Search Documents

By Carl R. Christiansen, James J. Scott

Advance mine planning, coupled with good mining practice, can be employed to develop underground space in stone mines for future industrial usage. To assure the developer the maximum return on his investment, initial planning should consider all aspects of the commercial operation, including surface layout, mining, and underground industrialization. The modular concept of mining to compartmentalize the space offers several advantages over conventional methods. Some expenditures can be considered as mining costs with a reduction of profit from stone production while lowering the capital requirements for conversion for usable space.

Jan 1, 1977

By Alwyn Birchmore Cox, Ian William Wark

In defending the chemical theory of flotation, Taggart, del Giudice and Ziehl have criticized1 the views of those who prefer to attribute the effects of certain flotation agents to adsorption. Perhaps with some justification, they describe the latter term as the "haven of refuge of writers lost in a morass of shaky experiment and muddy thinking." We prefer to regard it, however, as a haven of refuge for writers who seek a conventional term to describe the formation of films of flotation reagents on solid surfaces, because in many cases it is not yet possible to specify the forces that hold them there. Originally, as Taggart and his associates state, adsorption connoted a concentration difference and nothing more. In recent years, workers in the field of surface chemistry have tacitly added other meanings, and they now speak of orientated adsorption of unimolecular films on a solid sub-strate, of chemi-adsorption, and of exchange adsorption. Thus the term adsorption may connote simply the Gibbs layer of excess concentration at the surface of a solution, or a unimolecular film at the surface of a solid. Perhaps this has led to the misunderstanding of Taggart, del Giudice and Ziehl concerning the relationship between surface tension and adsorption at solid surfaces. The change in "surface tension" accompanying adsorption at a liquid surface can be used as a measure of the adsorption, and the Gibbs equation as quoted by these authors correlates these two conceptions. But, to correlate two conceptions docs not necessarily imply an attempt to explain either, although sometimes such an "explanation" is carelessly inferred. Use of "surface energy per unit area" instead of the numerically equal but more difficult and less definite conception of "surface tension per unit length " would lessen many of the present difficulties. (Compare with Adam.2) At interfaces involving a solid phase, neither '" surface tension " nor " interfacial tension "can have any meaning, but the conception "interfacial energy per unit area" call be understood by anyone who is familiar with the concept of free energy. While it is true that surface energy cannot be directly measured at a solid surface,

Jan 1, 1939

By Ian William Wark, Alwyn Birchmore Cox

In defending the chemical theory of flotation, Taggart, del Giudice and Ziehl have criticized1 the views of those who prefer to attribute the effects of certain flotation agents to adsorption. Perhaps with some justification, they describe the latter term as the "haven of refuge of writers lost in a morass of shaky experiment and muddy thinking." We prefer to regard it, however, as a haven of refuge for writers who seek a conventional term to describe the formation of films of flotation reagents on solid surfaces, because in many cases it is not yet possible to specify the forces that hold them there. Originally, as Taggart and his associates state, adsorption connoted a concentration difference and nothing more. In recent years, workers in the field of surface chemistry have tacitly added other meanings, and they now speak of orientated adsorption of unimolecular films on a solid sub-strate, of chemi-adsorption, and of exchange adsorption. Thus the term adsorption may connote simply the Gibbs layer of excess concentration at the surface of a solution, or a unimolecular film at the surface of a solid. Perhaps this has led to the misunderstanding of Taggart, del Giudice and Ziehl concerning the relationship between surface tension and adsorption at solid surfaces. The change in "surface tension" accompanying adsorption at a liquid surface can be used as a measure of the adsorption, and the Gibbs equation as quoted by these authors correlates these two conceptions. But, to correlate two conceptions docs not necessarily imply an attempt to explain either, although sometimes such an "explanation" is carelessly inferred. Use of "surface energy per unit area" instead of the numerically equal but more difficult and less definite conception of "surface tension per unit length " would lessen many of the present difficulties. (Compare with Adam.2) At interfaces involving a solid phase, neither '" surface tension " nor " interfacial tension "can have any meaning, but the conception "interfacial energy per unit area" call be understood by anyone who is familiar with the concept of free energy. While it is true that surface energy cannot be directly measured at a solid surface,

Jan 1, 1939

By R. W. Diamond

THREE mills are now operated by the Consolidated Mining & Smelting Co. of Canada, Ltd.: (1) The Sullivan Concentrator, Chapman Camp, B. C. (near Kimberley, B. C.), (2) the, St. Eugene Concentrator, Moyie, B. C., and (3) the. Tadanac (Customs) Concentrator,Trail, B. C. Differential flotation is the only concentration method employed in all three plants. Tables are used for pilot work only. Values in all ores treated are as minerals of some or all of the metals -lead, zinc, gold or silver. Occasional customs ores contain small amounts of copper. Sulfide iron content of ores treated varies from a FIG. 1.-THE SULLIVAN CONCENTRATOR, CHAPMAN CAMP, B. C. (NEAR KIMBERLEY, B. C.). low figure in some ores to 38 per cent. iron in Sullivan ore. Gangue minerals vary considerably. A few customs ores are somewhat oxidized and as a result present difficulties. Flotation equipment and control are similar in the three mills, and the flow sheets at the St. Eugene and Tadanac mills, while much simpler, are modeled after that of the Sullivan Concentrator. In this paper I will not detail treatment nor equipment in any of our plants but will describe special features in, or in connection with, all of them. I will then deal with flotation reagents, describing our use of each of them, particularly where differing from general practice. I will conclude with comments on special subjects related to differential-flotation.

Jan 1, 1927

By Kenneth Seaver

It is rather gratifying that in the field of the manufacture of refractories, in which, as a whole, foreign practice has surpassed us, the United States stands pre-eminent in the making of silica brick. In some instances European manufacturers have refused point-blank to credit the possibility of making to such specifications as are Common with us, until the actual completed shapes were shipped for inspection. But both the manufacturer and consumer in foreign lands are now frankly learning from us, and benefiting by our advanced practice in this field, as is evidenced by the orders placed here and the efforts put forth abroad to come up to the standard of American-made material. In no metallurgical operation has the employment of silica brick spread with such leaps and bounds as in the building of plants for the carbonization of coal, particularly in the byproduct coke oven. Today, in practically all types of oven, the structure above the floor level (except the facings) is of silica, while in the recuperative and in some regenerative types, its use is extended to that portion of the oven below the floor as well. By reason of the fact that there are a number of classes of refractories of higher silica content than the usual so-called fire-clay brick, there is sometimes a misunderstanding as to the class of material referred to as "silica" brick. We here refer only to a brick having a silica content of 94 per cent. or more and made usually from quartzite rock with a small percentage of lime as a binder. The term "silica" brick is sometimes rather loosely applied to brick from highly siliceous clays, or to a quartzite refractory of mingled fire-clay and quartz rock; but such products are not considered in this discussion. : Materials The rock from which practically all high-grade silica brick are made is a true quartzite or metamorphosed sandstone, variously known as

Jan 1, 1916

By R. T. Southin

Cast ingots of 99.99 pct purity A1 and aluminum/copper alloys containing up to 2 pct Cu have been found to contain four zones rather than the three previously accepted, i.e., chill, colummar, and equiaxed zones. The fourth zone consists of a coarse dendritic layer across the top surface of the ingot which is open to the atmosphere. It is also found that the grains in the equiaxed region have a "cornet" shape, with a head which is coarsely dendritic and a tail which grew with the same structure as the columnar grains. Experiments using mechanical barriers, and others involving the elimination of the surface dendrile layer, have indicated that nucleation of the equiaxed zone is caused by the showering of dendritic particles from this surface dendrite layer. These particles are the dendritic heads found in the comet grains. A mechanism of nucleation and growth of these comet grains is put forward. Experiments with a number of other metals and alloys suggests that these conclusions may apply generally to ingots cast without the addition of nucleating agents, and solidified under normal conditions. THE macrostructure of cast ingots may contain the following three zones: i) a peripheral zone of fine equiaxed grains, commonly called the chill zone; ii) a zone of columnar grains extending inwards from the chill zone; iii) a central zone of equiaxed grains; these are normally larger than the chill grains. All three zones are not necessarily present in any particular ingot since their existence and magnitude depend upon the casting conditions and composition of the cast material. The mode of formation of zones i and ii is fairly well understood. However, the cause of the central equiaxed zone remains a matter of conjecture. Previous theories put forward to explain the mechanism of nucleation in the equiaxed zone have been examined by Chalmers1 and Winegard.2 At the time when the present work was carried out the most re -cent hypothesis was that due to Chalmers,1 who recognized more fully than previous workers that conditions in this zone during solidification were not conducive to nucleation. In his hypothesis, he suggested that nuclei were formed near the mould wall during the very early stages of solidification, and that they can drift into the central zone by convective motion. This was supported by evidence from experiments using mechanical barriers to stop the drift of nuclei. A similar hypothesis had previously been put forward by Genders.3 More recently, Jackson et al. 4 have observed that dendrite arms in organic compounds can melt off during solidification. They have postulated that this occurs in metals and alloys, and that the dendrite arms which have been freed from the main dendrite act as nuclei for the equiaxed zone. In the present work, critical metallographic examination has shown that there is a fourth zone in the macrostructure of cast ingots which is a dendritic layer over the top surface of the ingot. It is also shown that there is a relationship between this zone and nucleation of the equiaxed zone. EXPERIMENTAL DETAILS The alloys examined were prepared from super -purity aluminum of 99.99 pct min purity (spectro-graphically detected impurities of Cu, Fe, Si, and Mg) and copper of 99.98 pct min purity (spectrographically detected impurities of Si, Zn, As, Fe, Pb, Bi, Ni, Sn, Mn, Ag, Cr, and Al). Three compositions of ingots were examined, containing 0.0, 0.1, and 2 pct Cu, respectively. The alloys were melted in an alumina-lined salamander crucible using a medium-frequency electric induction furnace; when the appropriate casting temperature was reached, the alloys were cast without degassing or fluxing treatment. The mould used was made of electrode graphite and had the following dimensions: external diameter 6 in., height 9 in., with a mould cavity 8 in. deep and a diameter tapering from 5 in. at the top to 4 in. at the bottom. Casting temperatures used were generally in the order of 70" to 90°C above the liquidus and the mould was at room temperature before casting. Inserts kere placed in the mould cavity in some experiments. These consisted of either an 18-g stainless-steel tube of 2 in. diam held axially in the mould i in. off the bottom and extending 1 in. out of the top of the mould or a "trap-door" barrier of stainless-steel gauze of 24-mesh held horizontally in the mould 31/2 in. down from the top. The construction of this insert is shown in Fig. 1. All inserts were preheated prior to casting to prevent chilling. RESULTS The macrostructures of ingots of the three compositions are described, in terms of the three generally recognized zones, in Table I, and illustrated in Figs. 2(a) to (c). The most interesting observation in this table is that relating to the shape of the equiaxed grains, which were not in fact equiaxed but of almost tear-drop shape. Closer examination of these grains showed that each consisted of a head which had a coarse dendritic structure and a tail which always grew in the opposite direction to heat flow, and which had the same structure as that of the columnar material of the ingot concerned; i.e., in the pure aluminum and 0.1 pct Cu alloy it was cellular and in the 2 pct Cu alloy it was cellular-dendritic. Identification of original cast grains was greatly hampered in the super-purity aluminum ingots, and to a lesser degree in the 0.1 pct Cu alloy,

Jan 1, 1968

YEAR or ELECTION 1913. FRANK DAWSON ADAMS Montreal, Canada. 1933. KARL EILERS New York, N. Y. 1922. FEDERICO GIOLITTI Q. Torino,Italy. 1906. SIR ROBERT A. HADFIELD London, England. 1921. FRANK WILLIAM HARBORD London, England. 1917. HERBERT HOOVER New York, N. Y. 1931. WALDEMAR LINDGREN Cambridge, Mass. 1921. C. MCDERMID London, England. 1913. EZEQUIEL ORDOAEZ Mexico City, Mexico 1935. ROBERT PEELE New York, N. Y. 1938. A. M. PORTEVIN Paris, France. 1937. Joan V. W. REYNDERS New York, N. Y. 1937. GEORGE S. RICE Washington, D. C. 1911. ROBERT H. RICHARDS Cambridge, Mass. 1934. T. A. RICKARD Victoria, B.C., Canada. 1933 Cambridge, Mass.

Jan 1, 1938

By F. W. Jessen, James N. Howell

The accumulation of paraffin deposits in tubular goods has been recognized as a major production problem since the inception of the petroleum industry. This problem is not limited to any particular geographical area nor is it limited to a specific type of crude oil.' Generally speaking, "paraffin" deposition pertains to the deposition of any predominately organic material in flow lines, and possibly even at the sand face, which would hamper the production of oil. In some fields, a continuous effort is required to remove deposits of paraffin and in order to accomplish this, many unique methods have been devised. The best solution to this problem, however, is to prevent the formation of such deposits. One method which has been tried in a number of fields is the use of plastic pipe. The purpose of this investigation is to compare the relative effectiveness of several plastic materials to aid in the reduction or prevention of paraffin accumulations in surface flow lines. COMPOSITlON OF PARAFFIN DEPOSITS By definition, paraffin deposits are those materials which are insoluble in crude oil at the prevailing producing conditions of temperature and pressure. Such deposits1 s usually consist of small particles of petroleum wax intermixed with resins, asphaltic material, and crude oil. They may also contain a variety of foreign materials such as sand, silt, water, various metal oxides, sulfates and carbonates of iron. barium, and calcium. The petroleum waxes deposited in flow strings usually consist of both a "hard" and a "soft" wax fraction. These waxes are largely aliphatic hydrocarbons with smaller amounts of aromatic and naphthenic compounds. Nathan' has classified the hard and soft wax fractions. The aliphatic hydrocarbons present are those of high molecular weight with high melting points. Reistle3 pointed out that these high molecular weight compounds first separate from the oil due to a sharp decrease in solubility as the melting point increases. The identification of the resins and asphaltic materials rests, at present, on an arbitrary solubility procedure. Under certain conditions, materials which are insoluble in pentane (ASTM D-893) are defined as resins and asphalts. Subgrouping of these materials is made on decreasing solubility in benzene and carbon disul-fide. Shock' found some correlation be-tween the solvent response and the pentane insoluble content of paraftins: higher pentane insoluble fractions are less soluble in any of the commonly used commercial solvents. PARAFFIN CONTROL METHODS The methods used in oil fields to prevent and remove paraffin accumulations can be grouped into four general classes: (1) operative methods, (2) physical methods, (3) chemical methods, and (4) combination of any of these. Operative methods attempt to prevent the formation of paraffin deposits while the other methods are concerned primarily with the removal of these deposits. Plastic coated pipe has been used for a number of years to prevent cor- rosion in wells, and in manv instances paraffin deposits have -been greatly reduced. Field observations have indicated that plastic coated pipe not only reduced paraffin accumulation but in some cases eliminated deposition completely; however, data are needed to demonstrate the relative effectiveness of plastic materials. Deposition Apparatus The pipe used to determine the effect of velocity on rates of deposition was %- and 2-in. nominal diameter, and 5 ft in length. Steel, butyrate, rigid PVC, kralastic resin-type plastic pipes, epoxy coated pipe, PVC lined glass fiber pipe, and aluminum pipe were tested. Steel pipe was used as a control. Fig. 1 is a schematic diagram of the apparatus showing the relative position of the separate units making up the equipment. In order to facilitate the installation and removal of the test pipes in the apparatus, O-ring seals capable of sustaining pressures of 50 psi were provided at each end. Test pipes were submerged in a cold water bath maintained at or below room temperature by circulating water through copper cooling coils packed in ice. A hot water bath equipped with immersion-type heaters, stirrers, and a thermoregulator was used to maintain the temperature of the oil prior to introduction into the piping manifold. The capacity of the oil reservoir was 30 gal. A 33-gal/min centrifugal pump, capable of producing turbulent flow velocities in the test pipes, was used to circulate the oil through the system when using %-in. pipe; and a 70-galjmin centrifugal pump was used in later tests using 2-in. pipe. A by-pass arrangement made it pos-

By J. J. Pye, J. B. Drew

The surface-diffusion coefficients of Ni63 diffusing on low-index planes of nickel single crystals have been measured over the temperature range from 400° to 1000°C using a precision autoradio-gvaphic technique. The activation energy for sur -face diffusion appears to he the same on the {111}, {110), and (100) planes and amounts to -0.60 ev. This is in good agreement with the value (-0.62 ev) reported for (111) planes obtained by mass-transport techniques. In an earlier paper, the authors have reported self surface-diffusion coefficients on silver.' In that work, a deviation of the diffusion coefficients from linearity in the Arrhenius plot was observed at high temperatures. This effect was attributed to a loss of tracer atoms into the bulk by volume diffusion. The purpose of the present work was to extend the technique developed to the nickel surface-diffusion system up to the point where volume diffusion would come into play. The nickel system especially lends itself to this technique due to the high efficiency of the isotope in darkening the film and the large absorption of the weak radiation (0.063 mev /3- particle of the trapped tracer atoms. The diffusion coefficients and ictivation energy for different orientations on nickel can also be compared with a report published by Blakely and Mykura 2 where a mass-transfer technique was used. This paper reports the self surface diffusion of nickel on the low-index planes over a wide temperature range using a precision autoradiographic technique. EXPERIMENTAL PROCEDURE The experiment is similar to that described in the earlier publication consisting of a radioactive needle as a source resting on a flat, smooth, chemically polished surface annealed in a dynamic dry-hydrogen atmosphere. The needle is held snugly on the surface by a holder fabricated from commercially pure nickel. The point source is made by grinding down a small-diameter nickel rod until a tip of approximately 0.1 mm radius is formed. It is then etched and the needle tip plated with the radioactive isotope Ni63. Nickel single crystals were used whose main impurities were spectrographically determined as Co 0.05, Fe 0.007, C 0.005, and S 0.003 pct. The surfaces, oriented to within 1/2 deg of the low-index planes, were carefully mechanically polished and etched in a 50-30-10-10 hot solution of acetic, nitric, sulfuric, and phosphoric acids giving a smooth polished surface. The crystals were then washed in distilled water and alcohol. Annealing temperatures ranged from 400° to 1000°C with a furnace arrangement in which the crystals could be brought up to temperature in times short compared to diffusing times. The temperature was maintained constant to ±10°C. In the temperature range investigated, the ratio of the surface-diffusion coefficient to the volume-diffusion coefficient (Ds/Du) was 105 or more and the mean bulk-penetration values, calculated from literature values of volume-diffusion coefficients,3 were on the order of 10-5 cm. After the diffusion anneal, the sintered needle is removed, and both the radius of the needle point and spot left on the crystal face are measured. The crystal is then placed on photographic film. Diffusion profiles are obtained by scanning the film with a recording microdensitometer which has a slit width of 10µ. DISCUSSION AND RESULTS The experimental conditions are such that the source strength and needle radius are essentially constant and the time is adjusted such that the mean bulk penetration is small. An exactly analogous heat-flow problem has been considered by Carslaw and Jaeger4 and the solution can be written in integral form as:

Jan 1, 1964

By A. U. Seybolt

Experiments on both suljidation and hot corrosion have been carried out using ternary Ni-Cr-X alloys and commercial nickel-base superalloys. It has been shown that lhere are certain micro structural similarities between sulfidation using H,S/H2 mixtures and hot corvosion using Na,S04 in "crucible" experiments or hot corrosion tests using a flame tunnel apparatus. It is proposed that two key processes in the hot cowosion process are: 1) formation of chromium sulfides which deplete the alloy matrix, and 2) oxidation which can be accelerated because of chromium depletion. Other processes play an important role in the hot corrosion process, such as accelerated oxidation attack due to the presence of a N& S04 or N&SO,- NaC2 film which inhibits the formation of a protective external oxide scale. However, this latter phenomenon was not studied in this work. THE term hot corrosion has come to mean a combination of sulfur and oxygen attack on nickel-base or cobalt-base superalloys used as gas turbine blades or partitions. This attack can be initiated by any combustion process in air involving fuel containing sulfur if the sulfur level is sufficiently high. Levels of 5 pet SO2l for example, in the combusting gas have been observed to produce hot corrosion attack on nickel-base alloys. The important immediate corroding medium in aircraft gas turbines, however, has been established to be Na2S04, formed from reaction between NaCl from sea air and sulfur in the fuel.' The Na2S04 concentrates the sulfur sufficiently so that superalloy parts heated in the range 1400" to 1900°F can become sulfided by reducing the Na2S04 film which forms on the parts, and this reaction allows sulfur to gain access to the alloy. The sulfur thus released diffuses into the superalloy and forms primarily chromium sulfides of various compositions, but frequently Cr2S, has been identified. Figs. 1 and 2 show the morphology typical of hot corrosion of a cobalt-base superalloy X-45 (25 Cr, 10 Ni, 7.5 W, 0.25 C) and a nickel-base alloy, Udimet 500 (19 Cr, 19 Co, 4 Mo, 3 Ti, 2.9 Al, 0.07 C). Both alloy samples were subjected to the same hot corrosion conditions: 616 hr at 1600°F in a combusted 2.9 pct S distillate oil containing 125 ppm Na as NaC1. It will be noted at once that the nickel-base alloy is much more severely attacked. The depth of corrosion is much greater and the number and size of the sulfides present are much greater. Both alloys show a duplex oxide scale, which is more noticeable in the X-45 alloy. The external scale is probably a spinel in both cases, with CrQ3 lying next to the alloy. Many investigators1 -"ve been concerned with hot corrosion phenomena, but there has been a lack of unanimity of opinion as to the details of the hot corrosion mechanism. More than one definition of hot corrosion is possible. Some investigators con- sider as a measure of hot corrosion only the weight gain due to an accelerated oxidation. However another point of view is that the total depth of affected alloy may be used as a measure. While it is recognized that surface oxidation attack is greatly accelerated by the presence of salts like Na2S04 or Na2S04-NaC1 mixtures, sulfur penetration into the alloy also undoubtedly produces very important effects. The region of sul-fide penetration which is so prominent in Fig. 2 is one of the outstanding characteristics of hot corrosion. For highly stressed parts, such as first-stage buckets, this sulfur-penetrated region can be more significant in mechanical property loss than the reduction of cross section produced by the formation of the massive external scale. In addition, evidence will be presented that this sulfided region can be less resistant to subsequent oxidation attack. Since it appears that the sulfided region below the surface oxide scale plays an important role in the overall corrosion process,

Jan 1, 1969

By J. E. McDonald, J. G. Eberhart

A model is discussed from which the work of adhcslon .tor liquid transition metals on aluminum oxide surfaces can he calculated, A close-packed (00011 oxygen surface on A12O3 is assumed with two different types of surface sites: one type involving metal-oxygen bonds and the other man der Waals into actions. The work of adhesion is thus expressed as the sum of these two bonsding free energies. Calculated works of adhesion for nickel, titanium, chromium, and zirconium on sapphire agree well with the experimentally determined quantities. The model is extentled to the calculation of the work of adhesion and shear stress required to remove a thin metal film from a sapphire substrate and is in good agreement with experimental values. The obsewed dependence of the work of adhesion on the free energy of oxide formation of the metal is shown to also provide an interpretation of the tittle dependence of thin-film adhesion. THIS paper presents a model for the type of bonding which occurs across a metal-A12O3 interface. The model is used to explain the results of two types of experiments in which such an interface exists: 1) the adhesion of thin metal films on Al2O3 substrates and 2) the wetting of A12O3 by liquid metal drops. The adhesion of thin films to various substrates has been the subject of a variety of investigations.'-' Benjamin and weaver3 and Bowie,6 using the scratch test developed by Heavens,10 studied the adhesion of metallic films to glass substrates. Their observations for noble-metal film adhesion agree well with an adhesion model involving a van der Waals type of bonding between the film and the substrate. For films of metals whose free energy of oxide formation. ?F°f, has a negative value. Benjamin and weaver3 and Bowie6 found a time-dependent adhesion with an initial value that can be interpreted in terms of van der Waals interactions but a larger terminal value which was related to ?F°f, Karnow-sky and Estill7 deposited films on sapphire at elevated temperatures and noticed no time dependence of film adhesion but a similar correlation with ?F°f. Because of the kinetic problems associated with thin-film adhesion it is desirable to examine adhesion in an equilibrium system. The wetting behavior of liquid-metal drops on Al2O3 provides such a system. Systems of this metal-ceramic type have been studied extensively.11 Humenik and Kingeryl2 have measured the wetting of A12O3 (and other substrates) by several metals and have pointed out that the wetting ability of these metals increases with increasing values of -?F°f. It is thus seen that thin-film adhesion and metal wetting on A12O3 are both related to the tendency of the metal to react with the surface oxide ions of the Al2O3 substrate and, because of this, both phenomena should be explainable by an appropriate model for the metal-Al2O3 interfacial bonding. In the sections that follow, wetting and adhesion data on A2O3 are reviewed and a model is presented by which these phenomena can be interpreted. ANALYSIS OF WETTING EXPERIMENTS In an equilibrium system involving a liquid-metal drop on a solid Al2O3 substrate, the work of adhesion, WAD, is defined by the Dupre, equation as WAD = ?s + ?L -?sL [1] where ?s and ?L are the surface free energies of the solid substrate and the liquid drop, respectively, and ?sL is the interfacial free energy. The work of adhesion is the work required to separate a unit area of the solid-liquid interface into two surfaces. The work of adhesion is usually determined from a sessile-drop experiment in which yL and the contact angle, ?, are measured. The Young-Dupr6 equation is then used to calculate WAD Wad = ?L (1+ cos ?) [2] The literature of this subject has been examined and Table I shows work of adhesion data for various liquid metals as measured on A12O3 substrates. The standard free energy of oxide formation of the metal at the temperature of the wetting experiment, ?F°f . is also tabulated in kcal per g-atom of oxygen. The data is grouped according to the gaseous atmos-

Jan 1, 1965

By J. Richard Maier

Short-range mine planning (less than five years) previously was accomplished using contour and isopac maps, pencil and paper, an abacus, and our lucky quarter. Through the use of both micros and mainframe time sharing, Glenrock Coal Company (GCC) has been able to virtually put the old equipment away (except the problem solving quarter). In the process, GCC has saved many man-days and eliminated the more tedious parts of mine planning, such as picking elevations off a map with an engineer's scale and repetitive calculations. These savings have allowed GCC to do a more extensive job of mine planning as well as offer more alternatives, making GCC better prepared for possible economic changes. Mine planning, simply, involves looking at what has been done and deciding what needs to be done using various constraints. The application of this concept is not as easy as it sounds. The need for experience and insight cannot be replaced by a machine, but machines can supplement a person's ability by doing the bookkeeping and the repetitive work. Through the application of computers and their accessories, GCC has brought mine planning to a more modernized state. The following paper will detail the development and use of one system as used at GCC. Please note: In the figures and tables following, some of the data has been altered to protect confidential information used in mine planning.

Jan 1, 1983

Jan 1, 1932

By John W. Wagner, Robert K. Willardson

Single crystals of Pbl-xSnXTe have been grown from The melt under liquid B2O3 using the Czochralski technique. The PbTe-SnTe crystals were grown from near-stoichiometric melts and from melts with slight deviations from sloichiometry. Crystal growth rates ranging from 1 mm per hr to 1 cm per hr were employed, the latter being generally used. Several investigations were performed to characterize the single crystals grown In this study. The phase diagram of the PbTe-SnTe system was examined. X-ray analyses verified the single-crystal character of the crystals, and powder pattern lattice parameter determinations showed that Vegard's law was followed within the limits of the experimental error. The as-grown crystals were p-type with apparent carrier concentrations of -8 x 1018 to -8 x 1020 carriers per cu cm. Hall coefficients, resistivities, and carrier mobilities were determined as a function of composition. Dislocations were revealed by an electrolytic etch, and the crystals were found typically to contain 2 to 4 x 105 dislocations per sq cm. Microhardness measurements were performed; no maximum in the Vickers hardness us composition curve was seen. Mass spectrometry was used for impurity analyses, and the crystals were found to contain 1 to 2 x 1017 total p-type impurities per cubic centimeter. Distribution coefficients were calculated for the major impurities which were Na, Mg, Al, Si, Cl, and Zn. RECENTLY interest has been stimulated in the preparation and characterization of many alloys of the binary compound semiconductors. This interest is due primarily to the almost unlimited possibilities of adjusting the semiconducting characteristics of these materials by varying the alloy compositions. One alloy system which has been receiving extensive investigation is the PbTe-SnTe system, since these alloys show promise of being useful as emitters and detectors of electromagnetic radiation in the spectral range of 8 to 14 µ. This paper reports on the growth of PbTe-SnTe single crystals by the Czochralski technique and investigations of the general properties of these crystals. The phase diagram of the PbTe-SnTe system was investigated so that specific alloy compositions could be attained. I) CRYSTAL GROWTH The PbTe-SnTe single crystals were pulled from the melt using the Czochralski technique. Generally, the crystals were grown from near-stoichiometric melts, although special growth runs were made from both lead-rich and tellurium-rich melts. Growth of single crystals from up to 5 pct lead-rich melts presented no problems; however, melts with tellurium in excess of -1 pct caused volatilization problems which generally made crystal growth impossible. All melts were prepared from high-purity materials as follows: 1) lead— 6 N— Cominco (Cominco Products, Inc., Spokane, Wash.); 2) tin—5N—Cominco; and 3) tellurium— 5N+— American Smelting & Refining Co., Plainfield, N.J. No further purification of materials was undertaken in this study. The elements were reacted at -1000°C in a vacuum-sealed silica tube for a few hours, a gentle rocking action being used to ensure thorough reaction. The cast ingots were then transferred to a silica crucible for crystal growth. A schematic diagram of the growth apparatus is shown in Fig. 1. The Vycor tube is sealed at both ends by O-ring flanges so that a vacuum or a positive pressure may be maintained in the growth chamber. The pull rod and crucible may be rotated; all crystals produced in this study were grown with the crucible sta-

Jan 1, 1969

By H. H. Power, C. H. Pishny

When an oil operator becomes a party to a proration agreement he may wonder, with good cause, whether production prorated .today is merely deferred until tomorrow or whether oil might be lost. Various types of evidence obtained from production records when studied quantitatively are of great assistance in arriving at definite conclusions. A study of individual examples cited in this paper leads towards some solution of the problem, particularly when they are considered in the aggregate. Many production curves on various pay horizons were studied. A disappointingly large number of these were of contributory value, but inconclusive. However, there were enough curves of similar type from the Wilcox sand at Earlsboro, Bowlegs, Seminole City, the Cromwell horizon at Little River, and the Simpson dolomite at Valley Center, Kansas, from which reasonably definite conclusions were drawn. Assuming that deferred production is later made up with no increase in ultimate recovery, a curve (Fig. 1) shows the normal flowing and pumping life of a composite well, contructed by the family curve method. The initial production of the well shown is 1700 bbl. daily and the allowed production is 25 per cent. On this basis the average daily allowed rate for the first month is 425 bb1., or the area BCDE, which is equivalent to the area AFDG under the normal decline curve. The potential production for the second month is 1500 bbl. and the allowed production 375 bbl. daily. By this procedure a potential curve for each succeeding month is obtained (points A, H, I, J and K). If the well is opened it should produce somewhere near its potential curve for a short period and then decline at a more rapid rate than the potential curve. This theoretical analysis is basic. Actual examples exhibiting all points raised by the ideal curve are rare. Proration in the Mid-Continent area has been effected mostly by leases rather than by individual wells; hence a well may produce any

Jan 1, 1931

By E. A. G. Colls

Discusses corrosion in Trail chemical plants producing ammonia, sulphuric, nitric and phosphoric acids, ammonium phosphates, sulphate and nitrate, together with miscellaneous allied material problems and their solution using erosion or corrosion proof materials. Conclusion, that for work of this nature, most costly material may well be cheapest in the long run.

Jan 4, 1950

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

The Bureau of Mines developed a detector for controlling sorting devices to separate the copper-bearing fragments from the barren portion of Michigan native copper and western prophyry copper ores. A successful sorter could be used to preconcentrate the ore and eliminate costly hoisting or hauling of waste. An induction balance unit was developed and used in sorting tests on crushed sized - 2.5 + 1.3-cm (- 1 + 112- in.) ores from the Kingston (0.9% Cu) and Centennial (1.6% Cu) mines of Upper Michigan. Concentrates of 4.0% and 7.5% Cu, respectively, were obtained at recoveries of 85 and 80% of the copper in the feed. Eighty percent of the sorted ore was rejected as tailing. Sorting larger fragments improved the separation efficiency. Tests on - 10+ 5-cm (- 4 +2-in.) sized Kingston (1.6% Cu) and Centennial (2.1 % Cu) ore samples yielded concentrates of 4.3 and 4.5% Cu, respectively, with corresponding recoveries of 92 and 91 %. A bout 60% of the sorted ore was discarded as tailing. Porphyry copper sulfide ores also responded to electronic sorting but at a lower separation efficiency. Sorting response was affected by the degree of segregation.

Jan 1, 1979

By AIME AIME

AS director of Battelle Memorial Institute and as Chairman of the important O.P.M. advisory committee on metals and minerals, Clyde E. Williams numbers his acquaintances in the mineral industries by the thousands and h because his principal hobby is liking human beings, most of his acquaintancs are also his friends. Clyde is one of the many outstanding metallurgist, in the United States who started as a chemist. After graduating from the University of Utah in 1915 he was successively chemist for U.S. Smelting Refining and Mining Co., and at the Bureau of Mines station at Ithaca, N.Y. He then got into, metallurgical work and in 1920 he was appointed superintendent of the Northwest Station of the Bureau of Mines at, Seattle. Subsequently he was assistant to H. Foster Bain in metallugical work for the

Jan 1, 1942

By W. H. Moore, E. T. Powell

IN the early days of mining in the Anthracite field, only the thicker and better seams of coal were mined, because of the limited mining and coal-cleaning facilities, therefore many of the thinner and less productive seams were permitted to remain unmined. With improvements in mining methods, the introduction of modem preparation plants, and the increased market demand for small-size coal, the thinner and more laminated seams have now become assets. In many instances these seams overlie the mined-out beds of the thicker and better seams, from which all recoverable coal was removed by the conventional breast-and-pillar method of mining. Some collieries in certain sections of the Anthracite field are now relying on these thinner and laminated seams. For the purpose of illustration, a large area in the Hickory Swamp-Ridge Basin of the western middle coal field has been selected, where as early as 1898 the No. 4, or Little Buck Mountain, seam was mined and pillars removed. The No. 5, or Buck Mountain, seam lying on a comparatively light pitch and with intervening strata of but 55 ft. of rock was not mined until 1935. Farther east, in the same basin the Nos. 8 and 9 seams, which are two splits of the Mammoth seam, have been mined and robbed and the workings have been abandoned since 1896. The overlying No. 9 ¾ seam, or the upper split of the Mammoth, and the No. 9 ¾ or 4-ft. seam remained virgin, with only an interval of 50 ft. of rock separating them, and with 40 to 50 ft. of rock strata separating the No. 9 ½ seam from the completely mined area of the Nos. 8 and 9 seams. These seams lie on a pitch of 45° on the south side of the basin and on 75° on the north side of the basin. Mining has been carried on in the 9 ½ and 9 ¾ seams for 3 years on both dips of the basin, for a distance of 3500 ft. In some sections the overlying strata of the thicker seams previously mined have settled without any apparent breaks in the upper strata, as indications have shown in the top split of the Mammoth; while in other areas the roof and bottom of this top split of the Mammoth have settled unevenly, thereby causing the bottom and roof to break into blocks. In attempting to mine over a large area of the No. 5 or Buck Mountain seam, a similar settlement has been encountered; the roof of the seam has been broken and a considerable amount of timbering has been necessary in order to make the mining of the seam possible. The conventional breast-and-pillar method, using shaker conveyors, has been used in the No. 5 seam, and a slant-breast method in the mining of Nos. 9 ½ and 9 ¾ seams. MINING OF LIGHT-PITCH SEAMS The No. 4 seam was mined and robbed by the conventional breast-and-pillar system. In this area the seam pitched from 5° to 25° on the north dip, averaged 8 ft. in thickness and had a slate bottom and a

Jan 1, 1941

By T. D. Tiemann

The chemical and mineralogical composition of Caribbean bauxite ores are described. Extraction of alumina by several processes from both Haiti and Jamaica bauxites is discussed and data presented. IMMENSE deposits of bauxite occur in the Caribbean islands of Hispaniola and Jamaica in the high plateau lands and have been excellently described by 0. C. Schmedeman.' The bauxite occurs as deposits in catchments or etched depressions in Tertiary limestone believed to have been deposited in the Eocene and Oligocene periods.' In appearance both the Haiti and Jamaica bauxites resemble a relatively high iron clay and have indeed been mistaken for such.' They are very soft and friable and disperse readily on vigorous agitation in water. The color range in general is light brown to red. Chemically, the outstanding characteristic of the bauxites is the low silica and high ferric oxide content. The extremely low silica makes them particularly valuable for the production of alumina in the Bayer plant since silica is responsible for the loss of both alumina and soda chemically combined as XNa,OYSiO2,ZAl2O2. The ferric oxide, only traces of ferrous iron are present, offers no interference in the production of high grade alumina. Typical oxide analyses of three types of ore are given in Table I2 and a list of the elements occurring in spectrographic quantities in Table 11." The size of the individual particles in the ore makes successful petrographic examination extremely difficult. The ores contain some relatively coarse grains of heavy minerals such as ilmenite, magnetite, and rutile, but other than occasional crystals of a few microns, the greater portion of the minerals are submicroscopic in size and approach colloidal dimensions. The mineralogic composition of the ores has been investigated by X-ray and differential thermal analysis.' These investigations indicate that the predominant mineral phases present are gibbsite (A1203.3H2O), boehmite (Al2O3.H2O), hematite (Fe2O3), and goethite (Fe2O3-H2O). There is no evidence of the occurrence of diaspore (Al2O3.H2O) in either the Haiti or Jamaica ores, but some type of "amorphous" alumina may be present in some of the bauxites of Jamaica." The temperature stability regions in the alumina-water system have been investigated and are given in recent literature. In the temperature range where the hydrated forms are stable, as determined by hydrothermal bomb methods," ibbsite is the stable phase to 155°C (311°F), boehmite from 155°C (311°F) to 280°C (536oF), and diaspore from 280°C (536°F) to 450°C (842°F). Although quite similar in many characteristics, the Haiti and Jamaica ore show a divergence in mineralogic composition that is reflected in the extractability of the alumina described in later paragraphs. Two principal differences occur in mineralogic composition. The iron-bearing mineral in the Haiti ores is predominantly hematite, while in the Jamaica ores goethite is predominant.4 Directly related to the extraction of alumina are the two minerals, gibbsite and boehmite. Boehmite is relatively high in the Haiti ores and in some of the less soluble Jamaica ores, while gibbsite predominates in the ores in Jamaica amenable to the American Bayer process of extraction. Pedersen and Related Processes In general, all processes for the extraction of alumina involving sintering or fusion of bauxite ores with limestone, soda ash, or a combination of limestone and soda ash followed by leaching, are based on the formation of alumina compounds that. yield alumina soluble in the subsequent leach. The principal idealized reactions in respect to alumina and silica for the three types of processes are as follows: Soda Ash Sinter: A12O3 + Na2CO3 = Na2O-Al2O, + CO2 SiO2 + Na2CO3 = Na2O . SiO2 + CO2 A12O2 + SiO2 + Na2CO3 = Na2O.Al2O8. SiO2 + CO2 Leach (with excess water): H2O + Na2O-A12O3 = 2 NaOH + A12O3 (insolution) H2O + Na2O-SiO2 = 2 NaOH + SiO2 (in solution) Soda Ash— Limestone Sinter: Na2CO2 + A12O3 = Na2O.A1203 + CO2 2CaCO3 + SiO2 = 2CaO . SiO2 + 2CO2 Leach (with excess water): Na2O' A1208 + H2O = 2NaOH + A13O3 (in solution) These latter reactions are the basis of the sinter process currently used for the recovery of soda and

Jan 1, 1952