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By Ross W. Smith, Nikhil Trivedi

The variation of point of zero charge (PZC) of both simple and complex oxide minerals was studied as a function of aging time in water. In most cases the PZC's of the simple oxides moved toward more basic pH values with aging time. Evidence to date suggests that this phenomenon relates to dissolution of disturbed layers on the mineral's surface accompanied by later readsorption of metal hydroxy species back onto these surfaces. The readsorption takes place after the solution becomes supersaturated with respect to some crystalline phase. The variation of PZC's of complex oxides as a function of aging time in water is apparently related to several different mechanisms. In a few cases PZC shifted toward more basic values with time. This shift could be attributed to much the same mechanism as for simple oxides. In most cases, however, PZC of complex oxides shifted toward more acid values with aging time, probably because of loss to solution of soluble cations whose oxides possess basic PZC's.

Jan 1, 1975

By S. Chander, D. W. Fuerstenau

The inherently sluggish nature of the reactions involving sulfide minerals, particularly molybdenite, in aqueous solutions under ambient flotation conditions make their investigation complicated and difficult. Since the physicochemical nature of sulfides is known to be controlled by electrochemical reactions, a number of attempts have been made in the past to study sulfide mineral-collector interactions through rest potential and electrode polarization measurements. The purpose of the present investigation was to study the interaction of potassium diethyldithiophosphate (KDTP) with molybdenite. In the present investigation of the interaction of KDTP at the molydenite surface, molybdenite electrode rest potential measurements and electrode polarization behavior were experimentally determined under various solution conditions. The standard reduction potential for the equilibrium between dithiophosphate ions (DTP-) and bis(diethoxythiophosphoryl)disulfide (DTP) [(DTP). + 2e :i7-± 2DTP- (1)] can be evaluated from the electrode rest potential measurements on a platinum electrode in deoxygenated KDTP solutions saturated with freshly prepared (DTP)2. Experimental A platinum wire was used as the electrode for potential measurements. Prior to each measurement the elec-

Jan 1, 1975

By J. J. Arps

This paper is a study of the effect of temperature on the electrical resistivity of sodium chloride solutions based on the published resistivity and density data in the International Critical Tables. This temperature effect is of considerable importance in quantitative interpretation of electric logs, where it is frequently necessary to correct mud resistivities measured under surface conditions to temperatures existing at the bottom of the bore hole. An empirical approximation formula was developed for this conversion which has proved to be very useful and seems to provide results well within the range of accuracy of the data involved. This approximation formula states: sistivities of sodium chloride solutions at temperatures of t and t degrees Fahrenheit, respectively. INTRODUCTION Research by various investigators during the past 20 years has clarified the physical principles of the phenomena which cause the natural or spontaneous electric potential in rotary drilled bore holes. The basic relationship which is most commonly used reads: in which the SP deflection, as measured from the shale base line, is expressed in millivolts. K is a constant, which appears to vary between 50 and 110; the low value applying to shaly sands, whereas the higher values are more common in carbonate rocks. A good average value for K = 70. for which value there is considerable theoretical justification." In order to calculate the resistivity of the connate water R and to estimate its "equivalent salinity" (as NaCl) from an electric log by means of this SP relationship from a knowledge of the static self potential and of the resistiv- ity of the mud filtrate R it is necessary to first correct the resistivity of the mud filtrate measured under surface conditions to the resistivity of this same mud filtrate in the well bore at a different temperature. In order to make this temperature conversion for the mud filtrate the variation of the electrical resistivity of sodium chloride solutions with temperature is commonly used. Since some discrepancies were found in the charts ordinarily used for this purpose, it was felt desirable to make a new study of this relationship based on the published measurement data. Because of the fundamental nature of these relationships and as an aid to other workers in this field, an attempt has been made in this study to show every step in the calculations. CONDUCTIVITY VS MOL CONCENTRATION The most complete published reference on the temperature relationship of sodium chloride solutions of different concentrations is provided in the International Critical Tables.' The basic measurement data on the electrical conductivity of aqueous sodium chloride solutions, at different temperatures, as given in these tables, are reproduced in Table 1. The electrical conductivity values in this Table 1 are expressed as 10' times the specific conductivity k in ohm-'cm'l per unit of concentration in milligram mols per liter of solution C, or: RESISTIVITY VS MOL CONCENTRATION These conductivity values from Table 1 were first converted to the corresponding electrical resistivity values (R) , expressed in ohm-meters, as is conven-

Jan 1, 1953

By C. W. Purington, H. B. C. Nitze

The Kotchkar mining-district, known as the Kotchkar System, is situated in the Orenburg government, in Eastern Russia, in the great plateau- or steppe-country immediately adjacent to the eastern slopes of the Ural mountains. Its longer dimension is north and south about 27 miles, while in the widest (northern) portion the distance across is 22 miles. The district lies 40 miles southwest of Miass, a station of the Trans-Siberian railway, and half-way between this village and that of Troitsk. It contains also the not inconsiderable settlements of Kotchkar and Eosobrodskoit., the last a Kossak town. So far as explored, the district is known to contain from 300 to 400 auriferous veins. ? Although the topography is generally of an exceedingly flat character, the country is traversed by several small rivulets running from west to east, and flowing into the Sanarka and Kamenka rivers. Since 1844 placers have been worked in the district, but it was not until 1867 that veins were discovered, and these have been worked only since the impoverishment of the alluvial deposits. The deposit with which this paper especially deals is known as the Ouspensky mine, one of twelve owned by MM. de Zelenkoff & Cie., five of which are situated in the Kotchkar System. An opportunity of visiting this mine was afforded the writers, in eonnection with an excursion of the VII. session of the International Geological Congress; held in Russia during the summer of 1897. The mine is reached by a 40-mile '(troika" journey from the railway station of Bichkil, itself

Jan 1, 1899

By George S. Rice

Instantaneous outbursts of gas in underground workings are similar in effect to great blasts of explosives, but without heat effects. Fortunately they occur only in a few localities in exceptional coal fields of the world and under exceptional geologic conditions. Such violent outbursts should not be compared with the ordinary outflows of gas into coal mines or with explosions of gas and dust. The phenomenon is essentially one of gas held in circumscribed areas under very high pressure and as a mining face or heading approaches such a place and the mining excavation sufficiently weakens the natural surrounding dam or shell, this is burst by the pressure just as by the discharge of a mass of explosives. The outbursts, so far as known to the writer, have been confined to coal beds and have not occurred in other mineral deposits. Hence, as discussed later, he believes that it is the relation of the gases to the coal material that is a factor in conjunction with others in producing conditions which permit the phenomena to occur when mining is done. The gases in most instantaneous outbursts have been hydrocarbon gases but in two coal fields they have been definitely found to be chiefly or wholly carbon dioxide. One of these localities in which CO2 outbursts have been frequent and have caused loss of life is in the southern part of the Gard basin, near Alais, in southern France. In 1919, the writer visited the Fontaine mine in this field the day following the occurrence of an outburst by which two men were smothered by carbon dioxide and fine dust. After 24 hr. the CO2 had not been entirely removed by the ventilating current. Occasional outbursts of CO2 have also occurred in other small basins in France, causing accidents, as in Puy-de-Dome. However, mines in the Gard basin, north of those in which CO2 outbursts have occurred, have experienced hydrocarbon gas outbursts. In the Lower Silesian coal field, Germany, there is a group of mines which have been subject to many instantaneous CO2 outbursts, some causing serious accidents, but the greatest disaster occurred recently

Jan 1, 1931

By J. J. Rutledge

I. DESCRIPTION OF THE CLINTON ORES AND ASSOCIATED POCKS. THE Clinton rocks in Stone Valley comprise (1) thick layers of deep-red shale, (2) layers of reddish-gray shale interspersed with beds of sandstone and thin beds of extremely fossiliferous limestone, and (3) yellowish-gray shales alternating with thin layers of olive-colored shales. These layers of shale are all very thin and are at no point massive.1 A bed of gray-white sandstone varying in thickness from 12 to 30 ft. occurs in the tipper portions of the Clinton shales. This is called the ore sandstone, a name given to it by Rogers and adopted also by the Second Pennsylvania Geological Survey. It is the surest guide to the presence of the iron-ore bed, which lies below its lower edges at distances varying from 10 to 20 ft. This ore sandstone, in the valley, lies generally at very low inclinations, but often is locally subjected to considerable changes in dip. At its outcrop this ore sandstone weathers very easily and yields a rather sparse crop of stone, Composed of dirty, iron-stained boulders. Upon the roads these boulders are quite well rounded, and bear fragments of crinoid stems and other fossil forms. The ore sandstone exhibits at many points evidences of former movements in this very great thickness of the shales, and as it is the only stratum in this series competent to transmit and record stresses due to structural movements, its evidence is of considerable importance in determining the occurrence of movements in times past.

Nov 1, 1908

By E. A. Jones

THE Southeast Missouri division of the St. Joseph Lead Co. normally hauls and hoists over 5 million tons of lead ore each year. This ore is mined in the stopes and headings of 20 mines, hauled to a main line system, see above, and transported up to 6.4 miles to ore-hoisting shafts. Average haulage distance is 2.16 miles. A few years ago a distinguished mining engineer visiting this area for the first time remarked, "You do not have a mining problem; yours is a haulage problem." Its relative importance may be gaged by the fact that mine haulage represents about 25 pct of the total cost of mining ore, the most costly single underground operation

Jan 4, 1953

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

By C. B. Foraker

THE Magma mine, of the Magma Copper Co., at Superior, Pinal County, Arizona, is 68 miles east of Phoenix and 21 miles west of Miami, Arizona, on highway U. S. 180. TEMPERATURES AND UNDERGROUND WATERS Surface Temperatures.-The average surface dry-bulb temperature at Superior is 72.4°; wet-bulb, 57.4°; with an indicated relative humidity of 38 per cent. The average yearly rainfall from 1921 to 1936, inclusive, was 18.74 in. The maximum condition of the atmosphere is in June, July and August, and the minimum is in January and February. The surface temperatures, of course, influence the temperatures of the down-cast shafts; however, the variation between winter and summer causes a difference of only 2° to 3° in the stopes and working places that are not close to the intake shafts. Average atmospheric conditions are shown in Fig. 1. Rock Temperatures.-Rock temperatures on the deeper levels of tile mine are as follows: LEVEL DEGREES LEVEL DEGREES 2000 109 3200 127 2250 112.5 3400 130 2550 116 3600 134 2800 120 3800 137 3000 124 4000 140 There appears to be no difference in rock temperature for any particu-lar horizon of the various formations or in the vein. Water encountered is always the same temperature as the rock from which it flows, and for this reason it is thought that the water is heated by the rock; not the rock by the water. The country rock apparently has been heated by the various intrusions, perhaps the vein itself, and has not yet had time to cool off. The geothermal gradient (Fig. 2) as indicated by the rock tem-peratures given above is 1 1/2 ° per 100 feet.

Jan 1, 1938

By F. L. Wolf, G. E. Alderson

The reclaiming of nietallics from slag and sweepings is of vital interest to every brass-foundry man, but the first cost and interest on the investment often make it prohibitive for the small foundry to enjoy the benefits of a complete concentrating unit. However, the cost of such an installation and the cost of operation are often exaggerated to such an extent that foundries dispose of their copper-bearing refuse at a great loss. This paper gives the actual costs and the returns obtained in the reclaiming plant used at the Ohio Brass Co. This plant is divided into two sections—the preliminary treatment and concentrating departments. In the former occur the screening, crushing, and hand-picking operations whereby rnost of the non-valuable and heavy metallic constituents are removed. The concentrating equipment consists of an elevator, bins, jigs, ball-mill, arid table. Preliminary Treatment The preliminary treatment varies, depending on whether the material is slag, foundry-floor sweepings, or brass casting-floor sweepings. Material of the first class is produced from the operation of six Steele-Harvey and six Schwartz furnaces; the second class represents sweepings from an average of thirty-five. molding floors per day: and the last is collected around the sprue cutters and knockout bench. Treatment of Slag The slag, analyzing 30 to 40 per cent. copper, is passed over a 3-mesh yard screen (Tyler standard mesh) stretched on an inclined rectangular frame supported by adjustable legs and equipped with a hopper which directs the undersize into a barrow. The fine product, running about 20 per cent. copper and representing 20 to 25 per cent. of the total slag, goes direct to a storage bin for concentrator frrd. The oversize is charged into a No. 2 Hill cinder crusher, which takes 175 to 200 11,. to a charge and crushes two charges per hour through 'a No. 4 riddle. It

Jan 1, 1921

By Howard V. Sears

ArcHodrilling (Arcuate Hole Drilling) of short radius overhead curved holes from within the working level with a new, small-diameter in-the-hole drill produces tangible, assayable chip samples from the entire height of the projected mine level where the hole arcs down immediately in front of the working face. Drilling through the projected level with diamond coring tools produces samples showing the competence of roof and floor strata as well as the geological and economic characteristics of the ore. Hand-portable solid state electronic surveying instrument has been developed to survey the ArcHole and a convenient nomograph plotting record sheet converts survey digital readouts to hole inclination in degrees, to radius of curvature in feet, and to attitude of the plane of curvature from vertical in degrees, all without calculation. The ArcHodrilling system offers a tool with which the exploration geologist can more nearly assess the true potential of old mining properties being reexamined and to reduce the number of surface diamond drill holes needed to secure development data about new ore bodies. It gives the mine geologist an opportunity to secure those data at a fraction of the cost of drilling from the surface. The mining supervisor has a convenient, cheap tool to look ahead to know what he will be mining tomorrow. The mill supervisor has an opportunity to reduce his mineral loss in tailings by being able to anticipate the grade of his mill feed.

Jan 1, 1973

By E. A. Holbrook

MINING Metallurgy, and Petroleum Engineering department in our colleges are facing a crisis; indeed, conditions that threaten their very existence. Unless the Army, Navy, and War Manpower Commission change their present policy, within two years mineral industries education as now carried on will die, because no ablebodied students will be left in the course. If this is the decision of our responsible governmental agencies we of the mining schools must perhaps accept it as a war measure. It might be well however, for the executive of our mining metallurgical, and oil companies to look ahead a, to where they are to recruit a supply of young technically trained engineers. You can no more operate a mine, a steel plant or an oil company without trained engineers than you can operate a battleship without mechanical and electrical engineers.

Jan 1, 1943

By George W. Maynard

IN the course of an examination of some of the California hydraulie mines in November last, I visited the property of the Gold Run Ditch and Mining Company, near Dutch Flat, Placer County. This is one of the most important and extensively worked mines in the district. The gold occurs in the characteristic blue gravel, which averages 175 feet in thickness, the lower 40-60 feet being made tip of cement gravel, which resists the action of water, and can only be loosened by blasting. The specimen which I have the pleasure of laying before the members was presented to me by Mr. I. L. Gould, the intelligent superintendent of the mines, who informs me that he found it in the old river channel, about twelve feet above the bedrock. The flattened water-worn nugget of gold, about the size of a kidney-bean, is imbedded in blue cement gravel, around which quartz has crystallized. When found the projecting portion of the nugget was enveloped in quartz, the core of gravel and gold having only been discovered after breaking the lump of quartz. On the quartz there is a shell of cement. The specimen is a remarkable confirmation of the theory of the deposition of quartz from solution. DISCUSSION. DR. T. STERRY HUNT, in commenting upon this occurrence, remarked that it is in accordance with what we already know of the recency of some of the quartz of this region, and cited the microscopic

Jan 1, 1880

By K. J. Gill, P. Chiotti, J. T. Mason

Thermal, metallographic, and vapor pressure data were obtained to establish the pkase boundaries and the standard free energy, enthalpy, and entropy of formation for the compounds in the Y-Zn system. Three coinpounds with stoichiometric formulas of YZn, YZn2, and Y2Zn17 melt congruently at 1105", 1080°, and 890°C, respectively. Four compounds with stoiclziometric formulas of YZn3, YZn4, YZn5, and YZn,, undergo perztectic reactions at 905", 895", 870º, and 685ºC, respectively. Three eutec-tics exisl in this system with the .following eutectic temperatures and zinc contents in wtpct: 875ºC, 23.2 Zn; 1015ºC, 51 Zn; 865ºC, 82 Zn. The YZn, pkase undergoes an allotropic transformation. In the two phase YZn2 -YZn alloys the trans.formation gives a weak thermal arrest at 750°C, whereas in the two phase YZn2-YZn3 alloys no thermal arrest is observed and the transformation occurs over a temperature range below 750°C. At 500°C the free mzergies of formation per lnole vavy from —18,090 for YZn to —53,430 fov YZr11 and corresponding enthalpies vary from -24,050 to -92,080. The free energies and enthalpies per g atom as a function of composition show a maximum for the YZn2 phase; the 500°C values are -9580 and -13,180, vespectively. 1 HE only information found in the literature on Y-Zn alloys was the observation reported by Carlson, Schmidt. and speddingl that Y-20 wt pct Zn forms a low melting alloy. The alloy was produced by the bomb-reduction of YF3 and ZnF2 with calcium in an investigation of methods for producing yttrium metal. The solubility of yttrium in zinc has been determined by P. F. woerner2 and reported by Chiotti, Woerner, and Parry.3 In the temperature range 495" to 685°C the solubility may be represented by the relation In these equations N represents atom fraction of yttrium and T is the temperature in degrees Kelvin. The purpose of the present investigation was to establish the phase diagram for the Y-Zn system and to determine the standard free energy, enthalpy, and entropy of formation for the compounds formed. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in the preparation of alloys were Bunker Hill slab zinc, 99.99 pct pure, and Ames Laboratory yttrium sponge. Arc-melted yttrium buttons contained the following impurities in parts per million: C-129, N-12, 0-307, Fe-209, Ni-126, Mg-13, Ca < 10, F-105, and Ti < 50. Some of the alloys containing 70 wt pct or more of Zn were prepared from yttrium containing 5000 ppm Ti as a major impurity. Tantalum containers were found to be suitable for all alloys studied and were used throughout the investigation. The pure metals, total weight about 30 g, were sealed in 1 in. diam tantalum crucibles by welding on preformed tantalum covers. A 1/8 in. diam tantalum tube was welded in the base of each crucible for use as a thermocouple well. Welding was done with a heli-arc in a glove box which was initially evacuated and filled with argon. The sealed crucibles were enclosed in stainless steel jackets and heated in an oscillating furnace at temperatures up to 1150°C. Homogeneous liquid alloys were obtained within a half hr at these temperatures except for alloys containing less than 20 pct zinc. The latter alloys were held at 1000º to 1100°C for 2 to 3 days in order to obtain equilibrium. After the initial equilibrations the tantalum crucibles containing the alloys were removed from the steel containers and used directly for differential thermal analyses. Further annealing heat treatments for alloys in which peritectic reactions were involved were carried out in the thermal analyses furnace. After thermal analyses the tantalum crucibles were opened and the alloys sectioned and polished for metallographic examination. In the following discussion alloys referred to as "quenched" were obtained by quenching the sealed stainless steel jacket containing the tantalum crucible and alloy in water. The differential thermal analyses apparatus used was a modified version of the one described in an earlier paper., The graphite crucible was replaced by an inconel crucible, the nickel standard and sampie container were separated by a 1/8 in. MgO plate, no getter was used, and provisions were made to

Jan 1, 1963

By C. M. Weld

In the course of my professional work in China during the fall of 1907, I had an opportunity to visit the iron-ore mines at Ta-yeh in Hu-pei province (long. 114O 50t E., lat. 30&apos; 20t N.). It occurs to me that a rescript and discussion of my notes taken at that time should be of interest, particularly as supplementing the exceedingly interesting recent paper of Thomas T. Read on The Mineral Production and Resources of China.&apos; Ta-yeh is situated near the right bank of the Yangtze river. The mines are at an average distance of about 16 miles from the river-port Shi-hui-yao, which in turn is some 70 miles SE. of Hankom. The ores are shipped to the works of the Han-Yeh-P&apos;ing Iron & Coal Co. at Hanyang, as also very largely to the Japanese government iron- and steel-works at Wakamatsu, Japan. Smaller qnantities have been exported to the Pacific coast of the United States. These ore-deposits have been briefly noticed in a number of publications, but, so far as I know, Mr. Read&apos;s description, in his chapter or1 the iron-ores of the Chinese Empire,2 contains the first attempt to define their geological character. In his more recent paper Mr. Read follows very closely the text of his earlier description. To quote briefly from the recent paper, he says : " The iron-ores at Ta-yeh .... lie along the contact between a marble and an intrusive body of a dark-gray syenitic rock." He refers to a figure which exhibits in plan, but not in section, the relative positions of the syenite, ore-bodies, and limestone. The contact is seen to trend approximately E-W., with the syenite on the north and the limestone on the south. " The syenite lies to the north of the marble, and a few miles farther north the marble again appears, iron-ore again being present along the contact." No litho-

Jan 1, 1913

By Walter Harvey Weed

INTRODUCTION. IN a previous paper upon the enrichment of mineral veins by later metallic sulphides,† the writer has shown that certain masses of rich ores, such as are found in many mines, either near the water-line or as bonanzas in depth, are of secondary origin, and are due to a leaching of lean ore and the concentration of the material by reaction between the solution and the unaltered ore below. The geological and mineralogical evidence is believed to form an adequate basis for a chemical and physical explanation of the phenomenon. In the present paper the writer will give a brief synopsis of this theory, and will apply it more particularly to deposits of the precious metals, laying special emphasis upon the dependence of such enrichments upon the presence of iron sulphide (as pyrite, etc.) in the primary ore, and upon structural features which control the circulation of the enriching solutions below the water-level. It is believed that many, though not all, of the bonanzas and pay-shoots of rich sulphide ores, especially those carrying gold and silver, which are encountered in ore-deposits, are of such secondary origin. Apparently it is essential that the occurrence and structural relations of such ore-masses should be understood, as the success of the mine is often dependent upon the finding and extraction of these ores. A legitimate deduction, too, is that such ore-deposits decrease in value with depth. As my own studies have been mainly in Montana, my illustrations must be drawn from the ore-deposits of this and adjacent States, with such as I have noted in hurried visits elsewhere. The literature of ore-deposits doubtless affords also

Jan 1, 1902

By B. V. P. Rao, H. L. Lovell, G. Simkovich

In the study described here, flotation tests were conducted on pure CaF2, on CaF2 doped at several concentration levels with either NaF or YF3, and on natural fluorite samples containing various amounts of impurities in an effort to extend previous knowledge of the influence of crystalline point imperfections on the flotation properties of solids. The results of these tests showed that although recoveries generally decreased as impurities increased, the differences in recovery were not nearly as striking as those detected in earlier experiments. A number of experimentalists have shown an interest in the way in which crystalline point imperfections affect the flotation properties of solids. As long ago as 1953, Welch hypothesized that it might be possible to control surface imperfections and thereby also control the flotation of solids.&apos; A few years later, in some rather extensive work, Plaksin and his coworkers varied the surface imperfections of a number of compounds by oxidation or reduction processes and found that significant variations in flotation properties resulted.2-4 More recently, Simkovich showed that the recovery of both AgCl and PbS could be markedly varied by adding solid-solution impurities, which acted as doping agents, to these compounds.5 Then Mular studied the flotation of ZnO as a function of the doping agents Al2O3 and Li2O.6 Once again, it was found that these impurities, even in very low concentrations, had profound effects upon flotation recoveries. From an imperfection point of view, the defect structures of the compounds tested previously are as follows:7 PbS — amphoteric semiconductor with a Frenkel-type defect structure in the cation sub-lattice.8 AgCl - ionic conductor-Frenkel type defect structure? ZnO — n-type semiconductor, zinc ion interstitials and quasi-free electrons.10 All of these works undoubtedly bear some relation to the findings that the flotation properties of seemingly identical minerals from different ore deposits often exhibit extreme variation in flotation behavior, i.e., that small amounts of analytically undetectable impurities often have a great influence upon flotation

Jan 1, 1969

By G. J. Heuer, J. N. Dew, G. C. Clark

The effect on well behavior of partial permeability barriers, changes in producing rates and well spacings have been calculated through use of a radial, unsteady-state, two-phase-flow mathematical model. This model allows for variations in permeabilities and porosities with distance from the wellbore. The numerical methods necessary to solve the problem require use of a highspeed digital computer, in this case an IBM 704. In each instance, pressure and saturation gradients, gas-oil ratios and recoveries around a well producing by solution-gas drive have been calculated as a function of time and distance from the wellbore. Comparisons are made to show the effect of changes in producing rate and of varying permeability near the wellbore and out in the formation on the production and pressure history of the well. The effect of different well spacings on producing rate and ultimate recovery is considered. Although the mathematical description of the reservoir is simplified in comparison to an actual reservoir, the results do give some insight into the difficult problem of spacing and proration in a heterogeneous solution-gas-drive reservoir. Results show that for the cases considered spacing has little effect on ultimate recovery and that permeability barriers removed from the well decrease producing rate for a period of time but have only a small effect on ultimate production. INTRODUCTION The effect of spacing and producing rate on the production characteristics and ultimate recovery of a well producing by the solution-gas-drive mechanism have been topics of interest to the oil industry for many years and the subject of many hearings before state regulatory bodies. The problem is very complicated because of the difficulty of simulating in the laboratory a reservoir producing by the solution-gas-drive mechanism under anything like normal field conditions. This paper gives the initial results of a study aimed at determining the effect of these factors on production from reservoirs simulated by a mathematical model. Two-phase, unsteady-state equations are used to calculate pressures, saturations, and rates of oil and gas flow as a function of time and distance from the wellbore. The model is radial, and reservoir properties may be varied with distance from the wellbore. A decrease in permeability at a given distance results in a low-permeability ring concentric with the wellbore through which all the fluids from more distant portions of the reservoir must flow. The current mathematical model allows for variation of permeability, porosity and saturations as a function of distance from the well. Any desired drainage radius for the well may be selected. Drainage radii of 745 and 1,053 ft, which correspond to 40- and 80-acre spacing, were chosen for the calculations which follow. A large amount of the input data has been held constant. No investigation was made into the effect of changes in fluid properties and relative permeability characteristics on oil and gas production behavior. Fluid properties and relative permeabilities are essentially those of the White Mesa portion of the Greater Aneth area in southeastern Utah. A recently concluded hearing before the Utah Oil and Gas Conservation Commission to determine spacing for the field aroused interest in the possible effect of permeability constrictions located some distance from the well on production and recovery. This interest stimulated the present study. In this paper, no attempt has been made to simulate any field production characteristics exactly. Only the solution-gas-drive mechanism has been investigated, and production by liquid expansion has not been considered. This investigation is exploratory in nature but does give some insight into the problems of spacing and proration in a solution-gas-drive field having permeability variations. THE MATHEMATICAL MODEL The mathematical model is similar to that proposed by West, Garvin and Sheldon.&apos; Approximately the same techniques have been used in arriving at a solution. The equations are nonlinear, partial differential equations which have been known for some time. The particular equations used for this study neglect the effects of capillary pressure and gravitational forces. The advent of modern digital computing equipment has made their solution practical. Basically, the method solves for pressure, saturations, and oil and gas flow rates as a function of distance and time. In our model, distance to the

By G. R. Speich

The interlarnmelm spacing, growth rate, and degree of segregation that accompany cellular precipitation in four Fe-Zn alloys containing 9.7, 15.2, 23.5, and 30.5 at. pct Zn have been determined in the temperature range 400" to 600°C. The chemical free-energy change for the reaction was calculated from the available thermodynamic data and the known compositions of the phases. The fraction of the chemical free-energy change for equilibrium segregation that is converted into interfacial free energy decreases from 0.43 to 0.08 as the magnitude of this free-energy change increases from 35 to 270 cal per mole. At constant temperature the cellular growth rate is proportional to the cube of the dissipated free energy. At 600°C newly 100 pct of the equilibrium segregation is achieved during cellulm precipitation whereas at 400°C only 85 pct of the equilibrium segregation is attained. During cellular growth, mass transport of zinc occurs by grain boundary diffusion; excess zinc remaining in the a! phase after the completion of growth is removed slowly by volume diffusion. A modified Cahn theory of cellular precipitation predicts the observed interlamellar spacing within a factor of two. In cellular precipitation reactions such as pearlite formation or discontinuous precipitation, the basic problem is to predict the variation of growth rate G, interlamellar spacing S, and degree of segregation P with composition and temperature. To accomplish this we need three independent equations relating these quantities. One of these equations comes from the diffusion solution. To obtain two additional independent equations, some assumptions must be made. cahnl has suggested recently that two plausible assumptions are 1) that growth rate is proportional to the dissipated free energy and 2) that the spacing which occurs is that which maximizes the dissipated free energy. According to the first assumption, this spacing also maximizes the growth rate and the rate of decrease of free energy per unit area of cell boundary. The present work was undertaken to test these assumptions. To test the first assumption it is necessary to study a cellular reaction over a wide range of supersatura-tions to establish a relationship between G and the dissipated free energy at constant temperature. This is possible only in discontinuous precipitation reactions since in pearlite reactions constituents other than pearlite form if the composition of the parent phase deviates even slightly from the eutectoid composition. The Fe-Zn system was chosen for study because 1) discontinuous precipitation proceeds to completion over a wide temperature and concentration range, 2) the degree of segregation within the cell can be measured by lattice parameter measurements,2 and 3) the thermodynamics of this system have recently been determined by Wriedt.3 In this system the cells consisting d alternate lamellae of a and r phases form from supercooled iron-rich a phase. The a phase within the cells is bcc as is the original a phase, cia, but has a different orientation and a slightly lower zinc content than the original a phase. The r phase has a zinc content of about 70 at. pct and a crystal structure isomor-phous with T brass. EXPERIMENTAL PROCEDURE Four Fe-Zn alloys with 9.7, 15.2, 23.5, and 30.5 at. pct Zn were prepared from carbonyl-iron powder (400 mesh, 99.8 wt pct Fe) and zinc powder (200 mesh, 99.99 wt pct Zn). The powders were ball-milled together and cold-pressed under 60,000 psi to discs $ in. thick by $ in. diam. The cold-pressed discs of the alloys with 9.7 and 15.2 at. pct Zn were sealed in evacuated silica capsules and heated slowly to 1100°C over a period of 1 week (3 days at 600°C, then 3 days at 80O°C, then 1 day at 1100°C). The alloys with 23.5 and 30.5 at. pct Zn were treated similarly except that the final homogenization temperatures were 1000" and 85O°C, respectively, to prevent melting. The alloys were quenched in iced brine from the final homogenization temperature. Specimens of each alloy were subsequently aged in salt pots at temperatures of 400°, 450°, 500°, 550°, 600°, and 650°C for times that varied from a few minutes to several hundred hours. At a late stage of this work, an alloy containing 11.2 at. pct Zn was prepared by vapor-impregnation of iron foil with zinc vapor at 890°C. This alloy proved useful for electron microscope studies because it was free of porosity. The homogenization and aging conditions were based on the recent Fe-Zn phase diagram of Stadelmaier and Bridgers4 rather than the earlier diagram of ansen.5 They consist of a homogenization heat treatment in the homogeneous a field followed by an aging treatment in the two-phase a + r field. The aged specimens were metallographically polished and etched in 2 pct nital and the radius of the largest cell in the microstructure determined. This radius plotted vs time gave a straight line whose slope is the boundary migration rate or growth rate G of the cell. To determine the interlamellar spacing, specimens were examined by surface-replica and thin-section electron microscope techniques. Because of the irregular nature of the lamellae within the cell, the average interlamellar spacing S .of the cell was measured by the method of Cahn and Hagel,6 where S is defined by:

Jan 1, 1969

By H. M. Shepard

THE copper industry operated at high capacity throughout 1947, with no serious tie-ups in operation as was the case in 1946, when almost the entire industry was shut down by a four-month strike. Refined copper production in the United States averaged 94,250 tons for the first eleven months and deliveries to domestic consumers, including foreign copper for domestic consumption, averaged 114,000 tons per month. On April 29 the import duty of 4d per lb was suspended until March 31, 1949. Copper prices fluctuated considerably for a short time thereafter. Over the year the price of domestic electrolytic copper at refineries on the Atlantic seaboard advanced from 19.225¢ on Jan. 2 to 21.200d on Dec. 24.

Jan 1, 1948