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By C. G. Fink, G. L. Putnam

The dissolution of gold by cyanide solutions was studied by determining the time required for the solvents to dissolve gold leaf. Minute traces, even 0.5 ppm, of sulphide ion retard the dissolution of gold, and this behavior cannot be accounted for by the presently accepted hypotheses involving oxygen-depletion or thiocyanate formation. On the other hand, traces of the salts of lead, bismuth, mercury, and thallium considerably accelerate the dissolution. The beneficial effect of lead is dependent upon the pH and cyanide ion concentration of the solution. ALTHOUGH cyanide solvents are used very ex-x*. tensively for the recovery of gold from ores and concentrates, the normal rate of solution of the precious metal as determined by Barsky, Swainson, and Hedley,1 and others2 is less than about 3 mg per sq cm of exposed gold surface per hour, corresponding to a corrosion depth of approximately 1.5 microns (0.00006 in.) per hr. Although the slow rate may be increased to some extent in certain cases, as, for example, when the the gold is partially imbedded in iron pyrites,3 the leaching operation is generally the most time-consuming step of the cyanide process. Frequently it is necessary for the leaching solvents to remain in contact with the ores for 50 to 200 hr in order to dissolve all of the gold particles.' Not only does the slow solution rate cause some increase in the capital costs, but the cyanide consumption also may be increased because of vaporization of hydrocyanic acid and secondary reactions with minerals such as malachite (CuCO3 • Cu(OH)2), and pyrrhotite, which often are associated with gold. It is not surprising that numerous attempts have been made to accelerate the dissolution of gold in cyanide solutions. Experimental Gold Leaf Test: The gold leaf test was apparently originated by M. Faraday, who, by means of it, discovered that dilute cyanide solutions would dissolve gold readily in the presence of oxygen. The usefulness and reliability of the test have been discussed elsewhere.5,6 Essentially, the method consists of determining the time required for 5-ml portions of cyanide solvents to dissolve squares of 23 carat gold leaf, 0.5 cm on edge, when shaken in 10-ml test tubes with the solvents. The weight of gold leaf per test was 0.051 mg as determined by the direct weighing of a leaf 8.6x8.6 cm (weight = 15 mg) and measuring the area of the test sample (0.25 sq cm). Gold leaf is of remarkably uniform thickness.6 Since gold leaf, like native gold, contains small amounts of copper and silver, the results are comparable with those one might expect in cyaniding gold ores. As six or more tests can be made simul- taneously, the relative efficiencies of the solvents can be evaluated readily. All dilute solutions of lead, bismuth, thallium and mercury salts were prepared by the ordinary dilution method used by chemists. Our C.P. sodium cyanide and buffering reagents had no detectable amounts of either sulphide ion or heavy metals. Soluble Sulphides in the Cyanide Process: The action of soluble sulphides is of interest in the study of the dissolution of gold in cyanide solutions. That gold ores which contain compounds of arsenic and antimony often are not amenable to direct cyanide treatment is well known, and it said that arsenic and antimony are "cyanicides."7 It is commonly believed that part of the sulphur content of such ores is soluble in alkaline solutions to give sulphide ion, which reacts with the free cyanide content of the leaching solutions to form inert thio-cyanates or reacts with the dissolved oxygen to form sulphites or sulphates.8 A purpose of this paper is to demonstrate that sulphide ion may behave in a manner that cannot be explained by either the oxygen-depletion or thiocyanate formation theories and to prove directly that concentrations of sulphide ion which cannot be detected even by colorimetric methods may retard the dissolution of gold.

Jan 1, 1951

By C. G. Fink, G. L. Putnam

The dissolution of gold by cyanide solutions was studied by determining the time required for the solvents to dissolve gold leaf. Minute traces, even 0.5 ppm, of sulphide ion retard the dissolution of gold, and this behavior cannot be accounted for by the presently accepted hypotheses involving oxygen-depletion or thiocyanate formation. On the other hand, traces of the salts of lead, bismuth, mercury, and thallium considerably accelerate the dissolution. The beneficial effect of lead is dependent upon the pH and cyanide ion concentration of the solution. ALTHOUGH cyanide solvents are used very ex-x*. tensively for the recovery of gold from ores and concentrates, the normal rate of solution of the precious metal as determined by Barsky, Swainson, and Hedley,1 and others2 is less than about 3 mg per sq cm of exposed gold surface per hour, corresponding to a corrosion depth of approximately 1.5 microns (0.00006 in.) per hr. Although the slow rate may be increased to some extent in certain cases, as, for example, when the the gold is partially imbedded in iron pyrites,3 the leaching operation is generally the most time-consuming step of the cyanide process. Frequently it is necessary for the leaching solvents to remain in contact with the ores for 50 to 200 hr in order to dissolve all of the gold particles.' Not only does the slow solution rate cause some increase in the capital costs, but the cyanide consumption also may be increased because of vaporization of hydrocyanic acid and secondary reactions with minerals such as malachite (CuCO3 • Cu(OH)2), and pyrrhotite, which often are associated with gold. It is not surprising that numerous attempts have been made to accelerate the dissolution of gold in cyanide solutions. Experimental Gold Leaf Test: The gold leaf test was apparently originated by M. Faraday, who, by means of it, discovered that dilute cyanide solutions would dissolve gold readily in the presence of oxygen. The usefulness and reliability of the test have been discussed elsewhere.5,6 Essentially, the method consists of determining the time required for 5-ml portions of cyanide solvents to dissolve squares of 23 carat gold leaf, 0.5 cm on edge, when shaken in 10-ml test tubes with the solvents. The weight of gold leaf per test was 0.051 mg as determined by the direct weighing of a leaf 8.6x8.6 cm (weight = 15 mg) and measuring the area of the test sample (0.25 sq cm). Gold leaf is of remarkably uniform thickness.6 Since gold leaf, like native gold, contains small amounts of copper and silver, the results are comparable with those one might expect in cyaniding gold ores. As six or more tests can be made simul- taneously, the relative efficiencies of the solvents can be evaluated readily. All dilute solutions of lead, bismuth, thallium and mercury salts were prepared by the ordinary dilution method used by chemists. Our C.P. sodium cyanide and buffering reagents had no detectable amounts of either sulphide ion or heavy metals. Soluble Sulphides in the Cyanide Process: The action of soluble sulphides is of interest in the study of the dissolution of gold in cyanide solutions. That gold ores which contain compounds of arsenic and antimony often are not amenable to direct cyanide treatment is well known, and it said that arsenic and antimony are "cyanicides."7 It is commonly believed that part of the sulphur content of such ores is soluble in alkaline solutions to give sulphide ion, which reacts with the free cyanide content of the leaching solutions to form inert thio-cyanates or reacts with the dissolved oxygen to form sulphites or sulphates.8 A purpose of this paper is to demonstrate that sulphide ion may behave in a manner that cannot be explained by either the oxygen-depletion or thiocyanate formation theories and to prove directly that concentrations of sulphide ion which cannot be detected even by colorimetric methods may retard the dissolution of gold.

Jan 1, 1951

Discussion of the paper of GEORGE S. Rice, presented. at the Pittsburgh meeting, October, 1914, and printed in Bulletin No. 94, October, 1914, pp. 2459 to 2492. WILLIAM GRIFFITH, Scranton, Pa.-I notice in the discussions and literature that emphasis is placed on rock dust, shale dust, and limestone dust, and I infer that these different. sorts of rock are ground up to produce this dust. -Is that right? MR. RICE.-That is correct, but we do not have to grind the limestone dust we are using in the experimental mine, as that is obtained from a quarry, and is used just as it comes; we can get it very cheaply, as it is a by-product of the quarries. MR. GRIFFITH.-Have any experiments been made with ordinary dirt out of the fields; could not that be used as ground dust? MR. RICE.-If you dry it and powder it enough so it will float in a, strong air current it might be all right for the barriers, but if it is damp there will be a tendency for it to mat together; then it would be quite useless for making a dust cloud. There might also be another disadvantage if used through the whole mine, if it had very much free silica in it, which is bad for the lungs. Limestone and selected shale dust would not affect the health of miners. MR. GRIFFITH.-In order to do very much good with any of those barriers, they ought to be rather extensively used throughout the mines, and there are few mines that have facilities for grinding up this rock into such a fine dust. If the ordinary earth from a plowed field could be used, even if it were not quite so good, it is more accessible and very much cheaper; therefore, in using it, with the universality of the supply through-out the country, it would tend to stop explosions. MR. RICE (communication to the Secretary*).-In closing, it is well to again emphasize that I do not advocate barriers being a "cure-all" for explosions. It will be generally agreed that prevention is best, not only by means of improved methods of using explosives, and ventilation to prevent accumulations of firedamp, but also by either thoroughly wetting the dust throughout the mine, or else so treating it with rock dust or other inert dust that an explosion cannot start. From my observations I believe that rock dusting. is a practicable method, and has the merit of visibility, and remaining effective for considerable periods, whereas the watering method has to be daily followed up, and if neglected for a short period the mine may become in a dangerous condition. The Germans

Jan 4, 1915

The following is an incomplete list of members and guests who called at Institute headquarters during the period Feb. 10, 1918 to Mar. 10, 1918: W. G. Anderson, St. John, N. B., Canada. Charles E. Locke, Boston, Mass. L. M. Banks, Camp Meade, Md. E. T. Lednum, Joplin, Mo. P. E. Barbour, Albany, N. Y. C.' K. McDonald, Washington, D. C. Alan M. Bateman, New Haven, Conn. C. T. Malcolmson, Chicago, Ill. Graham Bright, Pittsburgh, Pa. Stuart B. Marshall, Badin, N. C. J. F. Callbreath, Washington, D. C. T. C. Merriman, New Haven, Conn. J. E. S. Clark, Riverside. Cal. Arvid E. Nissen, Gary, Ind. G. H. Clevenger, Palo Alto, Cal. Herbert G. Officer, Conway, S. C. George C. Crossley, Trenton, N. J. J. E. Parker, Bulawayo, Rhodesia, S. Afr. R. H. Eagles, Palmerton, Pa. Francis R. Pyne, Elizabeth, N, J. Charles Enzian, Pottsville, Pa. Alfred Hull Ramage, Joplin, Mo. Albert H. Fay, Washington, D. C. H. H. Stoek, Urbana, Ill. David B. Gemmill, Crown King, Ariz. G. M. Taylor, Colorado Springs; Colo. Ronald Harris, London, Ont., Canada. Charles Tubby, St. Paul, Minn. Wm. J. Hayes, Colombia. So. America. J. B. Tyrrell, Toronto, Canada. B. B. Hood, Chrome, N. J. Edmund W. Westervelt, Ymir, B. C. 0. P. Hood, Pittsburgh, Pa. Carl Zapffe, Brainerd, Minn. H. M. LaFollette, LaFollette, Tenn. W. S. Boyd, formerly superintendent of mines of the Ray Consolidated Copper Co., has been appointed assistant general manager. William Campbell, Professor of Metallurgy, at Columbia University, is acting as metallurgist at the New York Navy Yard.

Jan 4, 1918

By W. Mckewan, W. M. Fassell

The oxidation rates of copper have been determined at temperatures from 600" to 900°C in oxygen from 14.7 to 400 psi total oxygen pressure. The oxidation rate of copper is unchanged by oxygen pressures within the range studied. The observed data extend Feit-knecht's conclusion concerning the pressure independence of copper from atmospheric pressure to 400 psi. All samples studied in the above-mentioned temperature and pressure range have both Cu2O and CuO present in the oxide film. NUMEROUS papers have been published on the oxidation of copper, some of which have noted the effect of oxygen pressure on the oxidation rate of copper. It must be noted, however, that no data on the oxidation rates of copper at pressure in excess of 1 atm have been reported in the literature. (Le Chatelier¹ reported that a black oxide of silver was formed at 300°C and 15 atm pressure.) This is likewise true for the other metals. This investigation was initiated to obtain experimental oxidation rate constants for pure metals at elevated temperatures and high oxygen pressure. Copper was selected as the first metal since probably more reliable data are available on its oxidation rates and related physical and chemical properties than for any other metal or alloy. As a general summary, the following conclusions appear well established for the oxidation of copper: 1—The oxide coating consists of Cu2O with a superficial coating of CuO providing the ambient oxygen pressure exceeds the equilibrium pressure for the coexistence of Cu2O and CuO.² The following sequence of phases is then Cu/Cu2O/CuO/O2 (gas). The Cu2O consists of large crystals that have no relation to the orientation of the metal crystals, except for a very thin layer adjacent to the metal." The CuO consists of very fine crystals randomly oriented. If the oxygen pressure is below the equilibrium pressure for the coexistence of Cu2O and CuO, the coating consists of Cu,O only. 2—The rate-determining factor in the parabolic oxidation of copper is the diffusion of Cu+ ions through the Cu,O layer.4,6,7 The Cu+ ions are accompanied by electrons to maintain electrical neutrality. The mechanism of the reaction at the Cu2O/CuO interface and the method of growth of the CuO is in some doubt. 3—On copper, there are three reported pressure effects: (a) At pressures below 0.3 mm Hg oxygen pressure, the oxidation rate increases directly with pressure.', ' .Vxygen starvation at the surface may account for this effect. (b) At oxygen pressures from 0.3 to 63 mm, the oxidation rate increases as the 7th root of the oxygen pressure providing the temperature is such that only Cu2O is present in the film. (c) At pressures from above the equilibrium pressure for the coexistence of Cu2O and CuO (varies with temperature) to atmospheric pressure, the oxidation rate is independent of the oxygen pressure.' Equipment In order to determine the oxidation rates of metals in an oxidizing atmosphere at pressures up to 400 psi, the equipment is somewhat different than for low pressure work as is shown in Figs. 1 and 2. A Leeds and Northrup Micromax recording controller (A) is used to control the temperature of the Ni-chrome furnace winding in conjunction with a Micromax electric drive unit. The drive unit adjusts a 20 amp Variac (variable transformer) to control the power input into the Nichrome furnace winding. Due to the "self heating" of the sample by oxidation, frequently encountered in oxidation rate studies, it is essential that the sample temperature be measured independently. This is done by means of a series of six chromel-alumel calibrated thermocouples located spirally around the oxidizing metal sample. Each thermocouple is partially shielded from the direct radiation of the furnace wall by

Jan 1, 1954

Institute of Metals Division Iron and Steel Division Extractive Metallurgy Division Council A W Thornton (ISD), Chairman, R W Shearman, Secretary, C S Barrett (IMD), J C Kinnear, Jr (EMD), John Chipman (ISD), J S Smart, Jr (IMD), A W Schlechten (EMD), M E Volin (MED), D S Eppelsheimer (MIED) Journal of Metals Editorial Advisory Committee J S Smart, Jr, Chairman, W A Dean, J J Golden,T D Jones, Evan Just, J C Kinnear, Jr, M Tenenbaum Pacific Northwest Regional Conference E R Marble, General Chairman, Marshall Huntting, Assistant General Chairman, W C Douglass, Mining Chairman, H C Hughes, Mining Chairman for British Columbia, W C Douglass, Mining Chair¬man for United States, Paul Billingsley, Geology Chairman, W D Nesbeitt, Miner¬als Beneficiation Chairman, H D Kelley, Industrial Minerals Chairman, J G Johnston, Metals Chairman, Lloyd Banning, Iron and Steel Chairman, W G Rouillard, Extractive Metallurgy Chairman, E C Roberts, Physical Metallurgy Chairman, D A Pifer, Mineral Industry Education Chairman, Frederick Brien, General Arrangements Chairman Metals Branch Membership Committee C M Squarcy, Chairman, R C Cole, Harold Mar¬golin, M E Nickel, S K Scovil Bylaws Committee A W Thornton, Chairman, W R Hibbard, Jr, J S Smart, Jr (IMD), John Chipman, T S Washburn (ISD), T D Jones, J D Sullivan (EMD)

Jan 1, 1956

Edward Halse, Puerto Berrio, Colombia, So. Amer. (communication to the Secretary*): The Taviche mining-district is generally known as " Taviches," being named from the two villages called respectively San Pedro Taviche and San Jero-nimo Taviche. It is so called by Jose G. Aguilera, in his paper on the Geographical and Geological Distribution of the Mineral Deposits of Mexico;' and in published reports by the late N. W. Rudston Read ;2 and by Juan de Dios Villarello3 The region is a large one, measuring about 24 miles long and 7 miles wide. Dr. Chance, in his interesting paper, tells us very little about the nature of the ores, and, with regard to the geology of the district, contents himself with observing that " the country, as a rule, consists of eruptive rocks; and no evidences of sedimentary strata appear near the mines." The latter part of the above statement is hardly correct. The formation is mainly

Jan 1, 1906

By Lane Mitchell

A ceramic product or processed material is a solid composed of materials which have been subjected to heat above 875°F. The raw materials, which are blended together (or in some cases used singly), are selected and utilized for various reasons such as ease of fabrication, aid to processing, to yield desired properties after processing, lack or controllable degree of toxicity or hazard, availability, cost, and perhaps other considerations. Almost all solid inorganic, some organic, and some liquid and gaseous materials have the potential to be used individually in some ceramic product. There are several fundamental functions to be fulfilled in every ceramic product and a number of secondary functions are desirable in specified products. These functions are generally met by the most widely occurring minerals and rocks of the earth and their debris. This fact characterizes ceramics as a field utilizing the raw materials most available to man. Of course, specified products utilize synthetics, organics, and rare inorganics to produce desired results. Any solid nonmetallic product processed by subjection to temperature above a red heat may be called a ceramic product. Widely used construction materials and units, domestic utensils and units, industrial parts to facilitate manufacture, technical components, and aesthetic creations are very often of a ceramic nature because of the durability, inertness, hardness, ease of fabrication, cost, and availability of the ingredients. Often, organics or metals cannot meet desired specifications for some of these products. The rocks and minerals and mineral debris of the earth are largely siliceous. Oxygen and silicon comprise roughly 75% of the earth's crust with aluminum, iron, calcium, and the alkalies following in abundance. Silica ( SiO, ) and silicates can be melted to form glasses. Alumina (A1,0,), present in a mineral com- pound, gives greater durability, hardness, and strength, but lessens the glass-forming property. Iron, calcium, and the other alkalies flux silica and reduce melting points. Thus, sand, which is generally almost pure SiO,, and clay, which is generally hydrated alumina silicate, are the most widely used of all ceramic raw materials-principally because of the glass-forming propensities of silicates. In ceramic formulations, clay is generally a refractory filler or skeletal material, having in the raw state a plasticity derived from its colloidal grain size and its water-loving nature. On the other hand, silica sand is a glass former or nonplastic filler. Clay and silica sand in pure forms are quite refractory, i.e., not easily melted. Clay, although siliceous, is less of a glass former than pure silica and is more refractory. Natural contaminants, such as iron oxide or limestone, adulterate many clays and some sands. These contaminants act as fluxes and reduce the fusion points of the mineral or blends. Glass is made from silica sand by fluxing the sand with strong bases, usually soda ash and limestone. Red building bricks are hard and durable because the sand and clay have been partially fused with help of natural iron oxide serving as a flux. The iron oxide per- forms a dual function, serving as a pigment as well as a flux. In a blend of clay and sand and iron oxide, the sand is more susceptible to fusion than is the clay. Although silica sand and clay are the most widely used raw materials in most ceramic products, many other minerals, and some non- minerals are utilized in products where these materials can produce or aid in achieving desired results. Limestone and dolomite, feldspars, pigmentary minerals, refractory oxides or carbides, and special property producers can

Jan 1, 1975

By W. B. Tucker

UNUSUAL interest has recently centered in the Mojave mining district of California, owing to new discoveries of gold ore at the Silver Queen mine, and subsequently at other neighboring proper- ties. These finds have proved that opportunities exist for the prospector even in old mining districts, where careful search may still be rewarded. The Mojave district is characterized by a group of small hills centering around Soledad Butte, four to six miles southwest of Mojave, in Kern County. This butte is 1250 ft. higher than the surrounding desert and 4000 ft. above sea level. Four miles west of Soledad Mountain are the so-called Middle Buttes, a group of flat-topped hills. Gold was first discovered in the district in 1894, and the following productive mines developed: Queen

Jan 1, 1936

By Peter R. Morris, Alan J. Heckler

THREE angles are required to specify the orientation of a crystallite with respect to a physical reference frame. The distribution of crystallite orientations in a polycrystal is thus a function of three angular variables. The most widely used experimental techniques for studying orientation in polycrystals lead directly to the pole figure representation, i.e., the distribution of the poles of certain crystallographic planes in terms of two angular variables. In recent years1-5 methods have been developed which permit determination of the (three-angle) crystallite orientation distribution from several (two-angle) pole figure distributions. In this work Roe's method has been applied to the study of orientation in hcp materials. The method is illustrated for commercial purity titanium sheet (Ti-70) which was cold rolled (65 pct reduction), annealed at 1450°F for 3 min, and air cooled. The grain shape was observed to be equiaxed after this treatment. EFFECTS OF PHYSICAL, CRYSTALLOGRAPHIC SYMMETRY In Roe's method the crystallite orientation distribution, w(?,?,F), is expanded in a series of generalized spherical harmonics 11(?,?,F) = E E E W^Zirmtye-tote-in* [l] 1=o ,,,=-I ,,=-I where { = cos 8. The set of Euler angles employed here is illustrated in Fig. 1. The axis for each rotation is denoted by a double arrowhead. The positive sense of each rotation is that of a right-handed screw advancing in the direction of the double arrowhead. The X, Y, and Z directions correspond to the rolling direction, cross direction, and normal direction, respectively. In the initial orientation (10.O), (12.O), and (00 . 1) planes are perpendicular to the X, Y, and Z directions, respectively. The IC/ rotation about the Z axis is carried out first by rotating X into X', Y into Y', and leaving 2 unchanged, i.e., Z' = Z. The 8 rotation about the Y' axis is carried out second by rotating X' into X", 2' into Z", and leaving Y' unchanged, i.e., Y" = Y'. The I$ rotation about the Z" axis is carried out last by rotating X" into X"', Y into Y"', and leaving 2" unchanged, i.e., 2"' = 2". Any specified orientation of the X'", Y'", and Z'" crystal-fixed axis system relative to the X. Y, and Z physical axes (rolling direction, transverse direction, and sheet normal direction, respectively) can be obtained by appropriate IC/, 8, and (F rotations. The Zl,, of Eq. [l] are the Jacobi polynomials, augmented by the square root of the weight function. The Zl,, are symmetric in m,n, i.e., Zl,,= Zlnm. For orthotropic physical symmetry and hexagonal crystallographic symmetry, the coefficients, W!,,, of the series are all real, W!mn = Wzfi, = Wlm~ = Wlfi~, 1 and m are even and n is restricted to 6k, where k = ...,-2,-1, 0, 1, 2, .-.. The determination of the Wlmn from pole figure data has been previously described.'~~ The Zl,, may be written in multiple angle form

Jan 1, 1970

By J. F. Myers

AT the Regional meeting in Columbus, Ohio, in September 1949, the authors presented a progress report of the first year's operation with a Hardinge tricone mill in closed circuit with a Dorr hydroscillator. The present report covers our findings on this grinding circuit to January, 1950. In order to clarify our position, the authors wish to state that no invention or discovery is claimed. The Tennessee grinding circuit is simply an engineered arrangement of known equipment arranged to incorporate all of the recognized efficiency factors of comminution as they are known today. As we concluded our first report, it was not clear how effective the Tennessee mode of operation would be on harder ores. The only information we had at that time was that the Bond grindability test at 48-mesh gave 6.04 g of undersize per revolution. A later test on the same sample at 100-mesh reduced this to 2.04 g, which is definitely in the harder ore class, and which makes the reported 8.80 kw-hr per ton of -200-mesh produced a very creditable figure.

Jan 1, 1950

By C. S. Yust, Lida K. Barrett

The change in shape of the void in a sirzterir~g copper mass has been investigated as a juntction of' density. A serial sectioning' technique was used to eoaltrate the irregular shape of the void at two levels qf density. A measure of the void size and configuration, the proximity number, is defined and used to describe the progress of void removal. The process of. void removal deduced front the observations of this study contrasts with current sintering models in that it takes into account the irregularity of structure of a sintering mass and demonstrates that isolated Porosity does not occur first as spherical pores, but as large, definitely nonspherical sections of the void void volume. The process of sintering, about which there is much practical and theoretical knowledge, has evaded a direct and thorough analysis despite the intensity with which it has been studied for 60 years or so. This is due, of course, to the complex structure of a sintering mass and the inability to observe directly the development of a fully dense solid from the initial particulate arrangement. Extensive theoretical analyses have been based on the adoption of one or another of several model systems, that is, by visualization and analysis of some sort of regular assembly or arrangement of geometric "particles" approximating the conditions of a sintering mass. It seems appropriate at this time to try to examine experimentally in some detail the extent to which a sintering mass of irregular particles dlffers from these models. Many models deal with neck growth and the initial stage of sintering and follow the direction established by ~ucz~nski' in 1949 for the sintering of spheres to flat plates. Recently Johnson and cutler2 have adapted these models to sintering of powder masses. coble3 has presented a mathematical model for sintering that applies to the middle and final stages of the process. These papers, without exception, assume a regular geometry, generally spheres in contact in a regular array. Rhines~ and coworkers, however, are studying the sintering process by applying a model based on the topological concept of genus which permits them to consider an irregular structure. whites has described the various models with the exception of that of Rhines et al., and the assumptions on which they are based and their shortcomings. The present paper examines the geometric changes that occur in the powder mass during sintering by examination of the void. The method is to analyze a series of partially sintered structures and to propose from this analysis the sequence of events which occur in the removal of the void space as a sintering mass progresses from a collection of individual particles to a solid body. The irregular nature of the stacking of particles and of the particles themselves will be taken into account. The significant points derived from this study are: first, accurate reconstructions of the irregular void shapes are presented; second, it is clearly established that closed porosity occurs first as widespread volumes of interconnected porosity, definitely nonspherical in shape; and third, a new factor, the proximity number, is defined, which serves in this paper as a tool for describing the void shape changes observed, and which will be used in a later paper as part of the basis of a mathematical model for sintering. While the specific material studied is copper, the observations are thought to be relatively general as indicated by comparison of the results with partially sintered structures in other materials presented in the literature, both metallic and nonmetallic. EXPERIMENTAL PROCEDURE Four series of specimens representing progressive stages of the sintering process were prepared by sintering high-purity copper powder for various time periods. A relatively large particle size was used so that the void-solid interface could be readily distinguished at low magnification. In three series of specimens a loose stacking of particles was obtained by pouring powder into an alumina mold and lightly tapping the mold. The green density of such compacts was approximately 40 pct of theoretical density. Two of these three series utilized irregularly shaped particles in the size range -230 +325 mesh, one series sintered in vacuum and one in hydrogen at 950°C. The third series of loosely stacked particles consisted of spherical particles in the size range -270 +325 mesh, sintered in hydrogen at 950°C. A fourth series was prepared from compacted irregular particles sintered in hydrogen at 950°C. The specimens for this series were formed by lightly pressing the irregularly shaped particles in a steel die; the green density of the pressed pellets was approximately 60 pct. The irregularly shaped particles used in this study are shown in Fig. 1. The density of these particles, measured by a toluene picnometer technique, is 98.2 pct of theoretical density. Each particle is highly convoluted, and in some instances appears in cross section to contain internal porosity. The density measurement, however, indicates that completely enclosed porosity is very small so that the individual particles have a highly irregular surface but are essentially fully dense copper. Therefore, most of the void space that appears in two dimensions to be isolated within the particle is actually at the particle surface and connected to the external void in the dimension not included in the plane of the cross section. The void space that appears as void surrounded by the par -ticle or within folds in the particle w~ll be r~fc\r?

Jan 1, 1968

By H. R. Froning, R. O. Leach

In wertability alteration flooding, a chemical agent is rnoved through a reservoir by the flood water to increase oil recovery by decreasing the degree of wetting of the rock by the oil. Substantial amounts of the chemical may be lost during movement through the reservoir. The extent of the loss, and therefore the economics of the process, depends in some cases on factors which are difficult to reproduce in the laboratory. Therefore, a short-duration, low-cost field test method is needed to permit evaluation of chemical requirements under actual field conditions. This paper describes a small scale rest conducted at a single well for measuring chemical requirements, thereby giving a more reliable evaluation of this important factor in the applicability and economics of the process. In the rest a small wafer slug containing the chemical agent and a nonadsorbed tracer is displaced into the reservoir by a known volume of wafer. The well is then placed on producrion. Chemical loss per barrel of pore volume contacted is calculated from [he fractional recoveries of the agent tested and the nonadsorbed tracer. The method has been used to determine within the actual reservoirs the chemical requirements for both a sandstone and a dolomite reservoir. Several chemical agents are potentially available for wettability alteration flooding, although none is universally applicable. For some applications of the method, chemical costs per barrel of additional oil recovered can be substantially less than one dollar. INTRODUCTION Wettability alteration flooding provides a means of increasing oil recovery from reservoirs by decreasing the degree of wetting of the rock by the oil and increasing the displacement efficiency of the flood water. Earlier studies demonstrated a relationship between oil recovery during waterflooding and the degree of wetting of a rock surface by an oil. The application of wettability alteration flooding to the Harrisburg field of Nebraska provided a field test' of this recovery process. Subsequently, additional laboratory and field tests have developed additional procedures for evaluating wettability alteration flooding, and have indicated where the process may be applicable. Applicability of this process to specific reservoirs is determined by a progression of tests to determine sus- ceptibility of the reservoir to alteration of its wettability, to indicate the degree of recovery improvement and to estimate the amount of chemical required to process the reservoir. The economics of applying improved oil recovery processes depends not only upon the degree of improvement in oil recovery achievable by the process but also upon the process costs and the timing of the income and the investment. Emphasis in this paper is on the expenditure aspects of the process. The work reported in this paper indicates that the chemical investments required for wettability alteration flooding are substantial. For evaluating the economics of a potential flooding application it is imperative that a sound estimate of the chemical requirements be made for the reservoir. Generally, true reservoir conditions are not adequately simulated in laboratory chemical propagation tests. Because of wide well spacings, many years might be required to obtain chemical propagation data from conventional pilots or inter-well tests. Consequently, n short-duration, low-cost method is needed to determine chemical requirements in the field. The potential applicability of wettability alteration flooding is discussed, as well as the economics of wettability alteration with respect to the inherent and imposed restrictions on the timing of income and investments. DETERMINATION OF CHEMICAL REQUIREMENTS In the process of moving a chemical bank through reservoir rock, some of the chemical agent lags too far behind the flood front to be effective or is otherwise lost to the reservoir system. The extent to which these losses occur overshadows the reductions in chemical concentration due to diffusion and to mixing with the reservoir fluids. Experience indicates that almost without exception, chemicals which induce a wetting change undergo either sorption reactions or chemical reactions with mineral constituents of the pore surfaces. Other reactions may occur between the added chemical and the reservoir oil and water. Even in limiting consideration to reactions of the relatively inexpensive inorganic salts, bases and acids, the reactions may be exceedingly complex. Reservoir pore surfaces consist of more than silica in sandstone reservoirs, and more than calcite or dolomite in carbonate reservoirs. Many mineral species are present, each exhibiting specific tendencies to react with an injected chemical. The reactions which occur can consume enough of the agent to have an important effect on economics. These reactions can cause a change in pH of the chemical bank, or may remove some of the active chemical by precipitation, adsorption or reaction to form a new chemical which may or may not be effective in

By J. L. Schroeder, W. G. Talman

EXPERIENCE has shown that certain known natural conditions and other indefinite characteristics combine to make a mining area vulnerable to mountain bumps. Some of the known conditions are heavy overburden, an overlying stratum of strong non-elastic rock, a structurally strong coal seam that does not crush easily and yet is the weakest stratum in the series, and a floor stratum of more than ordinary firmness. The indefinite characteristics could include resistance of top or bottom of a coal seam to lateral flow, effect of immediate top and bottom strata, nature of the coal seam, and other factors about which very little is known. It is in this area that exhaustive study is needed to achieve positive control of the dreaded mountain bump hazard. In the Gary district, West Virginia, two of the five operating mines have areas known to be vulnerable to mountain bumps.These are the No. 2 and 6 mines, which are working the Pocahontas No. 4 coal seam. In this area the seam is overlain at a zero to 10-ft interval by the massive Eckman sandstone, which is about 100 ft thick in the vulnerable areas. Total overburden, consisting of shale, coal seams, and sandstones, ranges from 700 to 1400 ft where bumps have occurred (Fig. 1). The coal seam is 4 to 8 ft thick and has a weak columnar structure of very soft and spongy or woody coal. The immediate top is either the Eckman sandstone or hard shale, both of which provide generally good roof conditions for mining operations. The bottom ranges from medium to hard gray shale. The incidence of bumps in the Gary district dates from about 1930 and can be correlated to some degree with the increased rate of extraction attained with mechanical mining. During early years of operation at the No. 2 and 6 mines, most of the work was development and under comparatively light cover. As overburden became heavier, together with an increasing percentage of coal coming from pillar extraction, mountain bumps began to occur. Before 1945 they were much less severe than in later years, and because there were no injuries or fatalities, no records were kept. But by 1951 the incidence of bumps had increased to such extent that it became evident a mining system would have to be designed to eliminate or at least minimize these occurrences. Drawing on experience with modified versions of old systems and certain characteristics peculiar to the Pocahontas No. 4 coal seam, the district mining engineer, Martin Hayduk, outlined the essential factors for bump control in the Gary district. These control factors indicated: 1) The highly stressed area, which lies within the limits of convergence effects, moves at approximately the same rate as the retreating pillar line. 2) There is a decided softening of the periphery of blocks which is greatest and deepest on the gob side. 3) Blocks less than 45 ft wide never have been known to bump in the Pocahontas seams. Fig. 2 shows the mining plan based on these observations—a thin-pillar system with a minimum of secondary development. It was recognized from the start that the Hayduk system had certain limitations. When pillar work backed up to an inevitable surrounded block it was no longer applicable; also, burnt bottom and/or unknown factors reduced the system's effectiveness in certain headings. Since there was no way to eliminate the loaded block, it was decided to experiment with auger drilling to attain controlled release of this stored-up energy. The decision to auger was made after consideration of three separate plants, which were: 1) To cut the solid block into pillars of maximum size by driving away from the fracture line and at such a distance outby that development

Jan 1, 1959

TECHNICAL COMMITTEES Iron and Steel JOSEPH W. RICHARDS, Chairman. J. E. JOHNSON. Js., Vice-Chairman. ARTHUR S. CALLEN, Secretary, 453 Chestnut St., So. Bethlehem, Pa. SUB-COMMITTEES IRON ORE DWIGHT E. WOODBRIDGE. Chairman. ERNEST F. BURCHARD, WILLIAM KELLY. CHARLES F. RAND, FELIX A. VOGEL. BLAST FURNACES H. A. BRASSERT. Chairman. WILLIAM H. BLAUVELT, AMBROSE N. DIEHL, JAMES GAYLEY, RICHARD V. McKAY.

Jan 10, 1915

By Ralph H. Sweetser

MUCH progress in -blast-furnace construction and in the manufacture of firebrick for furnace linings has been made since the publication of Bulletin 130 of the U. S. Bureau of Mines on "Blast-Furnace Breakouts, Explosions and Slips, and Methods of Prevention," by F. H. Willcox in 1917. At the time of publishing this report comparatively little information was available to blast-furnace men as to the fundamental facts relating to the character of blast-furnace refractories. Some of the accepted theories of only a few years ago have been completely reversed. The mortality of blast-furnace linings used to be so great that nearly every furnace plant had one or more complete linings in the brick shed ready for use in case of a lining suddenly "going out"; it was generally accepted that a furnace could not "keep her lines" more than two or three years at best, and often a hot spot in the shell would develop, or a breakout occur in the hearth or bosh within a year or two after blowing in on a new lining. In some respects these frequent relinings were not so detrimental as to he a complete loss because they afforded opportunities to take advantage of advances in blast-furnace practice. At present the cost of relining has greatly increased, but the life of a lining has also increased. Anything less than five years on a lining is now considered a short blast.

Jan 1, 1932

By Sidney Sigel, J. Gardner Brooks, Irvin R. Kramer

In 1942 Grossmannl proposed that the hardenability of a steel may be calculated from its chemical composition by considering the base hardenability associated with its carbon content and grain size and multiplying this base by factors for each element present. Since Grossmann's original publication, several investigaton2-6 have reexamined the multiplying factors for the individual elements and in general have found that the multiplying principle is valid. However, some of the individual factor curves developed have been in poor agreement. Inasmuch as the carbon-factor curve obtained by Grossmann was dependent Lipon the factors for all the other alloying elements present in the steel, it logically followed that his results were in need of correction in the light of the new data available for manganese, silicon, and the other alloying elements. Furthermore, in order to avoid the possibility that errors in the manganese, silicon, or other curves might influence the carbon-factor curve, investigation of iron-carbon alloys containing little or no manganese and silicon was necessary. That the effect of carbon on hardenability was greater than indicated by Grossmann is shown by a comparison of the diameters of completely hardened rounds of iron-carbon alloys with the ideal critical diameter calculated from Grossmann's factors. These alloys have a greater hardenability in a finite quench than predicted by Grossmann's factors for an infinite quench (Table I). Among the other important variables that were in need of further investigation were the effect of deoxidation practice on the grain-size correction curves and the effect of stable carbide-forming elements on the depth of hardening. Most Of the work by Kramer, Hafner, and Toleman4 was done on silicon-killed steels. It was not known whether Gross-mann's grain-size correction curves, determined on aluminum-killed steels, was valid when applied to steels with different deoxidation practice. More data on the

Jan 1, 1947

By J. Gardner Brooks, Sidney Sigel, Irvin R. Kramer

In 1942 Grossmannl proposed that the hardenability of a steel may be calculated from its chemical composition by considering the base hardenability associated with its carbon content and grain size and multiplying this base by factors for each element present. Since Grossmann's original publication, several investigaton2-6 have reexamined the multiplying factors for the individual elements and in general have found that the multiplying principle is valid. However, some of the individual factor curves developed have been in poor agreement. Inasmuch as the carbon-factor curve obtained by Grossmann was dependent Lipon the factors for all the other alloying elements present in the steel, it logically followed that his results were in need of correction in the light of the new data available for manganese, silicon, and the other alloying elements. Furthermore, in order to avoid the possibility that errors in the manganese, silicon, or other curves might influence the carbon-factor curve, investigation of iron-carbon alloys containing little or no manganese and silicon was necessary. That the effect of carbon on hardenability was greater than indicated by Grossmann is shown by a comparison of the diameters of completely hardened rounds of iron-carbon alloys with the ideal critical diameter calculated from Grossmann's factors. These alloys have a greater hardenability in a finite quench than predicted by Grossmann's factors for an infinite quench (Table I). Among the other important variables that were in need of further investigation were the effect of deoxidation practice on the grain-size correction curves and the effect of stable carbide-forming elements on the depth of hardening. Most Of the work by Kramer, Hafner, and Toleman4 was done on silicon-killed steels. It was not known whether Gross-mann's grain-size correction curves, determined on aluminum-killed steels, was valid when applied to steels with different deoxidation practice. More data on the

Jan 1, 1947

By A. L. Blomfield

THE Golden Cycle Mining and Reduction Co. operates its custom mill at Colorado Springs on Cripple Creek ores exclusively. These ores are straight sulpho-tellurides, with practically no base metals such as Pb, Cu, Zn, As, or Sb. Upon entering the mill, the ore all passes through the sampler to storage bins, where beds of 5000 tons each are made to insure uniformity in roasting. CLASSIFICATION OF ORES For efficiency, it has been found advisable to separate the ores into two classes according to their line content. Other constituents have their effect, such as alumina and magnesia, but, speaking generally, these are roughly proportional to the line, which, as CaO, is used as the indicator. Class A contains not more than 2 per cent. CaO and comprises about 66 per cent. of the ore treated. Class B contains over 2 per cent. CaO, and comprises 34 per cent. of the ore treated. Typical analyses of both classes are as follows: Class A Class B Insol 56.70 75.90 Al203 2.30 3.40 Fe 3.26 3.48 CaO 1.57 5.12 S 1.79 1.80 Mg0 0.21 1.08 Ignition loss 3.20 6.50 99.03 97.28 The beds of each class of ore are made as large as possible with the available ore as it comes in, to avoid changing from one bed to the other any oftener than necessary. Each roaster will handle 50 percent. more of class A ore than of class B, with practically the same results. This necessitates changing the rate of feed for each new bed and tends toward a poor roast and loss of tonnage at each change.

Jan 8, 1918

By John L. Lamont, Walter Crafts

STUDIES of the effect of composition of steel on hardenability by Grossmann,1 and as-quenched hardness by Field2 and by the authors,3 have made it possible to predict the results of quenching when the composition and cooling rate are known. In order to extend the application of the hardenability calculation to the quenched and tempered condition in which steel is finally used, a survey has been made of the hardness changes caused by tempering. From this study a method has been developed for the prediction of hardness and tensile strength of steel in the tempered condition. The method of calculation was developed from Rockwell C hardness tests on quenched and tempered Jominy specimens and is expressed in Rockwell C hardness units. It is of an additive type in which the degree of softening from as-quenched hardness is estimated. Tempered properties may be calculated within about plus or minus 5 Rockwell C hardness or plus or minus 15,000 lb. per sq. in. tensile strength. This degree of accuracy is less than that necessary for the control of heat-treatment, but is adequate for the comparative evaluation and selection of alloy steels. The formula indicates that tempered hardness is primarily dependent on as- quenched hardness and, as in the hardening reaction, the progress of tempering is controlled mainly by the carbon content- Alloys tend to retard softening by a secondary hardening mechanism in which the alloy appears to migrate from ferrite to the carbide phase. The factors for the effects of alloys in tempering vary so much from the effects of alloys in hardening that different steels of equivalent hardenability may, after lie heat-treatment, differ considerably in tensile strength. PROCEDURE In developing the method for calculating tempered Rockwell C hardness, simple and complex steels were tested over a range from 0.08-to 0.65 per cent carbon and up to 2.68 per cent manganese, 2.18 silicon, 3.50 chromium, 4.94 nickel, and 1.06 molybdenum. The steels were made as small induction-furnace heats at the Union Carbide and Carbon Research Laboratories, Inc. The accuracy of the method was finally checked on a variety of carbon, low-alloy and high- alloy types of heat-treating steels produced under commercial conditions. The method was based on a study of tempered Jominy bars, and its validity was tested by correlation with the center hardness and tensile strength of oil-quenched and tempered bars from ¼ to 4 in. in diameter. The method of calculation was derived from the differences in Rockwell C hardness between as-quenched and quenched and tempered Jominy specimens. Prenormalized Jominy hardenability specimens quenched from a normal temperature for austenitization were used to obtain a range of as-quenched Rockwell C

Jan 1, 1946