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By Y. C. Kim, C. B. Manula

This paper is concerned with the details of the derivation of an operations research model, specifically linear programming, to solve production scheduling problems. While some results are presented for an actual study, the calculation of cases of a more general nature have not yet been completed. Production managers from those segments of the mining industry that experience a seasonal or highly variable sales demand find it rather difficult to develop overall producing plans for their organizations. In an attempt to solve this technical problem, demands are usually met by keeping production corresponding exactly to sales. This results in a fluctuating production schedule which is costly to maintain because of overtime premiums in periods of high requirements and because of costs associated with an idle mine plant during slack periods. An alternate solution may be to produce part of the desired amount and make up any deficiencies by using overproduction in previous time periods. This tends to smooth the production pattern through the use of a stockpile. However, because of associated storage costs, the solution may again be undesirable if it yields comparatively large surpluses. In general, this type of scheduling problem has an infinite number of solutions which satisfy the requirements. These are largely dependent on the extent to which an operation is geared to changes in production and on the size of its stockpiling facility. The determination of an efficient schedule is implied, therefore, as one lying between two extreme solutions, i.e., one that minimizes surpluses and one that minimizes output fluctuations. These conflicting objectives result in an economic balance problem between the costs of carrying surpluses forward from slack periods versus the cost of high production levels during peak demands. Various methods of operations research have been developed to handle problems whose genesis is explained above. It is very seldom, however, that these quantitative means are used in practice by the mining industry. Those who are familiar with mining operations know that most managers have not progressed satisfactorily in this area. Production planning systems which most mines employ today are often no more than rough records of management's mental planning. For small mines these means are normally sufficient; but as operations grow larger and become more complex, this type of planning ability is no longer adequate. Managers may find themselves losing control of cost relationships, taking longer to outline production sequences, and becoming forgetful of certain resource availabilities. ORIGIN AND SCOPE OF A SCHEDULING PROBLEM The more fundamental aspects of the production scheduling problem can be brought into focus by demonstrating how it exists in a bituminous coal mine* located in southwestern Pennsylvania. This mine, operating in the Pittsburgh seam, uses a definite room-and-pillar block system of mining, which is planned and carried out with only slight variations to meet local conditions. The coal seam, which is firm and varying in thickness from 8 to 9 ft with the bottom 6% ft being extracted, is under 500 ft of cover and opened by a shaft. The bulk of the coal (60%) is obtained from the pillaring activity with the mains and sections, which are considered primarily as development activities, contributing the balance of 12% and 28%, respectively. All coal is won by a ripper-type continuous miner in conjunction with shuttle-cars directly behind a loading machine. Track haulage is employed to move coal from these machine centers to the shaft bottom. The coal, thus mined, is shipped to one destination as part of a mixture of coals to be used in the making of steel. A material flow diagram of this distribution scheme is illustrated in Fig. 1. PROBLEM STATEMENT From the above types of shipments and mining limitations, the basic problem is to determine an economic means of producing and stockpiling a single coal product produced in three different machine centers (main, section, and pillar). Fig. 2 shows total demand for coal as a function of time. Because of the extremely high peak demands, slack period production must be stored and then distributed

Jan 1, 1969

EUGENE McAULIFFE, * St. Louis, Mo.-The method employed by the Engineer's Committee in arriving at a proper selling price for coal and coke represents hard painstaking effort based on a thoroughly scientific foundation; and the United States Fuel Administration can well point with pride to the work of this committee. The results so obtained placed

Jan 12, 1918

By R. J. Marcotte, C. T. Eddy, R. J. Smith

THE objectives of the investigation herein reported were to determine: (I) the S-curves for certain selected cast steels, (2) whether or not the published S-curves for wrought steels are satisfactory for use on cast steels of similar composition, and (3) to prepare hardenability curves of the selected cast steels. In order to make the final comparisons between cast and wrought steel more completely tangible, it was deemed advisable not only to determine S-curves for the steels submitted in the cast condition but also to roll some of the cast-steel test bars and determine comparison S-curves on such wrought material. This procedure eliminates the composition variable and makes it possible to reveal the differences resulting from plastic deformation of the cast structure in addition to providing the comparison with published data on wrought steels. CAST STEELS The cast steels selected for the preparation of S-curves, or time-temperature transformation curves, were similar to S.A.E. series 1030, 2330, 4130 and 4330. Of these the 1030 was supplied by The Crucible Steel Casting Co., Cleveland, Ohio, and the other three by The Sawbrook Steel Castings Co., Lockland, Ohio. The steels were furnished in the as-cast condition. The manufacturers supplied the chemical analyses and the properties that could be obtained in the heat-treated condition-all of which is summarized in Table I. [ ] PROCEDURE The metallographic and dilatometric procedures and equipment were in general standard. The specific technique employed was described in a report of the Steel

Jan 1, 1945

By George Sachs

THE process of recrystallization has not as yet been explained satis-factorily. Some definite conclusions could be drawn from recent investi-gations, such as, for example, that recrystallization is a process of nucleus formation and crystal growth 1and that the orientations of the nuclei correspond to some fragments of the original crystals, which have been considerably distorted during deformation.2 There are, however, a number of metals and alloys crystallizing in the face-centered cubic system, which form a particularly simple orientation if recrystallized as a sheet.3 Such a sheet is almost a single crystal with the cubic axes parallel to the rolling, transverse, and normal directions of the sheet. This preferred cubic or (100) orientation of the recrystallized sheet has been considered to be very different from the rolling structure of the same metals,4 but there are two reasons why this last supposition remains open to controversial discussion. The first reason is academic: In practically all cases except the one mentioned above, close correlations and similarities between rolling and annealing orientations have been observed; for instance, in iron and steel sheet.6 Secondly, no deformed metal actually forms a-simple orientation. In any thoroughly investigated case a number of different orientations and considerable scattering or deviations from the ideal orientations have been found., It is generally true that investigations on single crystals have shown that a definite orientation is approached in stretching or in compression of an originally undisturbed crystal.7 In the special cases, however, where the initial orientation was close to an important crystallographic direction that differed from the final "ideal" orientation, the resulting orientation changed very little by deformation, staying somewhere in the vicinity of the initial orientation." Such deviations

Jan 1, 1940

By Barry H. G. Brady

A state of stable equilibrium is required in a mine structure to ensure that small increases in the mined void are accompanied by only small displacements of the rock mass. Methods of determining the stability of equilibrium in a rock mass currently require a geometrically regular stoping layout, and introduce a number of simplifying assumptions. The method reported in this paper models the mine near-field using Finite Elements, and the far-field using Boundary Elements. The stability of equilibrium in the modelled structure can be assessed directly from the value of selected principal minors of the global stiffness matrix.

Jan 1, 1981

By M. H. Gidel, D. C. Bard

These notes are based on the megascopic study of a suite of 2,400 specimens of minerals and ores from the Butte mines, combined with field observations at intervals over a period of several years. The estimate of average vein composition is based on field acquaintance with the veins. It is probably correct in its broader proportions, and should be of use for comparison. Chemical and Mineral Composition of Unoxidized Vein Matter. Per Cent. Oxygen,......48.00—Quartz, rhodonite, rhodochrosite, sericite, kaolinite, barite, calcite, and hübnerite. Silicon,...... 36.O0—Quartz, rhodonite, sericite, kaolinite, and willemite (very rare). Sulphur,.....5.0—Sulphides of iron, zinc, copper, lead, and sulphates of barium and rarely calcium. Iron,.......5.00—Ferric sulphides (pyrite, bornite, chalcopyrite), also in sphalerite, tetrahedrite, and rarely hematite and siderite. Manganese,.... 2.00—Rhodonite, rhodochrosite, and hübnerite. Zinc,.......1.00—Sphalerite, very rare wurtzite and willemite, and tetrahedrite and tennantite. Carbon,......0.50—Rhodochrosite and calcite. Capper,......0.75—Cuprous ( + ) and cupric (—) sulphides. Aluminum,.... 0.50—Sericite and kaolinite. Hydrogen,.... 0.50—Water, sericite, and kaolinite. Potassium,.....0.20—hicite. Lead,....... 0.20—Galena. Arsenic,......0.10—Tennantite and enargite. Barium,......0.10—Barite. Calcium,.....0.10—Fluorite, calcite, and rare gypsum. Antimony,.... 0.02—Tetrahedrite, famatinite, and silver sulphantimonites. Fluorine,.....0.05—Fluorite. Silver,.....1 —Argentite, and sulphantimonites. Tungsten,.... —Hübnerite. Phosphorus, • —Wavellite. Bismuth,' .... 0.05—Sulphide (?) Tellurium,... 1 —Telluride (?) Selenium,.... —Selenide (?) Cadmium,.... —Sulphide (?) Gold,..... —Native and telluride (?)

Jan 1, 1914

By R. P. Alger, C. A. Doh, M. P. Tixier

The principle, the equipment and field operation of sonic logging are described. The tfio-receiver system produces logs independent of hole size and mud. Field experience is given and forms the basis for the interpretation of the log. The derivaiion of porosity values from measured velocities is discussed, according to the type of formations (hard formations, compacted sands, and unconsolidated formations). The time-average equation proposed by M. R. J. Wyllie, A. R. Gregory and L. W. Gardner is uscd as a basis for the computation of porosity in limestones, cemented sandstones and compacted sands. Variations in the lithologic character of limestones do not seem to change the porosity calibration markedly. The compaction of sands is related to the compaction of shale adjacent to them; and, thus, the shale velocity is used for the establishtnent of empirical relations for the computation of porosity in un-consolidated formations. Various forrnu.las are tentatively presented to account for shale and fluid content. Field experience demonstrates that considerable attenuation of sonic energy takes place in unconsolidated formations, particularly when gas bearing, and in fractrured formations. Unusually large attenuation produces skipped cycles, a feature easily recognized. The application of sonic logging to structura1 studies is featured, showing its possible integration with the dipmeter. Correlation and its application to the irrterpretation of seisrmic surveys are reviewed. The paper is illustrated with field examples. Sonic logging is the recording of the time required for a sound wave to traverse a definite length of formation. Sonic travel-times are inversely proportional to the speed of sound in the various formations. The speed of sound in subsurface formations depends upon the elastic properties of the rock matrix, the porosity of the formations and their fluid content and pressure. Below the "weathered" or low-velocity layer extending from 50 to 100 ft or so below the surface, sound velocities may range from about 6,000 ft/sec in shallow shales to as much as 34,000 ft/sec in dolomites. In hard formations (well cemented and/or compacted), the sonic log reflects the amount of fluid in the formations; hence, it correlates well with their porosity. In unconsolidated formations, which are usually of fairly high porosity, the sonic log gives an approach to porosity determination, when its readings are corrected for lack of compaction, shaliness, and fluid content. In such formations the sonic log may also indicate the presence of gas and may distinguish between oil- and water-bearing beds. Field experience with the sonic log in soft formations is more limited than that in hard formations. As a result, interpretation in soft formations is not as well developed at the present time. In all types of formations the sonic log is of considerable value for correlation and for the more detailed and accurate interpretation of seismic data. EQUIPMENT AND PRINCIPLE FIELD OPERATION The basic features of the sonic log" are a two-receiver system and two available short spacings. The log is recorded on film using a standard field unit. An SP curve is run along with the sonic curve to give a more interpretable log and to establish absclute depth control for comparison with other logs run in the same well. If desired, a gamma-ray curve may be recorded simultaneously with the sonic curve. Fig. 1 shows the sonic-gamma ray combination sonde. The sonic portion consists of a sound transmitter and three receivers mounted 3, 4 and 6 ft from the transmitter. When the first and second receivers are used, a sonic log of I -ft spacing (distance between receivers) is obtainea. Use of the first and third receivers provides a 3-ft spacing. The transmitter emits pulses at the rate of l0/sec. After the transmission of a pulse the first arrival of sound energy at each receiver triggers its response system. The differ-

By Robert D. Pehlke, Robert G. Blossey

The solubility of nitrogen in liquid cobalt and a number of dilute cobalt alloys Was measured in the temperature range 1550" to 1700°C at nitrogen pressures to 1 atm. At 1600°C and 1 atm nitrogen pressure, the solubility in pure cobalt is 0.0047 wt pct [3.8 cu cm (stp) per 100 g Co]. The standard free- energy change for the solution reaction 1/2 N,(g) = gout pct in Co) is iF - 10,000 + 5.24 T cal per g atom N. The alloying elements Cv, Cu, Mo, Nb, Tu, W, and V increase the nitrogen solubility, while Al, Fe, Ni, and Si decrease the nitrogen solubility. THE solubility of nitrogen in cobalt was studied previously by Sieverts, Busch and Dodd,2 and Schenck, Frohberg, and Graf.3 Sieverts investigated the solution below the melting point of cobalt, and Busch and Dodd worked with the liquid metal; however, neither study found any solubility for nitrogen in cobalt. Schenck et al, reported a solubility of 0.005 wt pct N in cobalt at 1600°C. Seagle et al. 4 reported residual nitrogen in cobalt after electron-beam melting, although no reasons were ventured for the presence of this interstitial impurity. This investigation was undertaken to clarify these inconsistencies, and to provide additional data on atomic interactions in dilute metallic solution. EXPERIMENTAL PROCEDURE This study was well-suited to the Sieverts' method, which has not changed significantly since its introduction by Sieverts. 5 The apparatus was of the same design as that described by Humbert and Elliott, 6 with a reaction bulb similar to that reported by Weinstein and Elliott. 7 The buret was not water-jacketed, but the measured gas volumes were corrected for small changes in room temperature. The melt temperature was measured by a disappear ing-filament optical pyrometer sighted through a prism onto the melt surface. Temperature calibration was made based on a measurement of the melting point of pure cobalt taken as 1495°C. The difference between the reciprocal of the observed and the true temperatures was assumed to be a constant, neglecting the changes in emissivity with small additions of alloying elements. The total error in gas-volume measurement caused by accuracy limitations in reading the mercury level in the buret, variation in ambient temperature, and variation in melt temperature was about 0.5 cu cm. This represents approximately 10 pct of the total solubility, and is a larger relative error than in previous studies6-' because of the small nitrogen solubilities encountered in the present investigation. The source and purity of the materials used are listed in Table IA. Recrystallized alumina crucibles were used throughout the investigation. Examination of the crucibles after solidification of the melts showed no reaction or penetration. Alloying of the cobalt melt was accomplished with the dropping technique described by Humbert. 6 The investigation was started using cobalt from African Metals Corp. in shot form, but this material was not of sufficient purity and did not yield consistent solubility results. Sherritt Gordon Mines Ltd. cobalt was then used throughout the investigation. In experiments involving alloying elements which could react with oxygen dissolved in the melt, the cobalt was further refined by annealing at 1400°C in a dry-hydrogen atmosphere. This treatment, described by Woolley and Pehlke, 8 markedly reduced the oxygen content. The oxygen and nitrogen analyses of the cobalt used in this study are presented in Table IB. RESULTS Hot Volume. The hot volume was measured prior to each run and was 50 to 55 cu cm (stp) at 1600°C. It increased linearly with increasing pressure and decreasing melt temperature. Pure Cobalt. Measurements of the solubility of nitrogen in pure cobalt and the temperature coefficient of solubility are summarized in Table 11. At 1600°C and 1 atm nitrogen pressure, the solubility was found

Jan 1, 1967

By A. E. Powers, J. F. Libsch

THE simultaneous influence of time and temperature upon the tempering process in steel is well known. Hollomon and Jaffe¹ have expressed the effect of time and temperature upon the progress of tempering by a single parameter, T (c + log t); where T is the absolute temperature; t, the tempering time; and c, a constant characteristic of the steel and treatment. It was found that when hardness data for plain carbon and low alloy steels were plotted vs. this parameter, a master tempering curve was obtained which satisfied all the data for a given steel and a given hardening treatment. Roberts, Grobe, and Moersch² successfully applied the tempering parameter to various tool steels, including high speed steel for tempering times ranging from 6 min to 100 hr. The influence of tempering time and temperature upon the physical properties of high speed steel has also been extensively investigated.'" Recently, the use of induction heating for very rapid tempering treatments has received attention. The authors% have shown that tempering treatments of only a few seconds duration may be successfully applied to plain carbon and low alloy steel. However, the influence of such short tempering treatments in high speed steel has not been explored. Since high speed steel is a highly alloyed steel exhibiting physical reactions during tempering that are often relatively slow and large in magnitude, it is an interesting steel for the study of tempering reactions. It was the purpose of the present investigation, therefore, to study the early progress of reactions leading to secondary hardness in high speed steel, type 6-5-4-2, and to determine if induction-tempering treatments of a few seconds duration are able to produce results equal to those of more conventional long-time tempering cycles. Experimental Details The chemical compositions for two different heats of W-Mo high speed steel used in this study are given in Table I. Table II summarizes the heat treatment given various groups of specimens cut 21/2 in. long and centerless ground to ¼ in. diam. Hardening treatments consisted of preheating to 1600°F (870°C) for V2 hr and then oil quenching from 2250°F (1230°C). Heat I was subjected to the high temperature in a salt bath for 3 min, while specimens of heat II were austenitized in a carbon-block muffle furnace for 10 min. Specimens of series E were immediately refrigerated to — 318°F (— 195°C) in liquid nitrogen following the hardening treatment to transform the major portion of the retained aus-tenite. Specimens of series F and G were subzero cooled to — 100°F (-75°C) in a dry ice-alcohol mixture. Induction tempering was performed with a Lepel high frequency converter operating at a frequency of approximately 300,000 cycles per sec. Heating cycles were controlled and recorded for each specimen using a chromel-alumel thermocouple, percussion welded to the surface of the specimen, and a modified high speed instrument with a timer previously used and described.' Temperature oscillation of the specimens, while being held at the tempering temperature, was ± 15°F (8°C). Tempering Treatments: After hardening, specimens were tempered between 900" and 1500°F (480" and 815°C) to study the progress of retained austenite decomposition and secondary hardening. The specimens tempered in salt for 1 hr (series C, G, and I) were considered to represent conventional treatment and are used for comparison with rapid tempering treatments. Several induction-tempering cycles were employed: 1—flash tempering, i.e., induction heating to the tempering temperature and immediately cooling (series A, E, and F); 2—induction heating for 60 sec at temperature (series B); and 3—double-induction tempering by two successive heating and cooling cycles (series D). All specimens tempered by induction were heated at an initial rate of 450°F (250°C) per sec except those of series E, which were heated at an initial rate of 1300 °F

Jan 1, 1952

By Alton B. Cook, G. B. Spencer, F. P. Bobrowski

In estimating production gas/oil ratios and oil recoveries from reservoirs containing highly volatile oils it is highly important to include condensate that may be recovered from the gas produced from the reservoir. The volume of the hydrocarbon liquid condensed from the production of the solution gas that has been liberated. in some reservoirs may equal or even exceed the volume of recoverable stock-tank oil as estimated by present methods. The usual procedure1, 2, 3 in estimating future reservoir performance includes use of relative permeability data of the reservoir rock to gas and oil and includes material-balance calculations utilizing data on the volume of the reservoir fluids, oil and gas production and reservoir pressure decline, and data on the physical properties of the initial reservoir fluids. The inaccuracy in the procedure results from the false assumption that all of the free or liberated gas that enters the well bore of reservoirs containing highly volatile oils remains in the gaseous phase as it is produced. This paper presents a method for estimating future reservoir performance and oil recoveries based on special labora. tory analyses of reservoir-oil samples and recognition of the additional volume of hydrocarbon liquid that will be recovered at various stages of depletion from a solution.gas.drive reservoir. The method also includes calculations of the volume and composition of the hydrocarbon liquids that can be recovered by processing the produced gas in a natural-gasoline plant. The development of the method resulted from a study of laboratory analyses of reservoir samples and of field data obtained from two reservoirs containing oil of the highly velatile type. Relatively high pressures and temperatures prevail in oil reservoirs discovered at the greater depths of present-day drilling. The contained fluids may have high saturation -Dressures and large volumes of gas in solution. The oils and gases under these conditions may be almost identical in compositions and densities.4,5 Also, engineers have noted that, for a number of oil reservoirs and especially the deeper reservoirs, the API gravity of the stock-tank oil increaees as the production gas/oil ratios increase. They attributed this increase in API gravity of the stock-tank oil to the formation of condensate as the liberated gas in the reservoir is being produced. SOURCE OF DATA FOR CALCULATIONS Subsurface oil samples and well-test data were obtained from the E. Constantin-Lambert Well No. 1 in the Elk City Field, Okla., to demonstrate the need for and a method of calculating future reservoir performance when consideration is given to the recoverable hydrocarbon liquid from the production of solution gas that has been or will be liberated in a reservoir. The Lambert well is located in C, SW 1/4, SW 1/4, Set- 18, T-l0-N, R-20-W, Washita County, Okla. At the time of completion it was on the east edge of the development and Was producing from conglomerate through 30 perforations in the 5 1/2-in. casing at a depth of 9,859 to 9,864 ft. The well Was completed on July 9, 1949, and subsurface oil samples were obtained July 29 and August 1, 1949. Production gas/oil ratio data were obtained during the operation in series of two Separators at high and low-pressures of 314 and 44 psia, respectively, and at an average temperature of approximately 60°F. The flowing bottom-hole pressure at the time of sampling was 3,934 psis. The static bottom-hole pressure was not obtained at the time of sampling, as the well could not be shut in long enough for testing because gas produced from the well was used for fuel at an offset drilling well. However, the initial reservoir pressure was calculated to be 4,364 psia from knowledge of pressure gradients in other wells in the field and the depth of the casing perforations in the Lambert NO. 1 well.

Jan 1, 1951

By F. P. Bobrowski, G. B. Spencer, Alton B. Cook

In estimating production gas/oil ratios and oil recoveries from reservoirs containing highly volatile oils it is highly important to include condensate that may be recovered from the gas produced from the reservoir. The volume of the hydrocarbon liquid condensed from the production of the solution gas that has been liberated. in some reservoirs may equal or even exceed the volume of recoverable stock-tank oil as estimated by present methods. The usual procedure1, 2, 3 in estimating future reservoir performance includes use of relative permeability data of the reservoir rock to gas and oil and includes material-balance calculations utilizing data on the volume of the reservoir fluids, oil and gas production and reservoir pressure decline, and data on the physical properties of the initial reservoir fluids. The inaccuracy in the procedure results from the false assumption that all of the free or liberated gas that enters the well bore of reservoirs containing highly volatile oils remains in the gaseous phase as it is produced. This paper presents a method for estimating future reservoir performance and oil recoveries based on special labora. tory analyses of reservoir-oil samples and recognition of the additional volume of hydrocarbon liquid that will be recovered at various stages of depletion from a solution.gas.drive reservoir. The method also includes calculations of the volume and composition of the hydrocarbon liquids that can be recovered by processing the produced gas in a natural-gasoline plant. The development of the method resulted from a study of laboratory analyses of reservoir samples and of field data obtained from two reservoirs containing oil of the highly velatile type. Relatively high pressures and temperatures prevail in oil reservoirs discovered at the greater depths of present-day drilling. The contained fluids may have high saturation -Dressures and large volumes of gas in solution. The oils and gases under these conditions may be almost identical in compositions and densities.4,5 Also, engineers have noted that, for a number of oil reservoirs and especially the deeper reservoirs, the API gravity of the stock-tank oil increaees as the production gas/oil ratios increase. They attributed this increase in API gravity of the stock-tank oil to the formation of condensate as the liberated gas in the reservoir is being produced. SOURCE OF DATA FOR CALCULATIONS Subsurface oil samples and well-test data were obtained from the E. Constantin-Lambert Well No. 1 in the Elk City Field, Okla., to demonstrate the need for and a method of calculating future reservoir performance when consideration is given to the recoverable hydrocarbon liquid from the production of solution gas that has been or will be liberated in a reservoir. The Lambert well is located in C, SW 1/4, SW 1/4, Set- 18, T-l0-N, R-20-W, Washita County, Okla. At the time of completion it was on the east edge of the development and Was producing from conglomerate through 30 perforations in the 5 1/2-in. casing at a depth of 9,859 to 9,864 ft. The well Was completed on July 9, 1949, and subsurface oil samples were obtained July 29 and August 1, 1949. Production gas/oil ratio data were obtained during the operation in series of two Separators at high and low-pressures of 314 and 44 psia, respectively, and at an average temperature of approximately 60°F. The flowing bottom-hole pressure at the time of sampling was 3,934 psis. The static bottom-hole pressure was not obtained at the time of sampling, as the well could not be shut in long enough for testing because gas produced from the well was used for fuel at an offset drilling well. However, the initial reservoir pressure was calculated to be 4,364 psia from knowledge of pressure gradients in other wells in the field and the depth of the casing perforations in the Lambert NO. 1 well.

Jan 1, 1951

By Donald L. Johnson

REVIEWS on the applications of optical ellipsometry to the study of polycrystalline metal surfaces and oxidation-corrosion processes have been presented by Kruger and Hayfield, and white.' In view of the ability of this method to measure differences in film thicknesses to below 10A, ellipsometry was used to study nitrogen chromium surface reactions during the early stages of growth. Chromium specimens in the form of a vapor-deposited film on glass substrate were exposed to purified nitrogen for selected time increments at 700°F. This temperature was selected because it gave the best combination of exposure time and thickness change. Ellipsometer readings were taken immediately after exposure to determine polarizer and analyzer angles using monochromatic light at 5000A.2 After each set of readings was obtained, the specimens were exposed for an additional increment of time in nitrogen and a new set of readings taken. Film thickness was computed from LUCy's3 equation for nonabsorbing thin films. In Lucy's derivation, two equations for computing thickness were obtained. Peterson and Bashara4 have discussed the validity for using one of these equations when an independent value of the refractive index is used. The film was assumed to be Cr2N (Ref. 5) and was determined to be optically isotropic. Optical isotropy was determined by rotating the films about the surface normal and noting that the azimuth and phase difference did not change. Since Cr2N is reported to be hexagonal, it is assumed that optical isotropy results from randomly oriented grains of very small size. The thickness was computed using refractive indexes varying from 1.6 to 2.0. The maximum variation in computed thickness over this range for a given exposure was 20 pct. The data reported are based on a refractive index of 1.8. Reference readings on the metal surface were taken just prior to nitrogen exposure. No attempt was made to deoxidize or denitride the metal surface after vapor deposition, although specimens were observed to gain approximately 2A per day in air at room temperature. Twelve experimental exposures were made on a single sample over a total accumulative time of 132 min. Additional experiments over longer time intervals were made to determine the effect of heat up and cool down during and after exposure. As a result of these experiments, the thickness computed for each exposure was increased by 4A. Time profiles based on the linear law are similar to the oxidation profiles for many metals.' The rate of accumulation of the nitride film is rapid at first and slows down as the film thickness increases. The parabolic law x2 =k1t +k2 [11 gives a straight line in Fig. 1; therefore, it is concluded that the kinetic behavior is parabolic. Sey-bolt and Haman5 reported similar results for CrlN on chromium at 1000°C although the order of the thickness was much greater (10-3 cm). Analysis of thickness data based on other values of refractive index shows that the curves are shifted vertically but retain the same shape. According to Mott,7 it is expected that for thin films k2 is zero in Eq. [I]. Since the plot in Fig. 1 is linear through the origin, k2 is zero and the parabolic nature of the film growth is further indicated. The parabolic rate constant, calculated from the slope in Fig. 1, is 4.4 x 10-16 sq cm per sec. The corresponding work (+) required to bring an electron from the metal into the oxide is estimated to be 1.5 ev.7 The author thanks professor N. M. Bashara and D. W. Peterson, Electrical Materials Laboratory, University of Nebraska, for making the ellipsometer available and providing technical assistance. The Electrical Materials Laboratory is supported by the office of Naval Research, NONR 3718 (01). This work was partially supported by the Engineering Experiment Station and the Mechanical Engineering Department, University of Nebraska.

Jan 1, 1967

By Ronald J. McGregor, Anton R. Hendriksz

INTRODUCTION The NIMCIX contactor was developed in the late sixties at the National Institute for Metallurgy in South Africa, for the main purpose of extracting uraniuy from relatively low-grade uranium solutions. ' The concept was sufficiently developed by 1974 to permit the operation of a 1500 litre per minute column to treat unclarified urgnium-bearing solution under industrial conditions. The plant operated so successfully that several large-scale units have subsequent18 teen constructed and are operating efficiently. ' Total resin consumption figures as210w as 3 per cent per annum have been reported, and the extraction efficiencies of the installations have been exceptionally good. All the solutions treated have been acidic in nature and in every case have been of such a nature as to significantly depress the maximum uranium loading on the resin beads. The chemical constituents of the leach solution fed to the loading column determines the ease with which the soluble uranium can be absorbed by an ion exchange resin. The concentration of competing ions and various resin foulants define the nature of the continuous ion exchange equipment required for efficient extraction performance. The basic NIMCIX concept is retained in these various alternate designs, but batch or continuous elution methods with fully automated or manual control systems may be selected for the different process solution conditions. BRIEF DESCRIPTION OF THE NIMCIX CONTACTOR The NIMCIX ion exchange column is a multi-stage fluidized bed contactor which is designed to permit a counter-current flow of solution and resin in order to maximize extraction efficiency. The flow o resin is periodic, based on the Cloete and Streat 5 principle of reverse flow. The basic operating cycle can be divided into five periods, as illustrated in Figure 1. For the purposes of describing the cycle, the loading column is considered; how- ever, a similar sequence may be applied to the operation of a NIMCIX continuous elution column. S'I'EP 1: During the forward flow period, Solution flows up through the column and fluidizes the resin contained in each stage. The uranium depleted solution overflows the upper flared-section of the column as the tail solution. Step 2: The flow of solution to the column is temporarily stopped and the resin is allowed to Settle onto the plates in the column. STEP 3: During the reverse flow period, a fixed volume of solution is drained from the column to the transfer vessel. This flow causes resin transfer to occur from stage to stage and also out of the bottom stage. At the end of this period, which expires when the low level switch (LS) is actuated, some of the resin is left in the conical section of the column and the pipe interconnecting the column and the vessel. STEP 4: The cone flush period ensures that all the resin left in the cone of the column and the pipe is transferred to the transfer vessel before forward flow commences. STEP 5: The loaded resin in the transfer vessel, which has been isolated from the column, can either be hydraulically transferred to the top of the elution column or eluted in the vessel before being transferred to the top of the loading column. The major advantages associated with the NIMCIX concept are: (i) Simple method of operation (ii) Contactor can readily be scaled up to large diameters. (iii) Because the resin does not pass through pumps or airlifts, and valves cannot be closed on resin beads at any time, the resin losses are exceptionally low. (iv) Operating costs are low. (v) Relatively few valves in the system. (vi) Stable operation is achieved over a wide range of feed rates and concentrations.

Jan 1, 1980

By Garth M. Crosby

Hugh E. McKinstry (Professor of Geology, Laboratory of Mining Geology, Harvard University, Cambridge, Mass.) Pre-Cambrian age for the Coeur d'Alene mineralization, as indicated by isotope studies and recently discussed by Silverman, Long, and Kulp' would explain some features of the mineralogy of the district that have long been a puzzle. In the Silver Belt, especially in the Sunshine mine, lead-zinc min erali zation passes downward into tetrahedrite ore. Although commercially speaking this is a rich silver zone, the silver is, quantitatively, a mere impurity amounting to a small fraction of 1 pct. In effect the zonal change is from lead-zinc down into copper mineralization—-the usual zonal change that occurs in many districts. In the Burke-Mullan portion of the district, on the other hand, lead-zinc ore does not pass downward into copper mineralization of the Sunshine type. Instead, pyrrhotite appears in depth while the tenor in lead and zinc declines. The change occurs at increasingly greater depth away from the Gem stocks, deepening irregularly by some 3000 ft within two to four miles. As noted by Crosby, biotite, grunerite, and garnet appear in the deep zone. The marked difference between this apparent zonal change and the more nomal change to a copper zone is quite explainable if already existing pre-Cambrian veins have been locally metamorphosed by a Tertiary intrusive. The chief obstacle to this explanation is the evidence that mineralization cuts Laramide intrusives, but evidence on this point is conflicting as indicated by Crosby's observations and summary. This is not the first instance of a problem in determining the time-relationship of mineralization to a spatially associated intrusive. At the Noranda mine veins of chalcopyrite extend into a diabase dike which apparently cuts the ore, although Price2 concludes that the ore is later. However, at the Normetal mine diabase of a similar dike is thought3 to intrude the orebody but is cut by stringers of chalcopyrite. In the Sullivan Mine, B. C.,4 galena follows a fracture in a larnprophyre dike which, itself, cuts the main orebody. In the Sudbury district dikes of olivine diabase are clearly younger than the nickel ore, yet where they cut the Creighton orebody they contain stringers of chalcopyrite. In the laboratory, Hawley5 has developed veinlets of sulfide (chalcopyrite) it] silicate gangue by heating specimens of ore in a stream of H2S at 410 °C. From this and other evidernce. it seems clear that sulfides can be transferred from one site to another — at least through short distances — at temperatures well below their melting points. It would seem then that even if sulfide Mineralization in the Gem stocks can be shown unequ ivocably to be later than the intrusive the possibility of "remobiliza tion" need not be more than local. Thus the zonal relationships are quite in accord with a pre-Cambrian age for original deposition of the lead, zinc, copper, silver, and uranium in the Coeur d'Alene district. REFERENCES 1. A. Silverman, A. Long, and J. L. Kulp: Discussion of: The Gem Stocks and Adjacent Orebodies, Coeur d'Alene District, Idaho. Mining Engineering, May 1960, pp. 470-471; AME Trans., 1960, vol. 217, p. 117. 2. Peter Price: Geol. & O. D. at the Home Mine, Noranda, Quebec. Can. Inst. M & M Bull 263, 1934, p. 108; also,Trans. CIMM 1939, pp. 108-140. 3. w. L. Brown Nometal Mine in structural Geology of Canadian Ore Deposits, Montreal, 1948, p. 690. 4. C. O. Swanson and H. C. Gunning: Geology of the Sullivan Mine. Can. Inst. Mining & Met. Trans. vol. 48, 1945, p. 653. 5. J. E. Hawley: Heat Effects on Sulphides and Possible Applications. Univ. Toronto Studies, Geol. Ser. No. 46, 1941, p. 34.

Jan 1, 1961

By C. S. Smith, Chih-Chung Wang

TURNBULL and his collaborators1,2 have developed the theory of homogeneous nucleation as applied, inter alia, to solidification of liquid metals. Vonnegut³ and Turnbull4 have shown that if a liquid metal is subdivided into small droplets a vast majority of them will undercool very considerably before solidification, generally to as low as about 0.8 of the freezing temperature on the absolute scale. The nuclei effective at small degrees of supercooling in bulk metal seem to be internal or surface heterogeneities, relatively small in number. If the metal is subdivided, those droplets that happen to contain such nuclei will solidify at a temperature not greatly below the true freezing point, but only a small part of the whole volume will be affected and the majority of the drops will under-cool to the much lower temperature at which homo- geneous nucleation occurs as a result of fluctuations. It occurred to one of the authors that an appropriate subdivision to give effective freedom from random nuclei is produced during the solidification of many alloys that contain a minor amount of a phase of low melting point, and that one might then expect marked undercooling of the distributed phase. Experimental: The alloys selected for initial study were copper with minor amounts of lead and bismuth, and aluminum with tin. In all these alloys, the major component freezes at a temperature not much below that of the pure metal, and there is little further change in constitution on cooling until the lower melting point constituent freezes in an almost pure state. Cooling curves were taken using the controlled heat flow method permitting approximate specific heats to be obtained. Chromel-alumel thermocouples were used, with the standard emf tables, since extreme precision was not needed. The crucible (3/4 in. id, 5/16 in. wall) was made of B & W K-20 insulating brick. It held about 10 cc of the alloy being investigated. The cooling rate was 2.5" to 2.9°C per min under a controlled temperature difference of 20°. Approximate specific heats were computed from the inverse rate curves together with data from a blank run and from a standard run with a copper cylinder of known heat capacity. The alloys for investigation were made from high-purity metals (99.99+pct) and cast into graphite molds. The castings were machined to fit the crucible and to provide a hole for the inner thermocouple. Cooling curves were taken after heating to a temperature about 50" above the melting point of the minor, lower melting-point, constituent. Results The lead phase in an alloy of copper with 5 pct lead did not undercool more than 3" below the melting point of lead (327°C) either as cast or after annealing to produce a new dispersion of the liquid phase. A copper-zinc-lead alloy with 23.75 pct zinc and 5 pct lead undercooled more but showed no thermal effect below 319°C. A cast alloy of copper with 5 pct bismuth undercooled to 249°C (M.P. bismuth 27l °C), but once solidification started it was completed at the same temperature. This was anticipated, since the bismuth forms a nearly continuous phase between the grains of copper, and a solid crystal nucleated anywhere would rapidly* con- sume the entire network of liquid, unless the physical continuity of the liquid were broken through volume changes, inadequate fluidity, or gas evolution. Similar arguments apply in the case of copper-lead alloys, where the lead-rich liquid forms a network along grain edges, though not grain faces. In both cases there would be a few isolated particles

Jan 1, 1951

By R. P. McLaughlin

IN most branches of the mining industry it is a well-recognized fact that care must be taken to protect the mineral deposit from undue physical injury. It is comparatively easy to grasp this idea when the mineral is a solid and the lives of workmen depend directly upon the care with which it is removed from its natural position, but when the product is a liquid. drawn up from pools several thousand feet beneath the surface of the ground through openings only a few inches in diameter, it requires some imagination to picture underground conditions and the changes which must often occur. The development of the petroleum deposits of California has been attended by numerous accidents, the results of which are readily noticed at the top of the wells and in the profit and loss accounts of the operators. Determination of the cause of these accidents has been the subject of considerable study, which naturally has fallen upon men familiar with technical methods. The greatest damage to the oil deposits of California has resulted from water finding its way into the oil-bearing sands, and it is the purpose of this paper to set forth briefly this phase of the oil industry. Much of the material here presented has previously appeared inn publications issued by the California State Mining Bureau, which, under the direction of State. Mineralogist Fletcher McN. Hamilton, has investigated the subject and taken steps toward improvement of conditions. The writer, having been in charge of this branch of the Bureau work, has gained considerable knowledge of existing conditions.

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