroyed. Another aspect of this observation is that flotation machines though differing in detail to a considerable extent can produce similar metallurgical results. It must be concluded that having determined the correct reagent levels, establishing the correct operating conditions are at least as important as machine design. Since about 1960, after 30 years of fairly stable circumstances, manufacturers have been developing new types of machines whose major feature is emphasis on pulp flow characteristics by virtue of new im-peller-stator designs. As far as can be ascertained, these new designs necessitate radical departures from accepted impeller speed-air rate values. Performance data are still awaited. Flotation machine development has been empirical, as is selection of operating conditions. The purpose of the work at Columbia University has been to elucidate the fundamentals of the subject so that the purely mechanical aspects of the flotation process can be understood in hydrodynamic terms.1-6 Hopefully, this might lead to intelligent selection of a particular machine and its operating conditions for a specific ore based on a minimum of testing, or even to new types of flotation machines. The present investigation is the most comprehensive to date.7,8 Earlier work, which was largely exploratory, has been repeated and extended and employes the most accurate measuring techniques available. Additionally, sufficient hydrodynamic data were obtained under flotation conditions to delineate the relevant operating ranges. Attention has been given to scaling in that several geometrically scaled tanks and impellers have been constructed and tested; it has been pointed out elsewhere that undistorted geometrical scaling rarely pertains in flotation machine design.5 This paper is divided into sections dealing with relevant combinations of the three phases: liquid, air and solid. Summaries of the literature have been given in previous publications2-4 and will not be repeated here. Recently, several reviews of mixing have appeared, which can be usefully referenced.9-11 It is of interest to note that flotation is not included

Jan 1, 1970

By Arnold S. Epstein

Tlze green electroluminescence occurring at liquid-nitvogen temperature in epitaxial gallium phosphide diodes is exarnined using the donor dopants silicon and sulfur. Zinc is used as the p-type diffusant. Two tt~ain peaks are found, namely til 0.56 and 0.535 p. The intensity of the gYeen peak occurring at 0.56 is found to oary as -4"&apos; wlzere Jf is the forward current density and to first order appears to be dependent on the concet~tvation of ionized donovs. Tile vadintive lifetinze fov this process is -10-&apos;sec. The intensity of the 0.56-p lu~ninescence is nt least several ovdevs of magnitude greate,, at liquid-nitvogen temperature than that noted jor the 0.538 radiation for current densities up to about 35 amp per sq cm. The variation oj- the intensity of. the 0.538-p peak with current density caries according to the donor dopant. With sulfur as the donor one has a J12 dependence, whereas when silicon is the donov a J1.5 dependence is noted. Tl~e above can be fitted to a In molecular process (in first order) such as a band to band recombination. The constant B fir band to band vecombination) is found from our experitt~etlt to be of the order of 2 CZI cm per sec, zcl~ereas for tlze impurity vecombination peak (0.56 p]) tile A cotzstor~t is of the order of. 7 x 10-&apos; cu cm per sec. The structuve o/. the diodes at liquid-nitvog-en tett~peruture is oj tlze double injection type, and by carefi~lly selecting. the thickness of the structure one can regulate the onset of the 0.538-p radiation. The diode clzavaclevistics follow an I-Vx laiv where x is >1. Llregatiue resistance in these structures con be correlated with saturation of tlze 0.56- peak. ThE development of high-purity, large single crystals of epitaxially grown gallium phosphide is the ultimate aim of the studies to be reported. While a number of papers and reviews&apos; have been presented on properties of gallium phosphide grown from gallium solution and from the melt, less attention has been paid to the properties of epitaxial gallium phosphide grown from the vapor. In the studies to be reported we have examined the effects of shallow donor impurities, primarily silicon and sulfur, at liquid-nitrogen temperature, on both the electrical and green electroluminescent properties of carefully characterized single-crystal epitaxial Gap. I) EXPERIMENTAL PROCEDURES A) Material Preparation and Properties. The samules used in this investigation were single-crystal n-type epitaxial gallium phosphide. he single crystals were synthesized from the elements by vapor transport and epitaxial deposition on single-crystal gallium arsenide substrates. Typical transport agents used were chlorides. The growth procedures are described in more detail in Ref. 2. The samples were grown in the (111) orientation and had thicknesses up to 480 . Following the growth, the GaAs substrate was removed from the epitaxial Gap by etching in nitric acid. The Hall effect and resistivity of these n-type samples were measured as a function of temperature and analyzed for impurity content and compared with spectroscopic emission analysis. The results are given in greater detail in Ref. 3 but a summary is noted in Table I. In Table I, AED denotes the donor ionization energy, Nd is the donor impurity concentration, lvA is the acceptor impurity concentration, NI is the total impurity concentration, Rip vs temperature is the measured Hall mobility-temperature relationship from liquid nitrogen to about 400"K, n(77"K) is the measured carrier concentration at liquid nitrogen, and R/p(77&apos;~) is the measured Hall mobility at liquid nitrogen. Good agreement is noted between electrical and emission analysis for the major donor impurity, silicon, in the two materials where it is a major constituent. In the case of the two samples SC90-6 and AP138-3(111) B which were sulfur-doped the ionization energy found from the electrical data is in good agreement with that reported for sulfur.4 The acceptor impurities are not known, although from the presence of magnesium in the samples as indicated by emission analysis and its known role as an acceptor in GaP,4 magnesium could be present as an acceptor. Similarly, since silicon is known to be an amphoteric impurity4 it may also be present as an acceptor in the Gap.* The *A small band has been noted at 0.625 11 in samples SC90-6, SC76-4, and SC77-4, suggesting according to Ref. 5 that sillcon could be present as an acceptor In these samples since these authors have found this peak to represent a donor-silicon emission. presence of calcium deduced from emission analysis is not correlatable with the electrical analysis and its presence as an electrically active impurity should be questioned. B) Sample Preparation and Diode Fabrication. The original slices were of the order of 2 sq cm in area witi the (111)B face up. The material was cleaved and sectioned and the best pieces selected (i.e., those which visually appeared to have the least strain and defects). The samples were polished, lightly etched, and cleaned in trichloroethylene. Zinc was diffused in a closed tube at 800°C to form a p-n junction. Diodes were made from these samples. The depth of junction varied, but did not exceed 10 p depth. The back side of the slice was lapped back and a low-resistance n-type contact was formed (at 600°C in forming gas) to an Au-Mo tab with a hole in the middle for

Jan 1, 1968

By D. E. Wolfson, D. A. Reynolds, F. W. Smith

IN 1948 the U. S. Bureau of Mines began a three-phase program to evaluate the extent and quality of U. S. coking coal: 1) a factual appraisal of known recoverable reserves in beds of mineable thickness, 2) a study of preparation characteristics, and 3) a study of carbonization properties. A previous paper presented the methods used in assessing reserves.&apos; Although this investigation is only partly completed, data on coking properties of the Pittsburgh district coals are now available. The results are presented in this article. When coals are selected for manufacture of metallurgical coke more factors must be considered than for any other major use, as no basic industry requires coal of such high quality and uniformity. This is particularly true in the Pittsburgh district, where blast furnace practice is based on use of cokes from high quality coals. Although it is true that inferior coals are carbonized in other industrial areas, both here and abroad, the Pittsburgh coals are the best economically obtainable in the required tonnages, even though they are not the most desirable for metallurgical use. In the general evaluation of suitability of coals for coke making, particular attention is given to: 1) reserve, 2) ash and sulfur content, 3) inherent properties of forming strong, well fused coke, 4) expanding characteristics, and 5) blending properties. Items 1 and 2 are covered in detail in the first two phases of the survey, and coking behavior is considered in items 3 through 5. Problems is Coal Evaluation: Although not all coal beds of immediate or potential use to the coking industry in the Pittsburgh area have been tested for their coking properties, enough tests have been made to permit certain generalized statements. Virtually all the coals that will be used in this district are from the Appalachian region, and except for high oxygen coals from outcrops or stripping operations, they are coking coals. Hence the evaluation problem is not so much that of distinguishing between coking and noncoking coals as attempting to measure quantitatively differences in the coking and expanding properties of the better coking coals. Quantitative differentiation between good coking coals, is complex, since differences in their coking abilities are frequently of about the same magnitude as the precision of the test. Small-scale tests are generally unsuitable for measuring these slight differences, and there has been gradual acceptance of pilot-scale tests. Test Methods Employed: All the data reported here were obtained in two units known as the Bureau of Mines-American Gas Association (BM-AGA) carbonization apparatus and the sole-heated expansion oven. The BM-AGA unit, which consists essentially of a cylindrical steel retort about 18 in. diam and 26 in. high, carbonizes enough coal (180 lb) to allow evaluation of the coke by standard methods of the American Society for Testing Materials. The BM-AGA carbonization procedure and methods of testing the gas, liquid, and solid products have been described.&apos; Expanding characteristics of the coals were determined in the sole-heated expansion oven," wherein the coal charge, heated from the bottom only, is carbonized under a constant applied force and the linear expansion or contraction is measured. Although results in this oven have never been quantitatively correlated with the expansion behavior of coals in conventional slot ovens, they are useful in assessing expansion behavior. In this report discussion will be confined to results obtained from these pilot-scale units, although the following data are available for most coals: proximate and ultimate analyses, free swelling index, agglutinating value, and plasticity. Sources of Coals Tested: In selection of coals for coke manufacture, economic considerations are as important as quality, and each coke plant balances these two factors to meet requirements of the most satisfactory coke at lowest price. Although these economic factors may in some instances outbalance small differences in coke quality, they are usually specific to each coke plant and cannot be given in any general statement. Recognizing that coal and plant operating costs are beyond the scope of the survey, the USBM evaluates the coking quality of various coals without regard to their competitive economic status. For the purpose of this article, coals of interest to the Pittsburgh district are arbitrarily defined as

Jan 1, 1958

By William B. Plank

FOR the third consecutive year, I have collected the data on enrolment and employment of graduates from the schools in. the United States and Canada that grant degrees in mineral technology. The data were collected in the same way as formerly; namely, by questionnaire, dated Jan. 5, 1935, and are therefore comparable with the figures reported for former years. This year, along with the names of the 48 schools in the United States and the six in Canada, are listed the courses offered and the degrees granted by each, school, together with the names of the professors in charge. The names and addresses of the four schools in Mexico are also given. The list is on pages 450-1, which should he valued as a directory by those interested in mineral technology education. So far as is known, this is the most complete and up-to-date list that has ever been published.

Jan 1, 1935

By B. S. Butler

PART I SUMMARY CERTAIN relations between the formation of ore deposits and other geological processes are pretty generally accepted, namely: that many ore deposits are closely associated with igneous activity; that ore deposits accompany certain types of intrusive bodies, notably batholiths and stocks, and that they are concentrated near the tops of such bodies; that igneous activity occurs in belts of strong folding and faulting; that folding and faulting are greatest in basins of extensive sedimentation and least in areas of erosion or slight sedimentation; that areas of erosion or slight sedimentation and of heavy sedimentation persist over long periods and exert a major control over structure, igneous activity, and ore deposition; that cycles of erosion, deposition, folding and faulting, igneous activity, and ore deposition, have been repeated through geologic time resulting in rather definite periods in which metal deposits have formed. In short, ore deposition is but one phase of a series of closely related geological events. It is attempted in this chapter to point out the relations of these interreacting geologic processes to the distribution of ore deposits in the western United States. Three great periods of mineralization are recognized; pre-Cambrian, post-Jurassic, and late Cretaceous-Tertiary. In distribution the deposits of the three periods, with certain exceptions, show a concentration about two large positive areas, the Colorado plateau and the Columbia plateau, which suggests a causal relation. The most general age divisions of the rocks of the Cordilleran region of the United States are (1) pre-Cambrian, and (2) Cambrian and later rocks. The pre-Cambrian rocks are exposed mainly through the Rocky Mountain belt from the Canadian boundary southward to Arizona and westward through Arizona to southern California. They have commonly

Jan 1, 1933

Meeting, June 26, 1913).-On the petition of 29 members residing in and near San Francisco, Cal., the San Francisco Local Section was established. The territory of the St. Louis Local Section was established to include the following States and parts thereof: All the State of Missouri ; That part of the State of Illinois south of and including the city of Urbana ; That part of the State of Indiana south of and including the city of Indianapolis ; That. part of the State of Kentucky west of and including the city of Frankfort ; That part Of the State of Tennessee west of and including the city of Nashville That part of the State of Arkansas north of and including the city of Little Rock.

Jan 7, 1913