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By N. A. Gokcen, John Chipman

D. C. Hilty (Union Carbide and Carbon Research Laboratories, Niagara Falls, N. Y.)—This paper is a very nicely detailed analysis of a difficult problem. I would like to point out that the results that Mr. Crafts and I published a few years ago had no reference to activity, or anything else of a similar nature; our results were strictly empirical. It is quite gratifying that we now have a case where results involving activity coefficients and results derived from direct observations on actual steel melts are practically identical. When two different laboratories, working from two entirely different approaches, come out with results in such good agreement in their major significance, that is an achievement. It is something that was not possible 15 or 20 years ago. There is one question I would like to ask Dr. Chip-man. It has to do with a very minor point of disagreement in these results. When we reported the kink in the Si-O solubility curve I think you may recall that it came at the different temperature levels at about the order of 0.015 to 0.03 pct 0 and 0.03 to 0.07 pct Si—we also pointed out that we had difficulty in obtaining data at that level, although we finally did get some. I note in going through the data for the present paper, that there are no samples in those particular silicon and oxygen ranges. I wonder if that was purely accidental or was there a reason for it. D. E. Babcock (Republic Steel Corp., Youngstown, Ohio)—Mr. Hilty, do you have any explanation for that discrepancy between Dr. Chipman's curve and your own Mr. Hilty—Our explanation for it at that time was that for some reason our system probably was not in true equilibrium with SiO, that is, in equilibrium with the silica crucible at that level. We did observe, however, that that was the level at which both the metal and the slag became saturated with SiO,. On the average, in studying inclusion formation in small ingots permitted to solidify normally from the molten state, we observed pure silica inclusions at silicon contents over about 0.05 pct and FeO type inclusions at silicon

Jan 1, 1953

By Charles Meyer, Reno H. Sales

AT Butte, successive zones of sericitized and argillized quartz monzonite occur around every ore-bearing fracture regardless of its size, attitude, or relative age. The two types of alteration always occupy the same relative positions; sericite adjacent to the ore-bearing vein, clay minerals always between the sericitized rock and fresh quartz monzonite, except where overlap of alteration effects between adjacent fissures has eliminated the lower grade mineralogical products, as is the case in much of Butte's Central zone of pervasive sericitization. As long as active circulation continued in the channel, each zone migrated away from the fissure, that is, it grew at its outer edge and simultaneously receded at its veinward edge because of encroachment by the next innermost zone. The different mineralogical and chemical responses within the wall rocks to the attack by the ore fluid are dependent not on a drastic about-face change of composition of the fluid in the channel relative to its ability to alter the quartz monzonite but on continuously varying conditions of physico-chemical environment within the wall rock outwardly from the vein.

Jan 1, 1947

By A. G. Spillette, R. L. Nielsen

The purpose of this paper is to further the understanding of reservoir response to hot-water injection by desuribing a two-dimensional, mathematical model of the process. Key assumptions are that no gas phase is present, and that the injected fluid reaches thermal equilibrium instantaneously with the reservoir fluids and sand. The resulting system of three partial differential equations is solved simultaneously through the use of a "leap-frog" application of standard alternating direction implicit methods for the solution of the mass-balance equations and the method of characteristics for solution of the energy-balance equation. The utility of the mathematical model is demonstrated by comparing numerical and analytic temperature distributions for hot-water bank injection and by comparing calculated with observed field behavior. Additional calculations show that hot waterfioding can recover significantly more oil than cold waterflooding, and that a hot-water bank recovers, with less energy input, nearly as much oil us continuous injection. Introduction Consistent field success with hot fluid injection processes requires good reservoir description and a thorough understanding of recovery mechanisms. The latter is fostered by a combination of well designed experimental studies and physically sound mathematical modeling. The purpose of this paper is to further the understanding of reservoir response to hot-water injection by describing a two-dimensional mathematical technique, indicating its validity, and demonstrating its utility for studying the effects of reservoir and operating parameters. Published experimental studies of hot fluid injection processes are few." Even if extensive data were available, two considerations discourage exclusive reliance on laboratory or field work. First, because of the severity of scaling requirements," laboratory results must be interpreted with care. Second, because of the one-shot nature of field experiments — injectivity/productivity tests and pilot floods—results seldom are available over the desired range of operating conditions. These factors emphasize the need for devoting attention to mathematical modeling to complement laboratory and field work. Through the use of mathematical models, scaling uncertainties can be bridged and response can be predicted for unique combinations of reservoir and operating conditions. Numerous mathematical models developed during recent years enable us to calculate temperature distributions, thermal efficiency (or conversely, fraction of heat lost), and oil recovery behavior for hot fluid injection. Ramey" and Spillette' recently have provided reviews of these methods. Most models have concentrated on predicting temperature distributions and thermal efficiency; few have been directed at predicting oil recovery.'."1° Although these techniques are useful for estimating effects of reservoir parameters and operating conditions on process performance, results are limited by the assumptions made and by the methods of coupling independently solved fluid-flow and energy-balance equations. A computer-based method is presented for predicting total reservoir response to hot-water injection that obviates most simplifying assumptions. The model simulates fluid flow and heat transfer in two dimensions within a vertical cross-section spanning the oil sand and adjacent unproductive strata. Known numerical procedures are used to solve the governing partial differential equations. The mathematical model handles the effects of reservoir heterogeneity, gravity, capillarity, relative permeability and temperature-dependent fluid properties. In addition, a wide range of operating conditions can be modeled, including hot-water followed by cold-water injection. Mathematical Description of Hot-Water Injection Key assumptions in the mathematical model for hot-water injection are that (1) no gas phase is present and (2) the injected fluid reaches thermal equilibrium instantaneously with the reservoir fluids and sand. Relative permeability and capillary pressure are assumed independent of temperature. Darcy's law for multiphase fluid flow relates the velocities of the oil and water phases to the phase pressure gradients by the following relations:

Jan 1, 1969

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

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

Jan 1, 1931

By P. L. Allsman

A method of analyzing blasting action indicates that major cost savings are possible by revising practice and bringing the classical blasting formulas up to date; difficult problems such as taconite and throw-breakup can be attacked by engineering Denonation pressure — the peak pressure developed by the explosive reaction; "shatter blasting." Average detonation pressure — the average pressure over the time the reaction continues; "heave blasting." Radial presswe — the stress in a radially expanding sphere about the detonation. Corresponds to the diminishing peak pressure. Lateral stress - the stress in a circumferential direction, induced by outward movement of the rock away from the detonation. Limiting stress or Slim— the rock property at which failure will occur in the case at hand; may be tensile or compressive strength, or combinations. Recent developments in explosives technology, following the advent of nuclear explosions, have led to a rather complete understanding of their action. A survey was made for the purpose of uncovering any knowledge which might be applicable in the mining and quarrying industries, the principal users of explosives. Although no revolutionary techniques have become apparent, much basic data pertaining to blasting — fortunately not classified — have been developed by recent research, from which a good general understanding of the process can be derived. It is hoped this explanation of the scientific principles governing explosive action, together with a proposed analysis of blasting practice, will further the development of mining engineering. NATURE OF THE REACTION: The phenomenon of explosion, termed detonation, is in reality a rather complex chemical reaction, and as such is completely explainable by physical and chemical laws. Detonation is characterized by high temperature and pressure, extreme rapidity — often being complete within one microsecond — and most importantly by formation of a shock pulse which accompanies the reaction zone. As with any chemical reaction, there is a critical value of temperature and pressure below which detonation can not occur; this is termed the "critical point". Whereas an explosive substance will decompose slowly at ordinary temperature, with the formation of gases which readily dissipate; at elevated temperature the reaction is considerably speeded. If pressure is suddenly applied at some point in an explosive medium, adiabatic compression results, and the temperature is locally raised. When the temperature becomes high enough the decomposition will be so rapid that the gaseous products do not have time to dissipate, but contribute to a further build-up of pressure. This, in turn, furthers adiabatic temperature rise over a widening area, and with any heat generated by an exothermic reaction, causes a rapid increase in temperature. Both temperature and pressure are spontaneously built up in this manner until the critical point is reached, resulting in detonation. The values of pressure and temperature necessary to create detonation are established by the unusual nature of the process. If temperature alone is raised above the critical point, without sufficient increase in pressure, deflagration or "low-order detonation" occurs. In the true, or "high-order detonation", the shock pulse resulting from the violent decomposition becomes an integral part of the reaction, and itself aids in increasing the detonation

Jan 1, 1961

By Clarence Zener

THE internal friction of nonferrous metals vibrating at low stress amplitudes has so far always been successfully interpreted in terms of inhomogeneities of one sort or another. Examples are the fluctuation of stress across a specimen vibrating transversely,1,2,3 the stress inhomogeneities due to the elastic anisotropy and partial random orientation of the individual crystallites,4,5 localized weak regions introduced by cold-working,6,7 grain boundaries and possibly twinning planes.8.9 Perfect single crystals are, by definition, homogeneous. Actual single crystals usually, perhaps always, contains some imperfections. The present investigation was undertaken to determine whether the internal friction of single crystals may likewise be attributed to inhomogeneities. This study was made possible through the gift of a large single crystal of 70-30 alpha brass by H. L. Burghoff, of the Chase Brass and Copper Co. The specimen, 3-s in. in diameter and 10 in. long, was similar to samples previously described by Mr. Burghoff.10 EXPERIMENTAL METHOD The experimental method used has previously been described in Institute papers.5,6.9 The measure of internal friction adopted here, I/Q, is (p) X the logarithmic decrement, a measure used by some writers, and is also (I/2p) X the specific damping capacity, a measure used by other writers. In all measurements the stress level was kept so low that the measurements were independent of stress level. In all measurements in which the temperature was varied, observations were made as the specimen slowly cooled from its highest temperature. The specimen was vibrated transversely. Observations were made at the fundamental frequency and at the first overtone, of about 620 and 1710 cycles per second, respectively. No attempt was made to avoid acoustical losses. EXPERIMENTAL RESULTS The specimen was annealed for several hours at 450°C. The temperature dependence of the internal friction was then determined from room temperature to 400°°C. As shown in Fig. i, the internal friction increased by only a factor of 2 from room temperature to 300°°C., then by a factor of 100 during the next :too' interval. These measurements are consistent with the view that the observed internal friction is the superposition of two distinct parts. One, dominant at room temperature, is nearly independent of temperature. This part may be accounted for by acoustical losses and by transverse thermal currents. It was not further investigated. The second part, when plotted in the manner of Fig. I, lies upon a straight line. Therefore it has a heat of activation H; i.e., it varies with temperature as Internal friction ~ e-HI/RT [I]

Jan 1, 1942

By G. Krauss, W. Pitsch

The fine structure of the bcc martensite formed in an Fe-33 wt pct ATi single crystal of arrstenite is sho~on by transmission electron microscoPy to consist of combinations of transformation twins, stacking faults, deformation twins, and regular arrays of parallel screw dislocations. These structures constitute evidence for the multiple lattice-invariant deformations which operating during the formation of martensite could produce the real habit-plane scatter measured by a two-surface analysis of the plates formed in the single crystal of this investigation and reported in the literature for other Fe-Ni rnartensites. CRYSTALLOGRAPHIC theories1,2 of martensitic transformation show that the habit plane of martensite in a parent lattice is dependent in part upon an inhomogeneous distortion or lattice-invariant deformation which takes place on a fine scale within a martensite plate during its formation. Several recent theoretical papers3,4 have addressed themselves to an analysis of a wide variety of conceivable lat-tice-invarient deformations and the habit planes which they produce, while experimental investigation have been concerned with either the measurement of habit planes or the description and identification of the martensitic fine structure which reflects the nature of the lattice-invariant deformation operating during transformation. In Fe-Ni alloys with subzero Ms temperatures, the group of alloys with which this paper concerns itself, habit planes have often been found to scatter an amount greater than might be expected from possible experimental errors,5-7 and fine twinning has been identified as a major constituent of the fine structure of martensite.8-11 It has been suggested3,4 that more than one type of invariant shear occurs during martensitic transformation. This possibility has been experimentally supported12,13 by the observation of both dislocation configurations and twinning in a single martensite plate. The purpose of this paper is to report additional evidence for multiple lattice-invariant deformations in martensite and so to account for the real scatter in the habit planes of the martensite plates formed in Fe-Ni alloys. EXPERIMENTAL PROCEDURE The Fe-Ni single crystal was produced by pulling a high-purity iron and nickel charge through a single-crystal vacuum furnace in an alumina crucible. The crystal was double-melted to promote homogeneity and to increase its size by further additions on the second pass. In its final form the crystal was 4 cm in diam and 5 cm long. The nickel and carbon contents were analyzed at 32.9 and 0.006 wt pct, respectively. The austenite of this alloy first transformed to martensite by bursts at about -120°C, and, to preserve as much of the austenite as possible, all transformation was performed just below -120°C. Some observations were made on transformed samples which had been heated for 2 min at 340°C. It is assumed that the features of the martensite of these samples, Figs. 1 and 4, are the same as those of the as-quenched martensite. Orientation of the crystal by X-ray diffraction established 10.735 0.609 0.3161? as the axis of the crystal, an orientation that was checked within 2 deg by neutron diffraction. Further checks by electron diffraction of samples cut normal to the axis confirmed this orientation within the larger limits of error inherent in electron diffraction of thin foils. The X-ray orientation was the one used for the two-surface analysis of the martensite habit planes. A two-surface analysis was performed on the quadrant of the single crystal which had been oriented by both X-ray and neutron-diffraction techniques. Photomicrographs at X50 were made on two surfaces along an edge 2 cm long. Fiducial marks and the fact that many of the plates were almost completely surrounded by retained austenite made good matching of individual plates on two surfaces possible. The habit-plane trace on a surface was taken as the best line parallel to the long axis of a plate. A measure of the accuracy afforded by this criterion was provided by a family of very large plates which appeared at intervals along the entire 2 cm length of the edge. The plates all had habit-plane traces within 2 deg of one another. Many of the plates did not show midribs and, therefore, the use of midribs7 to represent habit-plane traces was not feasible in this investigation. The over-all experimental accuracy is estimated to be better than ±2 deg. Samples for transmission examination in a Siemens Elmiskop I at 100 kv were prepared by cutting 2-mm-thick discs from the single crystal, removing about 0.5 mm by chemical polishing,14 trans-

Jan 1, 1965

By S. C. Lindsay, D. J. I. Evans

With each year that passes hydrometallurgical processes are being more widely used to recover base metals from ores and concentrates. Generally these processes involve liquid-solid separation of metal-bearing liquors from barren residues. This may be done by countercurrent decantation, thickening and filtration, or filtration or centrifuging only. Choice of method is governed by chemical and physical characteristics of the pulps; cost of labor, power, materials, and waste disposal; and even by the amount of capital available when building plans are under way. Since all these controlling factors change with time and location and with technological advances, the separation method must be re-evaluated when new plants or expansion programs are contemplated. At the Sherritt Gordon refinery in Fort Saskatchewan, Alberta, an ammonia pressure leaching process recovers nickel, copper, and cobalt from the nickel concentrate produced at Lynn Lake, Manitoba.' Pregnant liquors are separated from the barren leach residues in a thickener-filter liquid-solids circuit. The decision to use this type of separation was based on a summation of economic factors during the pilot plant and design stages. Although countercurrent decantation was not incorporated in the refinery flowsheet, the problems solved in thickening the leach residues and the experience gained in operating the commercial plant are pertinent to countercurrent decantation, particularly where it is applied to slow-settling leach slurries or slurries having a relatively high vapor pressure of a valuable, obnoxious, or poisonous vapor. The nickel sulfide concentrate is leached under pressure with air and ammonia to dissolve the nickel, copper, and cobalt and most of the sulfur, leaving a residue of iron and siliceous material to be discarded.2,3 During a subsequent distillation stage to recirculate part of the ammonia used for leaching, copper is recovered from the solution as a high-grade sulfide. After further purification to remove traces of copper and undesirable sulfur compounds, the nickel is precipitated by hydrogen under pressure at an elevated temperature. The cobalt, together with unreduced nickel, is precipitated as a mixed metal sulfide by hydrogen sulfide for eventual cobalt recovery. The end solution is then evaporated to produce a crystalline ammonium sulfate byproduct. As shown in Fig. 1, the nickel concentrate is leached in a continuous, two-stage, countercurrent circuit. In the first stage, or adjustment leach, the fresh concentrate is partially leached (60 pct) in the liquor produced in the second stage, or final leach. This system is necessary to produce a solution suitable for treatment in the copper sulfide precipitation step. Both stages are carried out at 170" to 180°F under a total pressure, with air, of 100 to 120 psig in large, horizontal, water-cooled autoclaves. The autoclaves are divided by overflow weirs into four compartments to give a certain amount of staging during leaching. In each compartment a relatively slow-speed (100 to 150 rpm) agitator maintains the nickel concentrate in suspension. Adjustment leaching, carried out in two autoclaves in parallel, is followed by a thickener-filter liquid-solids separation. Final leaching is done in two parallel trains of three autoclaves using aqueous ammonia to extract metal values from the adjustment leach residues. This too is followed by a thickener-filter circuit. Here the residues are repulped once with aqueous ammonia and twice with process water and refiltered after each repulping stage, to insure a maximum recovery of soluble metal, before being discarded to the tailings pond. The adjustment leach is followed by a seven-disk Dorr-Oliver American filter, with an agitator in the filter boot to keep the residues in suspension. Agitators have also been installed beneath the four ten-disk filters following the final leach thickener. Slurry Characteristics: A typical analysis of the Lynn Lake nickel concentrate, produced by differential flotation,' is given in Table I. The concentrate comprises 35 to 49 pct pentlandite, (Fe, Ni)S; 3 to 6 pct chalcopyrite, CuFeS,; 1 to 4 pct pyrite, FeS2; and 24 to 42 pct pyrrhotite, Fe1-2S (where x varies between 0 and 0.2) together with various siliceous minerals such as actinolite, hornblende, and talc. During leaching, the sulfur in the pentlandite, chalcopyrite, and part of the pyrrhotite is successively oxidized through the thiosulfate and poly-thionate radicals to sulfate and sulfamate." Simultaneously the nickel, copper, and cobalt are converted to soluble ammine complexes and the iron in the pentlandite, chalcopyrite, and part of the pyrrhotite is oxidized to a spongy hydrated iron oxide. The hydrated iron oxide is readily broken down by the agitation needed to sustain the concentrate in suspension and to maintain a satisfactory mass transfer of the oxygen from the air to the slurry. Table I shows typical chemical, screen, and

Jan 1, 1961

By L. V. Wade

Abstract-US Bureau of Mines efforts under longwall research programs to develop the capability to predict support requirements for longwall/shortwall support systems are discussed. Ground control studies are being conducted in conjunction with several longwall/shortwall demonstration projects. Geologic, support performance, and strata behavior are being documented on these projects. A hypothesis is presented for the prediction of support requirements.

Jan 11, 1978

C. N. FEnner, New York City (communication to the Secretary) : A possible explanation of some of the' phenomena of amalgamation cited by Mr. Bayliss and others has occurred to me. We know that if, to a quantity of mercury, gold and silver are added until a putty-like paste is formed, and if this mass is spread on a flat surface and pressure is applied, a more fluid portion of the mercury will be squeezed out from the rest, carrying gold and silver with it. The proportion of gold to silver will depend, I think, upon various causes and conditions—the relative chemical affinity which gold and silver have for mercury; the amount of pressure used; the presence of other metals:

Jan 1, 1898

By R. W. Baldwin

On page 309, column 1, the second equation should read: Ma-M1 = dlog_Pa M2-M1 d log P2

Jan 1, 1961

Connecticut Geological and Natural History Survey, P O Box 1106, New Haven, Conn W. E Britton, Superintendent. A complete list of Bulletins available will be sent upon request. Address all inquiries for publications to: George S Godard, State Librarian, Hartford, Conn Fifty-one Bulletins have been issued, 15 of which are of particular interest, dealing with the geology of the state, and are available as follows; 4, The clays and clay industries of Connecticut, by G. F Loughlin (1905), 35 cents; 8, Bibliography of Connecticut geology, by H E Gregory (1907), 20 cents, 13, The lithology of Connecticut, by J Barrell and G. F Loughlin (1910), 45 cents, 18, Triassic fishes of Connecticut, by C. R Eastman (1911), 30 cents, 23, Central Connecticut in the geologic past, by J. Barrell (1915), 20 cents, 24, Triassic life of the Connecticut Valley, by R Lull (1915), 70 cents, 29, The Quaternary geology of the New Haven region, Connecticut, by F. Ward (1920), 60 cents, 30, Drainage modifications, and glaciation in the Danbury region, Connecticut, by Ruth S. Harvey (1920), 55 cents, 33, Geology of the Stonington region, Connecticut, by L H. Martin (1925), 60 cents, 40, The geology of the Shepaug Aqueduct Tunnel, Litchfield County, Connecticut, by W M. Agar (1927), 50 cents; 41, Guide to the geology of Middletown, Connecticut, and Vicinity, by W. N Rice and W. G Foye (1927), $1, 44, Report on the water resources of Connecticut, by R. H Suttee (1928), $1, 46, The physical history of the Connecticut shoreline, by H S Sharp (1929), 75 cents; 47, The glacial geology of Connecticut, by R F. Flint (1929), $2, 51, Minerals of Connecticut, by J F Schairer (1932), 75 cents Bulletin 51 explains the physical and chemical properties of minerals, their classification, and describes more than 100 common minerals found in Connecticut. A bibliography is included The Survey gratuitously distributes all its Bulletins to state residents, scientific institutions, etc. Prices quoted are to private citizens of other states

Jan 1, 1933

By Dever Ashmead

ANTHRACITE was first mined in the Wyoming Valley and sold as an article of commerce in 1808. As some preparation has always been necessary to make it ready to burn, the preparation of anthracite must date back over a hundred years. Two vital factors have determined to a large extent the degree and method of anthracite preparation. These are, first, the character of the beds worked and the methods by which they were mined and, second, the equipment used and practices followed in the burning of the coal. It is not the intention here to go deeply into these phases of preparation as a paper of no mean length could be prepared on the history of either. Rather, the intention here is to point out the main considerations and to show the influence they have exerted on the preparation of anthracite. MINING METHODS AND THEIR RELATION TO PREPARATION In the beginning f the nineteenth century, the coal beds were virgin with the possible exception of some outcroppings that had been worked, to a slight extent, by the Indians. It is known that the American aborigines had a knowledge of the use of this fuel, because when the Wyoming Valley was purchased from them, in 1754, they mentioned the fact that, by selling the land, they would lose their coal.

Jan 9, 1921

By H. Tabachnick, N. Hedley

The extraction of gold and silver from ores with alkaline cyanide solutions is well known. Cyanide solutions are also good solvents for many base metal minerals, particularly most of the copper minerals. Leaver and Woolf,1 who determined the solubilities of copper minerals in 0.10 pct sodium cyanide solution, showed that malachite, cuprite, chalcocite, and bornite are readily soluble in cyanide; least soluble are chalcopyrite and chrysocolla. The Mining Chemicals Laboratory of American Cyanamid Co. has studied the possibilities of using cyanide solutions for leaching base metals. In this article the authors present the results of their experiments with cyanide leaching to reduce the copper content of a zinc concentrate from 0.050 pct to the desired specification of less than 0.02 pct. Zinc Ore Sample: The sample of commercial zinc ore used in this investigation to produce zinc concentrates was ball mill feed ranging from 1/2 in. to fines. The ore was crushed to —10 mesh and riffled into 600-g charges for zinc flotation. Analysis revealed 4.54 pct Zn and 0.005 pct Cu. Examined microscopically, the ore consisted essentially of cream-colored sphalerite and carbonate gangue. It contained a small amount of pyrite, partly tarnished. The only copper mineral identified was chalcopyrite, mostly smaller than 20µ, some of which occurred as attachments on sphalerite. Flotation Procedure: Batches of zinc concentrates were made as required according to the following general procedure. A 600-g charge of —10 mesh ore was ground for 4 min at 60 pct solids in a laboratory steel rod mill. Screen sizing showed it to be all —35 mesh with 42 pct —200 mesh. The pulp was transferred to a Fagergren laboratory flotation machine, diluted to 25 pct solids and conditioned for 5 min with 0.6 lb per ton CuSO4, . -5H2O. It was then conditioned with 0.10 lb per ton Sodium Aerofloat promoter and floated for 5 min with pine oil as frother and creosote as froth stiff-ener. The pH during flotation was 8.5. A typical analysis of zinc concentrate subjected to leaching is 44.41 pct Zn and 0.051 pct Cu. The ratio of concentration was close to 10 to 1. Leaching Procedure: Aero Brand cyanide, technical calcium cyanide analyzing 49.5 pet NaCN equivalent, was used for all cyanide leaching tests. For each test three rougher concentrates floated as described were combined (total weight close to 180 g) and the water content adjusted to 150 ml. The percent solids in the pulp was thus 55. After a weighed amount of cyanide flakes had been added, the pulp was agitated on rolls for a given period, then filtered and washed. Filtrate and washed concentrate were assayed for copper content. The procedure for ammonia leaching was similar to the cyanide process. A series of tests was run in which the effects of ammonia as a solvent for copper in the zinc rougher concentrate were investigated. In each test 180 g of zinc rougher concentrate was leached with 150 ml of ammonia solution. Various strengths of ammonia and times of leaching were investigated. The results are shown in Table I. It is apparent that ammonia was a poor solvent for copper in the zinc concentrate; 60 min of agitation with a relatively strong NH:, solution extracted only 2 pct of the copper. CYANIDE LEACHING TESTS Effect of Solution Strength: The solvent effects of 0.125, 0.187, and 0.250 pct NaCN equivalent solutions were compared for leaching periods of 15 min. Residue and filtrate were assayed for copper content. The copper content of the filtrate plus wash was calculated back to the original volume of cyanide solution (150 ml). The effects of cyanide strength are given in Table II, It will be noted that 15 min leaching with 0.25 pct NaCN equivalent solution extracted 74.6 pct of the copper in the zinc concentrate. The leached product assayed 0.013 pct Cu, appreciably below the required specification of 0.020 pct. Effect of Leaching Time: Portions of zinc concentrate were leached with 0.25 pct NaCN equivalent

Jan 1, 1961

By T. E. Watkins, M. D. Nelson

A method of determining the lime content of drilling muds proposed by Battle and Chaney* has been examined both in the Field Research Laboratories of Magnolia Petroleum Co. and in field drilling operations. This proposed analytical method is condensed as follows: Titrate one ml of mud and one ml of mud filtrate, each with 0.02 N H2SO4, to the end point with phenolphthalein. The volume of acid in ml required for the mud titration is recorded as Pm and that of the mud filtrate titration as Pf Calculation of the lb lime/bbl mud is accomplished by use of the formula, lb lime/bbl mud = 0.6 (Pm - 1.3Pf) - 0.6 The analytical procedure outlined by Battle and Chaney was found to be quite satisfactory when reasonable precautions are used in mud sampling technique. Calculation of lime concentration by the method proposed in the above publication, however, has given values that varied as much as 100 per cent from the known lime content, for muds of either high or low solids concentration. By use of a formula, lb lime/bbl mud = 0.26 (Pm-F1.Pf), based on chemical equivalents of acid required for titration, both laboratory and field data have been satisfactorily correlated with the known amounts of lime present in the muds. In this formula a correction, F1, or volume fraction of liquid in the mud, is made for the solid content of the mud. Pm and Pf * Paper on "Lime Base Muds," presented by J. L. Battle (Humble Oil and Refining Co., Houston, Tex., and P. E. Chaney (Sun Oil Co., Beaumont Tex.), at the 1949 Spring Meeting of the Southwestern District API Division of Production, Dallas, Tex. The analytical procedure has also had wide distribution in a trade journal, Kembreak, published by the Accuracy Rig and Tool Co., Houston, Tex, †Derivation of equation lb/bbl — grams/350 ml 1 ml 0,02 N acid = 0.000741 grams of lime 1 ml 0.02 N acid/ml lime suspension = 0.26 lb of lime bbl lb of lime/bbl = 0.26 (Pm -F1, Pf ) have the same significance as in the Battle and Chaney equation. Table I shows typical data employing both formulas in calculating the lime content of various lime muds. This suggested procedure ignores lime which is in solution in the mud. The solubility of lime in water, normally about 0.5 lb per bbl, is greatly decreased by the addition of caustic soda, and, in a lime mud, it is probable that the concentration of dissolved lime is of the order of 0.1 lb per bbl. Such an amount of lime can be ignored, since it is within the range of accuracy of the method.

Jan 1, 1950

By A. F. Giamei, E. J. Freise

A discussion of the various factors affecting the accuracy of volume fraction determination by the direct comparison X-ray diffraction method is presented. To minimize errors introduced by nonrandomization effects such as preferred orientation and large grain size, as well as errors introduced by statistical effects, an iterative mathematical analysis is introduced. This analysis is applied to all observable diffractio~ spectra from a given specimen by means of computer techniques and is statistically superior to the standard direct comparison technique which utilizes only one or tm sets of intensity spectra. The computer program also presents a graphical interpretation of- the results which enables the investigator to visualize and readily assess the scatter in volume fraction estimates caused by deviations from randomness. Finally, the iterative analysis is applied to experimental data collected from a series of plain carbon steels in both the as-received and spheroidized conditions to determine the volume fraction of cemen-tite present in each case. The results show markedly good agreement with chemical analyses for all spheroidized specimens. In theory, quantitative X-ray diffraction is a power-ful analytical technique for precise determination of the volume fractions of various phases present in a multiphase poly crystalline aggregate. There are two generally used methods; both utilize the fact that the intensity of a diffraction line of a particular phase is a function of volume fraction of that phase present in the aggregate. The more common method is the so-called internal standard technique where a known amount of standard substance is mixed with the aggregate containing the unknown. The resulting ratio of the intensity of a particular diffraction line of the unknown to the intensity of a diffraction line from the standard is used to find the weight fraction of unknown material by reference to the intensity data obtained from a previously prepared set of standards containing the same amount of standard material. The details of this technique are outlined in standard works on X-ray diffraction.' The disadvantages of the technique are that it requires the use of powder specimens and that the powder mixture must be homogeneous near the surface to the maximum effective beam depth. The alternative technique is the direct comparison method in which the ratio of the intensity of a diffraction line of a phase in the aggregate to the intensity of a second-phase diffraction line yields the ratio of the volume fractions of each phase present. This method has been applied most extensively to the determination of the percentage of retained austenite in martensitic steels and to determining the amounts of hcp and fcc allotropic modifications in pure cobalt5 and the amounts of hexagonal and rhombohedra1 modifications in graphite.8 This method is applicable to bulk as well as powder aggregates and is the technique which will be considered in the following text. It is the purpose of the present communication to show that by combining the results of X-ray diffrac-tometry with the use of high-speed digital computers the results of the direct comparison quantitative X-ray analysis technique can be optimized by using all of the data available on a diffraction pattern. THEORETICAL DISCUSSION In optimizing any quantitative X-ray diffraction experiment, the problem of accuracy vs time to collect and analyze the experimental data arises. For any method to be practical, it is required that both experimental and analytical procedures are reasonably short. In most of the previous work performed by the direct comparison method, intensity data from only one or two sets of peaks were used to calculate the volume fraction of phases present in the aggregate. Consequently, rather long-time experimental measurements are required to assure that the intensity data are sufficiently accurate to justify the use of one or two sets of data. By using computer techniques to analyze the experimental data it becomes feasible to use all of the available data on a diffraction pattern. By so doing, the time spent in measuring any one diffraction maxima can be appreciably reduced. Although this results in poor counting statistics for any one maxima, the number of data points available for analysis is greatly increased. Based on the above discussion, it will be assumed that a continuous scanning counter-diffractometer technique will be used to collect intensity data from a two-phase mixture. The integrated intensity of the ith diffraction line from the a phase in the aggregate is given by:'" where is the volume fraction of the a phase, The various quantities in Eq. [la] are angular independent while those in [lb] depend on the hkl spectrum of a particular phase. The meaning of the individual quantities in Eqs. [la] and [lb] are given in Appendix 1. It is convenient at this point to outline briefly the factors which will affect the measured intensity of any one hkl spectrum. a) Extinction effects arise from two independent experimental conditions. Primary extinction arises from a high degree of crystal perfection and results in spectra having lower intensity than predicted by Eq. [I]. Any treatment, such as powdering, which reduces

Jan 1, 1968

By Donald J. Knight

HEAT Treatment at 1500' F of a mild steel containing 0.1 pct C, in an atmosphere which is oxidizing to both carbon and iron, results in the progressive oxidation of the metal surface with little or no change in the carbon content of the underlying metal. Further heat treatment of the scaled metal in either a neutral atmosphere or in a vacuum may or may not result in the decarburization of the metal depending upon the physical nature of the scale. It is apparent that if a continuous layer of oxide is present on the steel surface, the reaction OScale + Cmetal Cogas cannot progress since the SO formed gas would be unable to leave the oxide/metal interface. Thus, in order for the reaction to progress, the oxide must be cracked or porous. Vacuum heat treatment at 1500" F of samples with a thick continuous oxide scale showed no decarburization of the steel. However, when cracks were introduced mechanically into the scale prior to the vacuum heat treatment notable decarburization of the metal resulted and a structure as shown by Fig. 1 obtained, i.e., reduction of the crack walls to ferrite. With reference to the diagram of Fig. 2, it would appear that a mechanism of the following type takes place. Carbon atoms arriving at an oxide/metal/void interface, such as 'A', Fig. 2(a), can combine with oxygen atoms from the scale and leave the reaction site as Cogas thereby reducing the oxide to metal. On a greatly magnified scale, Fig. 2(b),this will appear as a ferrite projection along the crack wall. Carbon atoms entering this projection can react with oxygen atoms at point 'C', which is a new interface, and so on leading to a progressive growth of the ferrite along the crack wall and to the surface, Figs. 2 (c) and 1. It would appear that the only means by which thickening of the ferrite film can take place is by a diffusion of oxygen through the ferrite film to react with carbon at the newly formed ferrite/ void interface. Since the diffusion rate of carbon is reportedly much greater than that of oxygen, and since there is a low probability factor of oxygen and carbon atoms arriving simultaneously at the same site on the ferritehoid interface, there will be a tendency for more rapid lengthening than thickening of the ferrite layer, as is observed.

Jan 1, 1962

By Robert L. Akright

LOCATION AND HISTORY The Candelaria silver mine is located in an arid, isolated desert setting in Sections 3 and 4, T.3N., R.35E., and Section 33, T.4N., R.35E., Mineral County, Nevada (Fig. 1). Silver was discovered in 1863 by Mexican explorers, and high grade silver veins were mined from the early 1870s through the 1880s. Essentially all mining had ended by 1890. The veins were mined by underground methods typical of the period. As is the case in many mining districts, Candelaria was studied and explored by a number of companies. All these efforts were terminated short of mine development because of low silver prices and difficult metallurgy. On March 1, 1976, Occidental Minerals (Oxymin) entered into a Limited Partnership agreement, known as Candelaria Partners, as General Partner with Congdon and Carey Ltd. No. 4. Prior to the agreement, Congdon and Carey had acquired the candelaria properties as part of a bullish silver program and did considerable exploration which indicated the possibility of a large reserve of shallow silver mineralization. GEOLOGY AND ORE DEPOSITS Silver and gold mineralization in the Candelaria district occurs in high-grade fissure veins with silver values ranging from 0.6 to 7.8 kg/t (20 to 250 oz per st). These veins, combined with the low grade disseminated mineralization in the intervening material between the veins, form Manto- like deposits 15 to 46 m (50 to 150 ft) thick. Three such deposits are found in the Candelaria district: the Lucky Hill, Mount Diablo, and Northern Belle deposits (Figs. 2 and 3). The average ore grade of the Lucky Hill and Mount Diablo [ ]

Jan 1, 1985

By I. R. Taylor

Union Carbide has recently developed two open- pit vanadium mines in the Wilson Srpings area of central Arkansas about five miles southeast of Hot Springs. The ores from these mines, together with those from a larger vanadium deposit at nearby Magnet Cove, are processed at a new 1600- tpd plant built by the company in the immediate vicinity (Fig. 1). The Wilson Springs vanadium deposits are associated with the Potash Sulfur Springs intrusive, a circular igneous complex which is exposed over an area that is somewhat less than a mile in diameter.1 The complex has a crude ring structure similar to that of the larger Magnet Cove instrusive six miles to the east.2

Jan 4, 1969