Search Documents

By R. V. Higgins

This report presents computer instructions for calculating the performance of three-phase flow of gas, oil, and water. The calculated results for an illustrative example are presented. The example is the waterflood of a reservoir containing free gas in the reservoir as a result of the partial depletion of the oil by the expansion of the gas initially in solution. The flood pattern for the example is a 5-spot.

Jan 1, 1967

By J. Groyecki, M. Markuszewicz, J. Lassota, A. Zawada

The ratio of stable to unstable inclusions was found to ploy an essential role in the process of sccorldar-y recrystatlizalion in Si-Fe. The analysis of the free energy of inclusions in the range of heat-treatment of individual inclusions to be predicted. The effects MnS. ns inslable inclusions. were investigated. TO secure a high induction, the secondary recryslulliztt-lion associated wilh the texture is necessary. To obtain a low core loss an additional refiuing in the solid state is required. It has been found that sulfur can be more easily removed in racunm than in hydrogen and thai this process was hindered by the prescrzce of INCLUSIONS play an essential role in the development of cube-on-edge texture in Si-Fe. Their function consists in restraining the growth of primary grains up to about 900°C and in passing subsequently into solution at higher temperatures. This process is accompanied by the selective growth of secondary grains with (110)[001] orientation. The general effect of inclusions depends on such factors as the type of impurities, their amount. dispersion and stability, the conditions of diffusion in the space of lattice of metal, and the reactions at the metal/gas interface. In recent years, some of these factors were the subject of a special investigation. A positive influence of Mns, siN,' and vN3 has been established. The quantity of impurities4 and their dispersion5 have been found to be of major importance. Attention was called to the vital importance of diffusion and the conditions under which the impurities are removed from metal., It has also been demonstrated that in Fe-Si alloys by the techniques of powder metallurgy a special opportunity exists to obtain the (110)[001] type texture. 6 The aim of this work was to conduct qualitative investigations on the influence of inclusion stability on the development of cube-on-edge texture in a metal containing approximately 3 pct Si. Experiments were carried out on cast alloys and on those manufactured by powder-metallurgy techniques. The results obtained from these experiments were utilized to explain the phenomena involved and to analyze the relationships between stable and unstable inclusions and the magnetic properties of alloys. EXPERIMENTS AND RESULTS The raw materials used in these experiments were the powder of carbonyl iron with the analysis (in pct) 0.044 C, 0.01 Mn, 0.005 Si, 0.009 P, 0.002 S, traces of Cu, 0.06 Ni, 0.0015 Al, 0.03 Cr, 0.02 Mo, 0.01 Ti, 0.002 Co, traces of Pb, and the powder of silicon containing 94.14 Si, 0.003 S, 0.048 C. The powders were ground and mechanically mixed in 100-g batches. and then pressed at 9 tons per sq cm into 74 by 24 by 8 mm blocks. Sintering was carried out at 1100°C for 12 hr in vacuum (2 x lo-' Tr) or in hydrogen. In this instance the material was heated slowly and subjected to prolonged soaking at 350°, 650°, and 750 2C, respectively, to secure reduction of ferro-oxides. This was checked by making measurements of the dew point, which was found to change from -15" to -35°C after reduction. The compacts after sintering were hot-rolled to 2.4 mm, annealed at 800 C, and finally cold-reduced to 0.35 mm with intermediate annealing at 800°C at a gage of about 0.8 mm. Impurities were added in the powdered form and mixed with iron and silicon powders. Sulfur in the elemental state, electrolytic manganese, and pure aluminum oxide were employed. Besides, to obtain a material with low contents of impurities, especially

Jan 1, 1967

By J. L. Shultz

The Bureau of Mines extended its investigation of methanation catalysts. The noble metals (platinum, palladium, ruthenium, rhodium, osmium) and rhenium), molybdenum, and tungsten were tested in hydrogenations of carbon monoxide and carbon dioxide at 21 atmospheres in a temperature range between 200° and 600° C. From the 8 metals studied) 25 catalysts represent 5 catalyst types were prepared and tested. The impregnated 0.5-percent-ruthenium catalyst proved to be the most active and versatile of all the catalysts produced. Tungsten and the noble metals other than ruthenium were low in activity and usually required temperatures above 500° C for appreciable production of hydrocarbons. Molybdenum was moderate in activity, but further improvement in molybdenum catalysts seems possible.

Jan 1, 1967

By L. R. Woodyatt, H. J. Beattie, C. T. Sims

Theories correlating the formation of u and related intermetallic compounds to the electron-per-atom density of binary and ternary alloys have appeared regularly in recent technical literature. These same principles can be modified and applied to complex precipitation-strengthened alloys such as the iron-, cobalt-, and nickel-base superalloys and the stainless steels. Since these complex alloys contain carbides and other phases that normally precipitate before the U-type phases, the nature and amount of the precipitated phases must be calculated first. The following general formula is then applied to the residual matrix composition of the alloy: element. The magnitude of the resulting number is indicative of whether the alloy will form a a -type phase. When these calculations (which are computerized) are systematically applied to alloys of knoun phase analysis, a breakoff in average electron-vacancy number is noted between U-free and U-prone alloys. Alloys with an average electron-vacancy number higher than the breakoff form a-type phases, while those with lower ones do not form these phases. This method could then be used to eliminate from consideration all experimental compositions that would precipitate undesirable phases. It also is useful in evaluating analyzed heats of alloys where minor heat-to-heat variations determine whether the alloy is o-free or o-prone. THE highly significant development of strong, ductile superalloys to provide reliable construction materials in the 1000" to 2500° F temperature range has been due principally to unremitting application of Edisonian techniques and logic by the dedicated physical metallurgists who have shouldered this responsibility. Tools such as the electron microscope, phase analysis, and computers to accomplish regression analyses have been used heavily, but the effort has been essentially practice of an art, rather than a science. The objective of this paper is to describe and illustrate application of some relatively fundamental principles to certain of these alloy systems in an attempt to remove some of the empiricism from the technology. Specifically, the work presented here deals with the use of periodic-group relationships to predict the formation of intermetallic phases which can occur in primarily austenitic (fcc) structures. Calculations that have been developed might be applied in the design of new alloys and the evaluation of known alloys, and thus have the potential of eliminating vast areas of unnecessary alloy preparation and evaluation. ALLOYING CONCEPTS AND STRUCTURAL FEATURES OF SUPERALLOYS Strength is produced in austenitic superalloys by three principle mechanisms: 1) precipitation of y'; 2) formation of carbides; 3) solid-solution hardening by soluble refractory metals. The first mechanism requires the addition of aluminum and titanium, the second requires carbon and carbide-forming elements, while the third calls for the addition of molybdenum and/or tungsten. A considerable concentration of chromium is usually maintained to resist oxidation/corrosion, but it is also an important carbide-forming element. Fig. 1 shows a sketch and electron micrograph of the structure of a typical wrought nickel-base super-

Jan 1, 1967

By R. Lagneborg, R. Gullberg

An X-ray method for determinig volume fractions of phases in textured materials has been developed. The method involves measurements of the integrated intensities of reflections of each phase for one single orientation of the sample. The method was checked by evaluating the phase contents in samples from two stainless Cr-Ni steels containing austenite and ferrite in known amounts. In the present case measurements of about five reflections from each phase were required. The agreement between calculated and known volume fractions was found to be very close. AN X-ray diffraction method is often employed for determining the amounts of two or more phases in a material. The details of the method have been described at several instances.'" In short, the method is based upon the fact that the integrated intensity of a reflection is directly proportional to the volume fraction of the phase considered. In principle, the method only requires the measurement of the intensity of one reflection for each phase. The most severe shortcoming with this method is that it disregards influences from preferred orientation in the material. In a diffractometer, where this type of analysis is most conveniently carried out, the geometry is such that the diffracting planes for a specific Bragg peak are all parallel to the surface of the specimen. This implies that it must be required that the occurrence of the diffracting planes parallel to the specimen surface must be as frequent as for any arbitrarily oriented physical plane of the sample. This requirement will generally only be fulfilled for a material free of texture. Since all materials in reality always exhibit a preferred orientation to some extent. the deficiency of the method is quite serious. In cold-deformed material the texture is appreciable, but also annealed material will in many cases display a considerable texture. The problem of quantitative phase analysis in textured material is one of obtaining the integrated intensity averaged over all orientations of the specimen with respect to the X-ray beam. Lopata and ~ula~ have shown that this can be accomplished by integration of intensities over the whole pole figure, or by random rotation of the specimen in the X-ray beam, or by a combination of both. Hence, in this method the average integrated intensity for a specific reflection is obtained by directly determining the intensity for a sufficient number of physical orientations of the sample. However, since an excess of diffracting planes in a certain surface plane necessarily must be accompanied by a deficiency of another type of diffracting plane, it appears to be possible to obtain the correct average intensity for a specific diffracting plane by performing an appropriate averaging of intensities belonging to a large number of diffraction planes of different hkl when all intensities have been produced from one single orientation of the specimen surface. In the present work such a method has been attempted and tested experimentally for two stainless Cr-Ni steels containing austenite and ferrite. 1) THEORY The expression for the integrated intensity of a Bragg reflection diffracted from a phase in a polycrys-talline sample in a diffractometer is: where C is a constant only dependent on the incident X-ray power and the diffractometer geometry, v the volume of the unit cell, F the structure factor, m multiplicity of the diffracting plane, L Lorentz factor, P polarization factor, e-2 temperature factor, p average linear absorption coefficient of the irradiated vO1umej and V volume fraction of the phase 'Onsidered. Hence, the factor R in the abbreviated form of Eq. [I] can be calculated and depends only on 0 and the diffracting plane {hkl}. For an alloy containing two phases, a and y, we can write

Jan 1, 1967

By C. B. Alcock, M. G. Hocking

The kinetics of the growth of sulfate layers on blocks of Cu20 has been studied between 688" and 800°C. At 788c the over-all weight increases followed the parabolic rate law, with k = 216 30 sq mg per cm4 min, using a 1:1 entering gas mixture of SO2:02. At 757 after an initial linear period the parabolic rate law was followed, with k = 57.8 10 sq mg per cm4 min. The gas mixture required a platinum catalyst to produce the maximum SOs pressure. The sulfation rate at 757' and 788c was high until all the CUZO had changed into a core of CuO, when it became very much lower. At 757°C marker experiments showed that the sulfates (CuO. CuS04 and CuSO4) grow outwards from the oxide surface, but CuO. CuS04 mixed with CuO was found beneath the markers. At 688 markers were found at the CuO. CuS04/CuS04 interface. Visual observations at 757 showed a liquid eutectic moving beneath the sulfate surface. causing very rapid sulfation and extruding to solidify as thick 'needles" up to 8 mm long. Marker experiments have shown conclusi.cely that CuO grows on Cu20 in air by the outward migration of copper. ThermODYNAMIC measurements on the sulfate and basic sulfate of copper, reported recently,' are followed here by measurements of the rates of formation of these sulfates on cuprous oxide, in order to provide a background for the understanding of roasting processes. peretti2 and McCabe and Morgan3 have shown that the phase Cu20 lies next to Cu2S when the sulfide is roasted under conditions where sulfates will be formed. Since this would present too complex a system for kinetic study, the present work4 has been based on the kinetics of sulfation of the oxide phase. The results of a study of the kinetics and mechanism of the sulfation of cobaltous oxide have recently been reported.4,5 Results on the sulfation of cuprous oxide have also appeared,6 but are at variance with those to be reported here. This seems to be because the previous workers6 did not obtain constant SO3 pressures from the SO2/O2 sulfating gas mixtures used, as will be discussed later. Wadsworth, Leiter, Porter, and Lewis found that the sulfates produced when SO2/O2 mixtures are passed over Cu20 at red heats are CuS04 and the basic sulfate CuO.CuSO4. When the decomposition of CuS04 was followed' by differential thermal analysis, a stage corresponding to CuO .CuS04 was reached before decomposition into the oxide occurred. APPARATUS The vertical furnace used for quantitative studies was a conventional resistance-heated and propor- tionately controlled furnace with an even zone (1 deg) which was 4 cm long. The gas mixtures of SO2 and 02 were made by mixing measured flows from capillary flowmeters and drying over phosphorous pentoxide before passing them into the Pyrex top-piece of the furnace assembly. A mullite tube of bore 2% cm was used as reaction vessel and at the bottom of this tube was a trap for SO3, which condensed as a colorless liquid. The residual gas was led into a fume cupboard for ventilation to the atmosphere. The furnace used for visual observations of needle growth and other phenomena consisted of a transparent silica reaction tube of bore 3 cm, having an optically flat silica window sealed into its wall. The reaction tube was clamped vertically, inside a mullite tube of bore 4 cm and length 42 cm which was heated by Kanthal windings. The window in the silica reaction tube was arranged opposite a hole 3 cm wide and 2 cm tall which had been cut in the wall of the mullite winding tube 19 cm from its top end. A binocular microscope was used to look through the window, illumination being provided by a focusing microscope-lamp offset sideways and downwards. The oxide block to be sulfated was suspended from the removable Pyrex top-piece to the reaction tube, by means of which it was inserted at the start of the experiment, and through which entered the S02/02 gas mixture. The variation of the temperature inside the reaction tube with horizontal and vertical displacement from the window was investigated, and, while it can be said that the temperature was constant 1 deg, its value at a given position was known only to 12 deg. In both furnaces, the oxide block to be sulfated was suspended from a small silica hook immediately downstream from a platinum thimble used as catalyst, which was held on a long silica rod from a Pyrex spring attached to the removable Pyrex top-piece of the furnace. The spring was only included in the quantitative sulfating furnace; its sensitivity was 1.4 cm per g and it was found to be free from creep in a 16-hr test when carrying the working load. The extensions were followed by a cathetometer which could be read to 0.001 cm, corresponding to i0.7 mg. Extensions of the spring were measured on adding weights between 5 and 500 mg to the working load (thimble + oxide block), and Hooke's law was closely obeyed. SAMPLES Cuprous oxide blocks were prepared by oxidizing Johnson Matthey "Specpure" copper sheet of 1 mm thickness (impurities: iron at 3 ppm, silver at 2 ppm, lead, nickel, sodium, and silicon each at 1 ppm, calcium, chromium, magnesium, and manganese each at less than 1 ppm) for 6 days in air at 1000°C in a re-crystallized alumina boat. It has been reported7 that when Cu20 is prepared by heating copper sheet for 1 day the central plane of the blocks produced consists

Jan 1, 1967

By P. Beardmore, B. W. Howlett, B. D. Lichter, M. B. Bever

The heats of formation at 273°K of the compounds Mg2Ge, Mg2sn, and Mg2b, the heats of fusion and melting points of Mg2Sn and Mg2Pb, and the heats of solution of magnesium, germanium, and lead in liquid tin have been measured. The excess free energies of the liquid alloys and the free energies of formation of magnesium-Group IVB compounds at their melting points and their standard free energies of formation at 298°K have been calculated. The stability and bonding of the compounds are discussed with reference to these properties. Some thermodynatnic aspects of the liquid phases in the systems Mg-Sn and Mg-Pb are also considered. THE compounds of magnesium with the Group TVB elements, silicon, germanium, tin, and lead, have often been considered to constitute a nearly ideal homologous series. In particular, their thermodynamic stability has been assumed to decrease with increasing atomic number of the Group IVB element.' The binary-phase diagrams of the magnesium-Group IVB elements given by Hansen and Anderko2 have the same form. Each system has a single con-gruently melting compound of limited homogeneity range. The structures of these compounds, which have the formula Mg2X, are anti-isomorphous with the calcium fluoride structure. A recent investigation has found evidence of a second compound in the system Mg-Pb.3 The solid compounds Mg2Si, Mg2Ge, and Mg,Sn are semiconductors, while the conductivity of Mg2Pb approaches that of a metallic conductor. This difference suggests that other properties may also show a discontinuity. The investigation reported here is concerned with the thermodynamic properties of magnesium-IVB compounds and particularly their variations with the period of the Group IVB element. The heats of formation at 273°K of the compounds MgzGe, Mg2Sn, and Mg2Pb and the heats of fusion and melting points of Mg2Sn and Mg2Pb have been measured. The results, combined with published data, are interpreted in relation to the stability and the bonding characteristics of the compounds. Some thermodynamic aspects of the liquid phases in the systems Mg-Sn and Mg-Pb are also considered. In the course of the investigation the heats of solution of magnesium, germanium, and lead in liquid tin have been determined. 1) EXPERIMENTAL PROCEDURES 1.1) Samples. Samples of the compounds Mg2Ge, Mg2Sn, and Mg2Pb, supplied by Professor P. Aigrain, Compagnie Générale de Télégraphie Sans Fils, were used in measuring heats of formation, heats of fusion, and melting points. Samples of Mg2Sn and Mg2Pb, supplied by Dr. V. B. Kurfman, Dow Metal Products Co., samples of Mg2Sn, prepared at the Air Force Cambridge Research Laboratories, and samples of MgzPb, prepared in this laboratory, were used for additional measurements of the heats of fusion and the melting points. The samples were stored in evacuated Pyrex capsules or under nonreacting liquids. 1.2) Heats of Formation. The heats of formation at 273°Kof the compounds Mg2Ge, Mg2Sn, and Mg,Pb were measured by tin-solution calorimetry. In this method, samples of the compound and of a mixture of the constituent elements are added alternately from 0°C to a tin-rich bath. The difference between the heat effects, corrected for the change in composition of the bath, is the heat of formation of the compound. Details of the method have been given elsewhere. 4 The bath was maintained at 350°C for the dissolution of the compounds MgzSn and Mg2Pb. Since at this temperature the dissolution of Mg2Ge was too slow, a bath temperature of 400" or 450°C was used with this compound. At least three calorimetric runs, each of approximately six additions, were made with each compound. 1.3) Heats of Solution. The determination of the heats of solution of magnesium, germanium, and lead in tin was included in this investigation because they were not well-established at the time this work was started. To obtain the heat of solution, the difference

Jan 1, 1967

By James T. Curry

The steady growth of the Northwest portion of the United States over the past two decades, and the very rapid development of Northern California, Western Nevada, and Oregon in particular, led the Calaveras Cement Company people to Shasta County, California in 1957. The presence of a large deposit of high calcium carbonate limestone had been recognized for many years, but it required the momentum of an expanding economy to make these long known reserves valuable. This, plus the availability of a reliable supply of fuel in the form of natural gas, and the ready means of shipping the product to the consumer both by highway and railroad, seemed to offer the proper combination to launch a successful venture. The Calaveras Cement Company had been manufacturing cement by the wet process since 1925 at their plant at San Andreas, California. Starting with two small kilns, the plant in Calaveras County started an expansion program in 1945 that ultimately resulted in the plant as it exists today, consisting of five kilns with a combined production of 4.5 million barrels annually.

Jan 1, 1967

By Stanley A. Feitler

This Bureau of Mines report deals principally with the resources and economic aspects of feldspar in the United States east of the Mississippi River. Although in a strict sense, all phases of the feldspar industry affect its economic structure, emphasis in this study is on supply, demand, and marketing. Although feldspar was originally mined for use in the manufacture of pottery and other ceramics, the glass industry, which began to use feldspar in the mid-1920's, now consumes more than half of the annual output. Most mining is open cut, and the methods used are similar to those used in mining crushed stone. Excess plant capacity has been chronic, and production is usually about 50 percent of capacity fur the industry as a whole. Since 1947, feldspar consumption has grown more slowly than the average for all U.S. industry. This has fostered intense competition, especially for the glass market. Prices have not kept pace with inflation, and profits are small. The trend of consumption through 1.970 for glass feldspar is expected to be upward; less rapid growth in consumption of ceramic feldspar is anticipated.

Jan 1, 1967

By Edward A. Vitunac

The emerging importance of pneumatic conveying systems for bulk materials is becoming recognized by more persons responsible for materials management as consultants, at the corporate level and at the plant level. They have learned that the economic advantages of a pneumatic system are frequently decisive when compared to alternate methods. Included in these advantages are relative simplicity, ease of installation, flexibility, ease of maintenance, cleanliness, safety and ease of automation to the degree desired. In general, installed costs favor a pneumatic system when compared to competing mechanical systems if the transporting distances are long or to and from many points. In addition, supplemental use such as cooling, heating, or drying may supply the incremental value required to justify its selection. (1). The main disadvantages of a pneumatic system is the greater horsepower required per unit weight of material conveyed and material limits in abrasiveness and density. In addition, there is a tendency to increase material breakage at changes of direction and at any obstruction such as the imperfect butting of one, piece of pipe to another in the conveying line. Classification of the material at the discharge may also cause problems in dusting and segregation. Materials weighing less than 4 pounds per cubic foot tend to cause feeding and collecting problems although they can be conveyed easily. Material between 4 and 20 pounds per cubic foot can be handled with less problems but flow rate is hard to predict. The 20 to 60 pounds per cubic foot range offers best results; whereas, over 60 pounds per cubic foot, materials tend to drop out of the air stream and settle in the pipe line unless careful provisions are made to prevent it. (2).

Jan 1, 1967

"Many advances in glass technology and processing are being made and the possibilities for glass as a material in the future appear unlimited. Float glass, glass-ceramics, high-strength sheet and container glass, glass-reinforced plastics, glass for electronic equipment, aerospace glass, glass fibres, glass vehicles, glasses with selective-reflective coatings and glare-reducing glasses, to name a few, provide areas of significance at present and for the future. There appear to be great opportunities, in certain localities of Canada, to develop new sources of raw materials for an expanding Canadian glass industry.New developments in the structural clay products industry have centered around facing brick as a structural load-bearing material, prefabricated brick panels, large-sized units, isostatic pressing of sewer pipe and auto-matic settmg of brick. Fast-firing techniques, using prefired or calcined raw materials, and the development of high-strength products will result in the use of a wider range of raw materials in the whiteware and structural clay products industries.Porcelain enamel, a material used for many years in domestic appliances and for sanitary ware, now is used extensively in architecture, agriculture, water tanks, highway signs and reflectors, and in products where resistance to corrosion-plus-temperature is important. Exotic composites of ceramics and metals, and specialized ceramic coatings applied on metals by various techniques such as flame spray, plasma jet, or vapour and chemical deposition have proved useful in materials for aircraft power plants, rockets, missiles and nuclear applications."

Jan 1, 1967

By E. A. Zawadzki

The problem of pollution of water by mine drainage is at least as old as the mining industry itself. However, research on the formation, composition, treatment, and abatement of mine water is a relatively recent historical event. At Bituminous Coal Research, Inc., acid mine drainage control has been an important area of work since 1944, at which time BCR began sponsorship of research at West Virginia University. The work at West Virginia University involved a detailed study of the acid mine drainage problem and led to the identification of iron oxidizing bacteria as important factors in the formation of acid mine water. The results of this research were summarized in 1954 by Temple and Koehler (1) who concluded that "no practical solution for the problem" of controlling acid mine drainage is yet known.?

Jan 1, 1967

By A. W. H. Morris, G. H. Laurie, J. N. Pratt

Using- galvanic cells of the form Sn(liq)/Sn" (LiCl-KC1-SnCl,)/Sn-Ag (alloy), measurements have been made of relative thermodynamic properties of the a, C, E, and liquid phases of the Ag-Sn alloy system. Partial heats of solution of the components in the liquid alloys lzave also been observed by direct cal-orimetric measurement in an isoperibol calorimeter. The thermodynanzic quantities are disczlssed in relation to structural and other properties and the existence of anomalous minor fluctuations in the partial heats and entropies of solution in liquid alloys is tentatively suggested. In the course of a recent electro motive-force study of the thermodynamic properties of Sn-Ag-Pd liquids,' some measurements were also performed on the Ag-Sn binary system. Most previous thermodynamic studies of this system have been concerned with the liquid state. Measurements confined to the limiting heat of solution of silver in liquid tin have been made by many calorimetric workers2 while high-temperature calorimetric measurements of the heats of formation of the full range of liquid alloys are reported in the early work of Kawakami~ (1323°K) and more recently by Wittig and Gehrin~(1248°K). Electromotive-force studies on liquid alloys have been made by Yanko, Drake, and Hovorka' (606" to 686°K; 86 to 99.4 at. pct Sn) and by Frantik and Mc Donald' (900°K; 30 to 90 at. pct Sn). The only known measurements on the solid state are of heats of formation of the a, £, and c phases; these values were obtained using tin-solution calorimetry, at 723"K, by Kleppa,~ whose investigation also yielded heats of formation of liquid alloys containing more than 64 at. pct Sn. The present experiments on the Ag-Sn alloys include a re-examination of the liquid phase and, because of the dearth of free-energy data for the solid state, attempted measurements on the a, c, and E phases. The principal new feature of electromotive-force results obtained for the liquid phase was an indication of anomalous fluctuations in the partial heats and entropies of solution of tin at certain compositions. However, since the values for these thermodynamic quantities were determined from the temperature coefficients of cell potentials, which are commonly subject to considerable error, confirmation by calorimetric measurements was considered desirable. A detailed investigation of the partial heats of solution of the components in the binary liquids was made using a liquid metal solution calorimeter. I) GALVANIC CELL STUDIES a) Experimental Details. Measurements were made, as a function of alloy composition and temperature, of the potentials of reversible galvanic cells of the form: ~n(liq)/~n++/~n-Ag (solid or liquid alloy) Details of the apparatus and experimental techniques have been given elsewhere.' so that a brief account will suffice here. Molten salt, 58 mole pct LiC1-42 mole pct KC1, containing small amounts (1 to 2 mole pct) of stannous chloride was used as the electrolyte. The salts were dehydrated by pre-electrolysis and vacuum -drying techniques. Cells were established under an argon atmosphere by immersing tin and alloy electrodes in the molten salt contained in a large silica tube, heated in a vertical resistance furnace. The tube was sealed at the top by a head plate provided with openings permitting the simultaneous insertion of six electrodes, a central thermocouple sheath, and connections to vacuum and argon lines. Temperatures were controlled to *0.2"C over prolonged periods, with maximum variation over the electrodes at any time of 0.l°C. Temperatures were measured with a standardized Pt/13 pct Rh-Pt couple. The electromotive force of this and the cell potentials were measured on a Cambridge Vernier potentiometer and short-period galvanometer. Alloys were prepared from Pass "S" tin (99.999 pct) and Johnson-Matthey high-purity silver (99.999 pct) by melting in evacuated silica capsules and quenching in cold water. For liquid phase experiments, pieces of the resulting alloys were remelted into prepared silica electrode units, while solid electrodes were prepared by remelting into 3-mm bore tubing, inserting a cleaned molybdenum lead wire, and quenching to produce uniform rods about 3 cm in length, with soundly attached leads. In all cases remelting was done under an argon atmosphere. The solid electrodes were subsequently annealed in evacu ated silica tubes for 14 days at about 20°C below the solidus and quenched. Analyses showed that these techniques produced uniform electrodes with no significant change from weighed out compositions. b) Results and Discussion. Measurements were made on about forty alloys in the solid and liquid states, over varying ranges of temperature between 550" and 1050°K. Stable, mutually consistent, and reproducible electromotive-force data were obtained with most liquid alloys and these are shown in Fig. 1. Investigations were extended below the liquidus tem-

Jan 1, 1967

By R. S. Silo

A new process for leaching oxidized copper ore (CuO) is presented. Its principle advantage is that it requires low cost raw materials. For large operations the only materials used are sodium chloride (NaCl) and calcium carbonate (CaCO3). In those operations of medium size, sulfur, which is abundant in the North of Chile, is used. However the process may also be applied to small copper plants provided low cost sulfuric acid is available as a substitute for sulfur. That is, it may be applied to those small capacity plants where large additional installations for the regeneration of the leaching solution are not needed. The method is comprised of six stages, namely: Crushing, Leaching, Washing of the Solution, Precipitation, Regeneration of the Leaching Solution, and Fusion. A flow diagram for this process in a large or medium-sized plant is given. LEACHING This process requires hydrochloric acid as the leaching solution for treating copper ores. This is easily produced from sulfuric acid and sodium chloride as follows: A small excess of NaCl is advisable to avoid the presence of free sulfuric acid. The experiments reported here were performed with 36 grams of HC1 per liter of solution to obtain a free acidity equivalent to 50 gpl of H2SO4 (the usual leaching solution concentration). Hydrochloric acid leaching may be done by either of the usual methods; i.e. percolation or agitation. The method selected depends on the characteristics of the ore. No matter which method is chosen, low pressure air can be used either as an air lift for circulation of the solution, or for agitation of the pulp with "Pachuca" tanks. In either case, there are no problems with respect to oxidation. Leaching by agitation produces good recovery; but at times, the problem of high consumption of leaching solution or the overproduction of grinding slimes which interfere with contact between phases negates this advantage. The percolation method was used in this study. Percolation took place in four 15-liter containers, 11 1/2 in. diam. by 12 in. height, having hemispheric bottoms. Each container was fitted with a wooden bottom having 1/4 in- holes. The air lift was a 3/4 in. plastic tube 10 in. high. Air at 6 psi was supplied from a rotating laboratory compressor. 10 kg of ore were charged to the container and counter-current leaching was used. The leaching solutions were fed through the center pipe in order to use the ascending solutions to reject the air in the charge. The solution circulated through the air lift in order to facilitate the movement according to the increase in density produced by the reaction between the phases present. Specific observations made in this report cannot be generalized because the leaching characteristics are dependent on the nature of the ore used, the method of leaching, and the production of primary or secondary slimes while crushing or leaching.

Jan 1, 1967

By Howard N. Egan

The importance of coal as the major energy source has led to wider interest in the recovery of waste coal fines as a usable product. An additional incentive for fine coal recovery has been the increased emphasis on environ- mental pollution control and conservation of the nation's natural resources, Accordingly, a series of studies and tests were performed to investigate the feasibility of the recovery, concentration, balling and pelletizing of coal fines as a marketable adjunct to existing mining and beneficiation operations. These studies were conducted at the existing operations of the Eastern Coal Corporation at Stone, Kentucky, and the Metallurgical Laboratory of Arthur G. McKee & Company in Cleveland, Ohio. The purpose of the investigations was to recover the fines from the effluent waste waters of an existing preparation plant and transform them into a high carbon, low sulfur and ash product capable of being handled with a minimum of degradation and dusting problems. The fines were relatively high in ash content prior to processing, and flotation pretreatment served a combined function of beneficiation, recovery and water clarification, The minus 28 mesh coal concentrate containing 40 to 45 percent minus 325 mesh size material had an ash content varying between 5 and 7 percent and a sulfur content of less than 0.5 percent. Chemical and size analyses of the effluent and concentrated fines are presented in Table I for comparison.

Jan 1, 1967

By A. K. Snelgrove

At a time when water resource planning is proceeding on a continental scale, such as the proposed $100 billion North American Water and Power Alliance, which would redistribute water among three nations, including seven provinces of Canada, 35 of the United States, and three States of Mexico, the selection of a single river basin for study may seem to require an apologia. None is offered because of ( 1) the magnitude of the Indus , itself a part of the great Indo-Gangetic Plain drainage system, with Himalayan sources, upon which the thickly populated northern sub-continent of Indo-Pakistan depends for agriculture and hydroelectic power; (2) the extraordinary problems created by dismemberment of the world?s largest irrigation system through legal beheading of the Eastern Waters under the Indus Waters Treaty of 1960; and (3) the herculean effort to contain the twin encroachments of waterlogging and salinization in a basin which faces a shortage of fresh water. The British irrigation system of barrages and canals on the Indus was a venture admirable in conception. Unfortunately, it is now a legacy burdened with unwanted consequences, due to interference with the hydrological regimen, particularly the rise of water table occasioned by leakage.

Jan 1, 1967

By C. A. Komar

The Bureau of Mines conducted experiments on one synthetic and three natural sandstone samples to investigate the effects of acoustic energy on the flow of brine in porous media. Ultrasonic energy at a frequency of 20 kc per second and an intensity of 55 watts per cm2 was irradiated in the direction of the fluid flow and in the opposite direction for distances of 1/2 and 2 inches between the vibrating device and the sample face and under conditions of suppressed and nonsuppressed cavitation. Forty tests were conducted: 32 with a pressure differential of 0.64 psi across the samples, 2 with 5 psi, and 6 with 15 psi. Acoustic waves altered the rate of flow of the brine through the samples, but this effect was observed only at low differential pressures and from a practical point of view was insignificant. As a result of irradiation, however, the samples exhibited reduced permeability. This reduction was probably caused by the shifting of solid particles dislodged by the acoustic waves.

Jan 1, 1967

By J. B. Kitchin

"The design of conveyor belting for use in mines poses problems to the manufacturer that are unique. The challenge to be met is that of the production of a conveyor belt which can withstand use and misuse in an environment that may differ vastly from one country to another, and even between one mine and its neighbour.The development of a product to meet such varying requirements necessitates a protracted program of trials, both in the laboratory and in the field; a new successful development, the only criterion, can be said to have been achieved only after very long-term usage under actual, deliberately chosen, arduous mining conditions.New developments in conveyor belt construction can never stop, no more than can developments in new and advanced mining techniques. A new problem is set-an answer must be found. Some of the problems are noted here, and answered where possible, in what must after all be little more than an excursion into a very comprehensive and detailed subject."

Jan 1, 1967

By Arthur Miller

Most of the production of copper in the United States comes from a few large companies. Often overlooked, however, are the more numerous small mining operations, which collectively produce a significant portion of the nation's copper. The objective of this paper is to describe the operations of a small mining company - Ranchers Exploration and Development Corporation - how it views its place in this industry of giants, how it exploits the advantages offered by its relatively small size, and how it protects itself from the hazards being small introduces. Environment is, of course, a critical factor for such a company because it does not have the resources which help large companies weather periods of financial stress. Ideally, this environment is characterized by a heal thy economy, strong product demand, relatively stable prices , adequate grades and tonnages of ore commensurate with depth and over-burden, ready access to utilities, a dependable labor pool, and suitable technical "know how". When the environment is right, properties which were previously uneconomical to operate attract the attention of companies whose primary interest is a return on investment commensurate with risk over a reasonable period of time. Naturally, the amount of the investment and the duration of operation determines the size of the company which would be interested in such a venture. Such is the case with Ranchers Bluebird Mine at Miami, Arizona - a small property operated by a small company in a favorable economic environment.

Jan 1, 1967

By J. Larsen-Badse

The resistance to dry sliding abrasion us been measured for some hardened and tempered carbon steels. The wear resistance, defined as the reciprocal of the volume loss per unit sliding distance, is found to vary linearly with the hardness of the abraded surface. The data fit two lines, one, of high slope, for the pure metals and for the annealed steels and another, of smaller slope, for the hardened and tempered carbon steels. A relationship is developed showing the alwasion resistance to be proportional to the hardness of the material and to en, where n is the exponent of work hardening. The values of n and of the hardness FOR most materials a high resistance to abrasion is generally associated with a high value of indentation hardness. Brine11 even used the abrasion resistance as a measure of hardness in an attempt at expanding the hardness range covered by his indentation-hardness test.' When comparing different types of materials there is, however, only a very general relation between abrasion resistance and hardness. Sample brittleness seems to contribute to the deviation from a direct relationship. In general, increased brittle- are those relating to the heavily deformed abraded surface. However, for materials having n constant or varying m a regular manner over a wide range of strailts, the wear resistance will also be a linear function of the bulk hardness of the material. For tempered steels containing a dispersion of cementite in ferrite the increase in wear resistance due to the dispersion is found to be a linear function of the volume fraction of Fe3C and of the reciprocal of the mean free ferrite path. This indicates indirectly that the yielding of this material, when it is already heavily deformed, follows the Orowan criterion. ness leads to decreased abrasion resistance.' When comparing materials in the same group, e.g., the metals, the spread is less. Kruschov found that the abrasion resistance of pure metals and of annealed steels is directly proportional to the hardness of the metal. For hardened and tempered steels he obtained another linear relationship, one of smaller slope and intersecting the line for the pure metals at the location of the data for the annealed steels. He also found that the abrasion resistance of cold-worked metals is independent of the degree of cold working. This shows, as he concluded, that the process of abrasion work hardens the metal in the surface region to a very high degree.

Jan 1, 1967