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By J. E. Andersen, J. Halpern, C. S. Samis

In the presence of oxygen, galena is oxidized in an aqueous medium containing sodium hydroxide, in accordance with the following reaction: PbS + 2O2 + 3OH ? HPbO2 + SO4 = + H2O A novel method was devised for following this reaction which takes place in an autoclave under oxygen pressure, by measuring the concentration of HPbO2- in the solution with a cathode ray polarograph employing stationary platinum electrodes. Using this procedure a study was made of the kinetics of the reaction, in which the effect of a number of variables, including temperature, oxygen pressure, NaOH concentration, and agitation, on the rate, were determined. The results of this study are described and discussed, in terms of possible mechanisms for the reaction. IT is known that sulphide minerals can be oxidized in aqueous media in the presence of oxygen under pressure. Reactions of this type can be classified in two categories depending upon whether the products of oxidation are insoluble or soluble in the aqueous medium. An example of the first type of reaction is the oxidation of pyrite in alkaline solutions, giving rise to an insoluble iron oxide. The kinetics of this reaction have been investigated and its mechanism established.' It has been applied in the oxidation of iron sulphides present in refractory gold ores to improve the subsequent recovery of gold by cyanida-tion.' The second type of reaction finds application where it is desired to recover the metal by leaching during oxidation. In this case a medium is selected in which the oxidized mineral is soluble. For example, nickel, copper, and cobalt sulphide ores can be treated by oxidation in the presence of a solution of ammonia dissolving the nickel, copper, and cobalt as the metal ammine sulphate salts.:' A similar treatment has also been reported to apply to zinc sulphide ores.' It is known that lead sulphate is soluble in solutions of sodium hydroxide or ammonium acetate. It should therefore be possible to dissolve the lead from galena ores by aqueous oxidation with oxygen under pressure using either of these solutions. The applicability of the ammonium acetate treatment has been investigated and confirmed in a recent study.' The present paper describes the results of a similar study in which the kinetics of the oxidation of galena in sodium hydroxide solutions have been investigated. The object of this investigation was pri- marily to obtain information of a fundamental nature relating to the kinetics and mechanism of this reaction. The use of pulps of comminuted ore in a study of this type is undesirable because of the difficulty in controlling and measuring the surface area. The measurements were therefore made using galena crystals of measured surface area and in this way absolute reaction rates were obtained. The reaction was found to proceed as follows: PbS + 2O2 + 3OH ? HPbO2 + SO4 + H2O [I] The products are sodium plumbite and sodium sulphate salts which dissolve in the aqueous solution. The reaction studies were carried out in an autoclave in which a desired pressure of oxygen was maintained. The reaction was followed by measuring the concentration of lead in the solution with a cathode ray polarograph. The results obtained in this investigation are presented and discussed in the present paper. Experimental Materials: The crystals of galena were obtained from Violamac Mines, Sandon, B. C. The following impurities were indicated by spectrographic analysis carried out by the Provincial Assay Office, Victoria, B. C.: Sn, 0.02 to 0.2 pct; Sb, 0.07 to 0.7; Zn, 0.01 to 0.1; Si, Fe, Mg, As, less than 0.05 pct; Ag, 126 oz per ton, the latter determined by standard fire-assaying procedure. After cutting a specimen measuring approximately 5x7x12 mm, the crystal surfaces were ground parallel to the 100 axes using No. 2 emery, washed with water, and the dimensions were measured with a micrometer. Oxygen gas was of commercial grade and supplied in cylinders by Canadian Liquid Air. Solutions were made up with chemicals of chemically pure grade and distilled water. Equipment: Autoclave: The autoclave used in these studies was constructed of stainless steel and

Jan 1, 1954

By Reed W. Hyde

SOME information has been published on the sulphur dioxide concentration of gases from Dwight-Lloyd machines sintering lead ores but most of this relates to the customary practice in which the charge is relatively high in lead and is sintered in two passes over the machine. It is thought, therefore, that the following observations on sintering in one pass a low-lead, low-sulphur charge may be of interest. The data were obtained in sintering lead sulphide flotation concentrates mixed with minus 20-mesh oxide ore, the mixture carrying 16.8 per cent Pb and 5.3 per cent S. No returns were used because of the limited amount of sulphur available as fuel, but the mixture pelletized readily to make a satisfactorily permeable bed on the sintering machine. As there was a possibility that the SO2 might be utilized, a series of runs was made to determine the concentration of S02 in the gases at different points along the wind box, and the effect on this concentration of changes in the wind-box vacuum. Several runs each were made with vacuums (as measured in inches of water at the wind box) of (1) 2 to 1 1/3 in., (2) 4 to 3 1/2 in. and (3) 6 to 5 1/8 in. The averages of the determinations from each series are platted on the graph (Fig. I). The vertical scale shows the percentage by volume of SO2 (as determined by the Reich method), and the horizontal scale shows the time expressed as percentage of the total sintering time. Sintering was considered to be complete when no S02 could be detected in the gases. In all cases the depth of bed was 4 ½ in. and the weight of dry charge per square foot of hearth area was 45.2 lb. Other data are given in the table. The volume of gases corresponding to the several points along the wind box at which S02 determinations were made could not be measured, but has been calculated from the S02 content and sulphur elimination on the assumption that the volume is uniform throughout the sintering period. This is not strictly true, as with a given vacuum the volume will usually drop slightly toward the middle of the period and increase toward the end. However, this assumption is a reasonable approximation. Several interesting features are brought out by these data. In general, the published data on S02 concentration in sintering under ordinary conditions show a high S02 concentration in the early stages followed by a rapid decrease in concentration and with relatively little SO2 in the gases from the last half or third of the operation. In other words, the greater part of the sulphur elimination is obtained in the first third or half of the period. In these runs, the 6-in. vacuum, which approximates the usual operating condition, gives a curve that follows this customary pattern. Maximum S02 concentration is obtained 2 ½ min. after

Jan 1, 1942

Alexander Forsyth, Southport, Me. (communication to the Secretary): In Mr. Irving's able and interesting paper he describes minutely the appearance of the wolframite and its association with the refractory siliceous gold-ore. He also describes this gold-ore, but fails to mention the important pockets of metallic gold found in the Lead City occurrence of it. I use the term " metallic " in preference to the more usual " free," for it has been found that this gold is not easily amalgamated. Metallic gold is comparatively rare in the refractory siliceous gold-ores of the Black Hills; hence its occurrence in considerable amounts in the Lead City wolframite district deserves notice. I possess a beautiful specimen from the Harrison mine. It is a lump of drusy, granular ore, about 6 in. in diameter. The gold .is " shot" through it in large and small pin-heads; and in two specially oxidized areas, each about 11/2 in. in diameter, it is peppered full. The famous " Grantz strike," made in the Lead City wolframite locality, produced many beautiful gold specimens. This district affords an excellent example of the repeated discovery of new mineral values upon old ground. By reason of its proximity to the Homestake vein, this wolframite deposit was inevitably traversed many times by experienced geologists, mineralogists and mining engineers, who evidently must have thrown aside, with no thought of wolframite, the lumps of " black iron " lying about. I have the admission of an able geologist that, six months before the wolframite was discovered, he visited some of the very mines where it occurred, and passed it by as magnetic iron-ore. At the time of the discovery, the mineral was scattered over the gold-mine dumps in no small quantities, having been culled as worthless out of the gold-ore. It remained for

Jan 1, 1902

By K. B. Nowels

The attainment of efficient flooding to a large extent depends upon a knowledge of fluid movement through porous media and the pressures used in controlling this movement. Little has been understood con-cerning the fundamental principles involved in the forced drive of water-flooding and an attempt will be made to present some data which may be of interest. Considerable data and technical information pertaining to natural and artificial water-flooding have been presented in the past by Torrey, Umpleby, Fettke, Panyity and others. Their papers have thoroughly covered the description of past and present-day methods of oil recovery by flooding in the Bradford field, especially an article by Torreyl in the Petroleum Engineering Handbook. A bibliography of papers devoted to watcr-flooding, published in Mr. Torrey's article, is appended to this paper. No attempt has been made, therefore, to describe the installations and procedure necessary in flooding, thus permitting the writer to deal exclusively with the mechanics of water movement in flooding operations and its relationship to well spacing. Artificial water-flooding will probably always be the most successful in oil fields described by Herold as being under "capillary control"" and will probably be useless in fields naturally under hydraulic or volumetric control. The natural water drive in an oil field under either of these two controls may give efficient recoveries, as a result of the regulated encroachment of edge water. Such a "natural flood" resulting from the influence of edge water must not be confused with the term as used in this paper, however. Any reference to "natural flood" will here refer to the old method of flooding formerly used in the Bradford field. This was discovered largely by accident and utilized the hydrostatic pressure created by a column of water standing in a watered-out oil well in forcing the oil to an adjacent producing well. The same principles are involved in either natural or artificial flooding, and the latter method simply

Jan 1, 1933

By C. S. Smith, W. M. Williams

THE quantitative study of grain shape in three dimensions has been a difficult one from the practical standpoint. Experiments on grain shape have usually been based on indirect observations of two-dimensional metallographic samples or on grains separated by intergranular corrosion or fracture. The latter method was used in particular by Deschl in 1919 in observing the shapes of ß-brass grains which had been separated with mercury. The similarity in detail of shape and packing that exists between bubbles in a soap froth and metal grains was noted by Desch who remarks that: "Surface tension has an. important share in determining the form of the crystal grains in a solidifying metal and such grains have a tendency to assume the shape of foam cells." More recently the relation between grain shape and grain growth has been studied by Harker and Parker.' The importance of surface tension forces in determining microstructure has been discussed by Smith," and an analysis of the topologi-cal rules that apply to such structures has been made by the same author.' Biologists have made valuable contributions to the general problem of shape and form in an assembly of space-filling cells subject to surface tension forces. Particular mention must be made of the extensive researches of Lewis5,8 on botanical and anatomical tissues, and Matzke and Nestler,7,8 who have made painstaking studies of bubble shapes in different kinds of foam. The present paper introduces a new method of studying individual grains in particular alloys—a method which may well find use in other metallurgical researches, and which seems also to be applicable in biological problems. Metal Grains in Three Dimensions The individual grains in a piece of metal or the bubbles in a soap froth must satisfy two conditions —they must be in juxtaposition so as to fill space and their interfaces must conform to the laws of surface tension. If a further restriction is imposed, namely, that only one type of polyhedron be used, then the sole possibility is an assembly of "minimal" tetrakaidecahedra," each polyhedron having eight doubly-curved hexagonal faces and six plane quadrilateral faces, the angles between adjacent faces being 120". Such cells could be stacked on a body-centered cubic lattice and would be quite stable. For many years it was believed that soap bubbles actually possessed the shape of this ideal body, and the hypothesis was the starting point for several investigations on the shapes of soap bubbles, biological cells, and metal grains. These investigations have shown, what might have been obvious in the beginning, that if the condition of symmetry is relaxed the tetrakaidecahedron is almost never found. If we retain only the rule that all contacts should be in local surface tension equilibrium and that the assembly should fill space, metal grains may then take a nearly infinite variety of shapes and no single one may be regarded as an archetype. These two conditions, which are fully discussed in one of the previously mentioned papers,' lead us to think of a typical grain in an annealed metal as having the following characteristics: 1—A grain may have any number of faces, but usually between nine and eighteen. The faces (each of which is, of course, shared by two grains in the assembly) may have any number of edges, but usually between four and six. Pentagons are by far the most frequent. 2—In the assembly of grains each edge is shared by three faces and by three grains. Each vertex is a point shared by four grains, six faces, and four

Jan 1, 1953

By P. A. Beck, S. Kohara, M. N. Parthasarathi

IT has been shown1,3 that many observed phenomena related to annealing textures in f.c.c. metals can be adequately accounted for, at least in a qualitative way, by considering the orientation dependence of the boundary mobility, without any hypotheses concerning preferred orientation of nuclei. It was noted1 that this approach is particularly successful in the common cases of primary recrystallization in highly cold-worked polycrys-talline metals, where nuclei occur in great abundance, and that in the other extreme case, where the number of nuclei is very limited, or even only a single crystal is grown, the orientation dependence of boundary mobility has only a small effect, or none at all, on the orientations resulting from annealing. Recently Dunn described examples3-6 where observed secondary recrystallization textures apparently cannot be accounted for on the basis of oriented growth alone, but also require oriented nuclei, or at least the absence of nuclei in certain orientation ranges. In general, the great difficulty in correlating the preferred orientation of recrystallized grains with that of nuclei is inherent in the fact that nuclei are by nature very small, and that they are usually identifiable as "nuclei" only after growth, i.e., after they have already been subject to growth selectivity. An investigation was carried out by Liebmann and Lücke,' and also a very similar one by Graham and Cahn,' to obtain quantitative information on the orientation depend- ence of boundary migration rates in the recrystallization of slightly deformed aluminum single-crystal rods or plates, in which artificially nucleated recrystallized grains of predetermined orientation were grown. Liebmann and Lücke foupd maximum boundary mobility for boundaries across which the misorientation corresponded to a rotation of 40 deg around a common [Ill] axis, in accordance with earlier conclusions.9,1 Also, they confirmed that such an orientation relationship predominates among crystals growing into slightly extended single crystals from presumably random artificial nuclei. On the other hand, Graham and Cahn found no preferred orientation among crystals grown in a similar manner. It is not as yet known how these observations may be reconciled with each other. The view has been expressed in various papers5'10,21 that selective growth based on the orientation dependence of boundary mobility is not in itself sufficient to account for the formation of sharp re-crystallization textures, such as those often observed in highly deformed polycrystalline metals after annealing. The present work was undertaken to ascertain whether or not it is possible to obtain a sharp re-crystallization texture in a case where random nuclei are assuredly present in large numbers. It was previously found1' that high-purity aluminum crystals rolled 80 pct on the (110) plane in the [1T2] direction, when suitable precautions are taken, may be annealed for periods of about 1000 sec at 350°C without recrystallization. It was also found that the reluctance to recrystallize in this case is due to the scarcity of material in sufficiently deviating orientations to serve as nuclei. By using such a matrix,

Jan 1, 1959

By J. H. Faulk

An examination is made of the various factors influencing drilling rate and drill bit life in various diameter holes. It is concluded that drill bits in the size range 4% to 6 1/4 in. can be used to attain substantially the some daily drilling progress as conventional size bits in soft rock drilling operations. An examination of the most important factors influencing "hazard of losing the hole" in the different hole size results in the conclusion that the smaller hole sizes can probably be drilled at reasonably low risk. However, this risk will be somewhat greater in the smaller diameter holes, requiring that special drilling and mud engineering practices be used to make small diameter holes practicable in soft rock drilling operations. An engineering analysia is made of the power and hydraulic requirements of several drill string-hole combinations to test the feasibility of drilling .small diameter holes in soft rock areas. Large econormies in rig power requirements appear possible by drilling .smaller .size holes in these operations. INTRODUCTION The industry now is re-examining the utility of small diameter holes in the light of substantial technical advances made in recent years. Faced with increasing cost of finding reserves and with proration after developing them, the industry must either develop methods of economizing or receive a lower rate of return on investments. Small diameter holes appear to involve an attractive method of economizing. Our objective is to determine if this is technically possible in soft rock operations. Soft rock, as used in this report, refers to those formations of a "drill-ability" corresponding to that of all Gulf Coast formations shallower than and frequently including much of the Eocene rock system. An important phase of technology which we shall examine is relative drilling rate and bit footage which may be obtained with various size bits. Rig operating efficiency, particularly as influenced by hazard, is also discussed in detail. The technical conclusions resulting from these examinations are used to develop sample drill string design and rig horsepower requirements for drilling holes as smaH as 4 3/4 in. and larger. The principal criterion used for the drill string design is that approximately the same daily drilling progress would be possible in all size holes in soft rock operations. This facilitates a comparison of rig size required for drilling the hole sizes in the range between 4 3/4 and 8 3/4 in. BROAD PROBLEM OF DRILLING RATE AND BIT FOOTAGE The three factors controlling daily drilling progress are: (1) drilling rate of bit while on bottom turning, (2) bit footage, and (3) rig operating efficiency. Let us look now at the first two of these factors. Drilling technology has progressed to the point that a semi-quantitative analysis of the effect of various operating variables upon these factors can be made. Those factors which apparently limit both drilling rate and bit footage for bits now in use are: (1) bit design, (2) weight on bit, (3) hydraulic cleaning capacity for bit cutting surfaces and hole bottom, and (4) rotary speed. (We neglect the effect of mud and formation properties because these factors arc the same for the various size bits.

Jan 1, 1957

By J. Szekely, V. Stanek

Heat and gas flow interactions in nonisothermal packed beds were examined in the paper. A study was made of the response of the system to a step or pulse change in the inlet gas temperature, with a fixed value of the overall pressure drop across the bed. Under these conditions the heat flow and fluid flow transients are coupled because the convective heat transfer rate is alfected by the mass flow rate of the gas which, in turn, for a fixed pressure drop will depend on the temperature profile in the system. The Problem was stated in terms of differential equations, which were integrated numerically. The parameters used in the computation were so chosen to reflect the operation of the stack region of blast furnaces and sinterbeds. The computed results showed that the pressure drop-flou1 relationships and the rate of progress of the temperature fronts (waves) were strongly interrelated and were also markedly affected by variations in particle size and in void fraction. MANY metallurgical processes involve the contact of solid particles with a gas stream in a packed bed arrangement under nonisothermal conditions. Examples are shaft furnaces, regenerators, pebble heaters, and the sinter process. Although the heat and mass transfer aspects of packed bed processing have been extensively studied, the associated flow phenomena and in particular the effects of nonisothermality on the flow, have received little attention to date. :In fact, most of the previous workers considered the flow rate of the carrier gas time invariant and independent of the heat or mass transfer processSzekely and carr2 have shown that the pressure drop-flow relationships in nonisothermal packed beds may be strongly affected by the temperature profile within the system. These authors have devised a method for relating the pressure drop to flow for a given temperature profile. thus providing an extension of the Ergun equation to steady nonisothermal systems. Finally, in a recent paper willmot3 examined the response of regenerators to externally imposed changes in the gas flow rate. Both these investigations were somewhat specialized since, in general, neither the temperature distribution nor the gas flow rate may be regarded as truly independent variables, thus the heat transfer and the fluid flow problems have to be solved simultaneously. The work reported here is divided into two parts: in Part 1 the general formulation is given and a detailed discussion is presented of fixed bed systems. Part is devoted to systems in which a gas and particulate solids are contacted in a counter flow arrangement. FORMULATION Consider a nonisothermal fixed packed bed, extending from through which a gas is flowing. The problem is to develop a relationship between pressure drop and gas flow (with the gas flow being the dependent variable) and to evaluate the rate at which a change in the gas temperature, imposed at the inlet, travels through the system. Let us consider an infinitesimal section of the bed and establish differential heat, mass, and mechanical energy balances over this region. In addition, relationships are needed describing the temperature dependence of gas density (equation of state) and the temperature dependence of viscosity. These may be written as: where c, and are constants. It is noted that in this formulation we neglected any temperature gradients within the solid particles, thus assuming these to be either sufficiently small or of sufficiently high thermal conductivity to meet this condition. The justification and consequences of this assumption will be mentioned in the discussion.

Jan 1, 1970

The first mention of the mining and use of coal in the Pittsburgh district refers to the mine under Duquesne Heights that furnished coal for the garrison at the fort at Pittsburgh in 1760. Coal had been dug and used as fuel just outside of Brownsville, Fayette county, in 1759, but this was not a regular mine as the opening was in an outcropping. Maps of Ohio in 1770 showed "Cole Mines" at various points. The Penns purchased all the coal south of Kittanning in southwestern Pennsylvania from the Chiefs of the Six Nations for a reported price of $10,000. During the Revolution, coal from Herron Hill, Mincrsville, and Coal Hill, all within the present city limits, was used in Pittsburgh. There is today one custom pit opened in Coal Hill (Duquesne Heights). The first steam engine was set up in Pittsburgh in 1794 and used coal as fuel. The first mine in the Youghiogheny gas district was opened in 1796. In 1803, the first shipment of coal by water was made from Pittsburgh down the Ohio river and landed at Philadelphia, where it sold for approximately $9.50 per ton. The mines along the Monongahela were naturally the first to be opened. With the completion of locks and dams in 1844, permitting slack-water navigation, the industry began to thrive. The No. 8 field of Ohio and the Fairmont region of northern West Virginia were opened in the period 1840 to 1855. From that time on there has been a continuous development of the coal rcsources of this district, until at present productive capacity is enough to supply 30 per cent. of the country's needs of bituminous coal. The original method of working the Pittsburgh seam was to drive under cover at some easily accessible point on the outcrop with a single entry, usually 1½ yd. wide. Rooms or gangways were turned to the right and left from this entry and ventilation was usually poor and inade-

Jan 1, 1927

By M. I. Jacobson, M. L. Hammond

The solid solubilities of high-purity silver, aluminum, chromium, copper, and iron in zone-refined beryllium have been determined. Diffusion couple sandwiches of beryllium with aluminum, copper, and silver foil and diffusion couples of beryllium with two-phase alloys in the Be-Cr. Be-Fe, and Be-Ag systems were analyzed by electron beam micro-probe techniques. This paper describes the material used, the experimental methods for preparing the diffusion couples and the alloys, the analytical techniques, and the results obtained. The results are compared with those of previous investigators who used materials of lower purity. ~NVESTIGATORS of beryllium phase diagrams have often been hampered in their interpretations of certain phase boundaries because of the relatively low purity of the beryllium used. This has sometimes resulted in the appearance of three phases in the regions where only two should exist. Advances in purification methods, specifically zone refining, have made available beryllium that is considerably purer than the material previously used for phase diagram studies. The primary object of this investigation was to reex-amine portions of the beryllium-rich end of the binary systems of beryllium with silver, aluminum, chromium, copper, and iron to determine more accurately the limits of terminal solid solubility. The five elements—silver, aluminum, chromium, copper, and iron—include some which are commonly found as the major impurities in beryllium, some of which are being used as solid-solution alloying elements, and some of which are used in ductile matrix alloys. They are thus of considerable importance to physical metallurgists who must work with beryllium but who must rely on the present inaccurate or incomplete diagrams. The determination of more reliable diagrams would aid researchers concerned with the problems of alloying, heat treatment, and ductility. MATERIAL The beryllium was acquired from the Franklin Institute in the form of a single-crystal, 6 in. long by 1 in. in diam, zone-refined in three passes from Pechiney SR-grade beryllium bar. The principal impurities, as determined by mass spectrography at Battelle Memorial Institute, are shown in Table I. Vacuum-melted copper, silver, and aluminum, and electron-beam zone-refined iron were obtained from the Materials Research Corp. in the form of 1/2-in.- diam bars. Iodide chromium was obtained as flakes from the Chromalloy Corp. Analyses supplied with these metals are shown in Table 11. EXPERIMENTAL PROCEDURE Preparation of Diffusion Couples. Two types of dif-fusion couples were used in this study. For the copper, silver, and aluminum systems, the couples were sand-

Jan 1, 1969

By J. F. Butler

The degree and type of carbide dispersion resulting from changes in the cooling rate from austenite determine the amount of carbon remaining in solution after slow cooling- from a subsequent subcritical annealing treatment. A difjusion model has been proposecl to explain the effect of carbide dispersion on the amount of carbon retained in solution and the amount of carbon in solution has been related to the degree of carbon strain aging. COTTRELL and Leak' have shown that the rate of strain aging in low-carbon steels is dependent upon the amount of carbon and nitrogen in solution. Carbon can be effectively removed from solution as Fe , C by quench aging at temperatures of 200" C or lower; however, the relatively higher solubility of nitrogen at these temperatures prevents sufficient removal of nitrogen as iron nitrides. For this reason, nitrogen in solution has been considered the major cause of strain aging in rimming grades of commercial low-carbon steels. Nitrogen can be effectively removed from solution and nonaging steel produced through the addition of aluminum to form the stable nitride, AlN; however, the aluminum also causes deoxidation resulting in a killed steel. III an attempt to produce a rimmed steel which was also nonaging, Morgan and Shyne 2 investigated tile strain-aging properties of low-carban steels containing boron and found that strain aging was suplx-essed in steels containing as little as 0.007 pet B. The original purpose of this investigation was to determine the mechanism of strain-aging suppression by boron. Early in the study, the function of boron was discovered to be much like that of aluminum in that the formation of a nitride, BN, removed the nitrogen from solution.' However, during the course of the investigation, an effect of heat treatment upon the strain-aging properties and the amount of carbon in solution was found which could be related to the microstructure of the steel. The purpose of this paper is to examine these relationships among heat treatment, microstructure, carbon in solution, and strain aging in steels where nondetectable amounts of nitrogen are present in solution. EXPERIMENTAL PROCEDURE The investigation was carried out using 0.030 in. by 12. in wire specimens which had been cold swaged and drawn to the final diameter. Table I lists the compositions of the low-carbon steels used. Those with 'V' designations were vacuum melted and cast; the alloys designated 'AISI' were prepared from high-purity iron obtained from the American

Jan 1, 1962

By Floyd C. Kelly

A. HUltgren, .Söderfors, Sweden (written discussion*).—From the results obtained in his own experiments as well as those of Austin and of Grube Mr. Kelley derives a general law, expressed tentatively in the following words: "whenever two metals are brought into intimate contact at a temperature at which diffusion takes place, a comparatively rapid, or abnormal, grain growth results." It is suggested that,, in order adequately to represent the facts, this definition should he restricted by the following qualifications: a and b are the two metals, b diffusing into a. A. At the temperature in question a should exist as phase a 1 having a limited solubility for b. B. The supply of b by diffusion should be sufficient, in view of the rate of diffusion into a 1, to increase the concentration of b above the saturation value in a 1 so as to cause a new phase a2 to form. (7. The phase a2 should have a range of solubility for 6, thus rendering continued diffusion possible. D. In order that the columnar grains may be preserved in the structure the phase a2 should, of course, not suffer transformation on cooling. The phenomenon thus defined may be described as progressive transformation by diffusion. Its mechanism would appear to he as follows: Fig. 17 shows a portion of the equilibrium diagram a-b, Fig. 18 the distribution of b in solution after various periods of diffusion, Fig. 19 represents the structure in cross-section of a cylindrical rod of a at the end of heating period 3. 1. The first effect of diffusion of b into a will be to establish a concentration gradient in phase a1 (1, Fig. 18). When the saturation value for the temperature of the experiment (m, Fig. 17) is reached at the surface, nuclei of, a2 of composition n will form here, and later develop into a continuous layer. Assuming that diffusion proceeds without irregularities and that transformation at any point sets in without lag—i. e., in the moment saturation is exceeded—the transformation a1-a2 will advance inwards on a cylindrical surface concentric with the surface of the rod. The discontinuity of composition at the transformation surface in the position it happens to have at the end of the treatment (3, Fig. 18) will be preserved at room temperature, if the cooling is not particularly slow, and be recorded in the structure as a marked, smooth line, in agreement with Grube's and the author's observations. The shape of the distribution curves in Fig. 18 is also corroborated by the analyses given by Grube. 2. During diffusion, since the secondary phase a2 is always in immediate contact with the saturated part of the primary phase a1, there should be very little lag in the transformation. This means that the first a2 grains formed should grow in preference to the formation of independent nuclei; in other words, columnar growth results. It does not seem necessary to assume, with Green,' whose conception of the phenomenon

Jan 1, 1929

By Floyd C. Kelly

A. HUltgren, .Söderfors, Sweden (written discussion*).—From the results obtained in his own experiments as well as those of Austin and of Grube Mr. Kelley derives a general law, expressed tentatively in the following words: "whenever two metals are brought into intimate contact at a temperature at which diffusion takes place, a comparatively rapid, or abnormal, grain growth results." It is suggested that,, in order adequately to represent the facts, this definition should he restricted by the following qualifications: a and b are the two metals, b diffusing into a. A. At the temperature in question a should exist as phase a 1 having a limited solubility for b. B. The supply of b by diffusion should be sufficient, in view of the rate of diffusion into a 1, to increase the concentration of b above the saturation value in a 1 so as to cause a new phase a2 to form. (7. The phase a2 should have a range of solubility for 6, thus rendering continued diffusion possible. D. In order that the columnar grains may be preserved in the structure the phase a2 should, of course, not suffer transformation on cooling. The phenomenon thus defined may be described as progressive transformation by diffusion. Its mechanism would appear to he as follows: Fig. 17 shows a portion of the equilibrium diagram a-b, Fig. 18 the distribution of b in solution after various periods of diffusion, Fig. 19 represents the structure in cross-section of a cylindrical rod of a at the end of heating period 3. 1. The first effect of diffusion of b into a will be to establish a concentration gradient in phase a1 (1, Fig. 18). When the saturation value for the temperature of the experiment (m, Fig. 17) is reached at the surface, nuclei of, a2 of composition n will form here, and later develop into a continuous layer. Assuming that diffusion proceeds without irregularities and that transformation at any point sets in without lag—i. e., in the moment saturation is exceeded—the transformation a1-a2 will advance inwards on a cylindrical surface concentric with the surface of the rod. The discontinuity of composition at the transformation surface in the position it happens to have at the end of the treatment (3, Fig. 18) will be preserved at room temperature, if the cooling is not particularly slow, and be recorded in the structure as a marked, smooth line, in agreement with Grube's and the author's observations. The shape of the distribution curves in Fig. 18 is also corroborated by the analyses given by Grube. 2. During diffusion, since the secondary phase a2 is always in immediate contact with the saturated part of the primary phase a1, there should be very little lag in the transformation. This means that the first a2 grains formed should grow in preference to the formation of independent nuclei; in other words, columnar growth results. It does not seem necessary to assume, with Green,' whose conception of the phenomenon

Jan 1, 1929

By E. Marburg

Most ingots complete solidification vertically rather than transversely. This conclusion is based on complete solidification patterns of big-end-up and big-end-down ingots developed from dumped and split ingots. New mechanisms for segregation in ingots are proposed. Internal soundness in ingots is found to depend upon adequate width of vertical core. A LTHOUGH it has long been recognized that the A internal soundness of ingots is principally been recognizedthatthedependent on the process of solidification, knowledge of this process is still only fragmentary. The mechanisms causing the several types of segregation in ingots, which mechanisms are necessarily related to the solidification process, are not well understood. In absence of a better conception of the solidification process, it seems hardly surprising that mold design varies widely. Guiding principles for mold design are needed. At stake in the improvement of ingot quality are not only improved properties of steel but also appreciably higher yields of sound steel, which would considerably decrease manufacturing costs. In the present study, following a general description of the several types of segregation in ingots, Fig. 1, complete solidification patterns of a big-endup and a big-end-down ingot, including the zones of accelerated solidification, have been reconstructed. In both ingots, a core of vertical solidification extends from the base cone to the hot-top junction. Based on the finding that ingots complete solidification vertically rather than transversely, as has been previously assumed, new mechanisms for segregation in ingots are proposed. Internal soundness in ingots is found to depend upon the width of the vertical core, which in turn depends principally upon the width to height (w/h) ratio of the ingot. Solidification patterns of ingots are of three general types: 1—those in which vertical solidification does not reach the top, 2—those in which vertical solidification just reaches the top of the ingot, and 3—those in which vertical solidification reaches the top some time before transverse solidification would reach the middle of the ingot, so that a vertical core of definite width at the top of the ingot is developed. Axial defects vary characteristically with the solidification pattern. Examples of ingots of each type are presented. Dumped ingot data reported by Nelson' have been used in developing families of curves of transverse and vertical solidification, and in deriving the effect of the w/h ratio upon the solidification pattern. Photographs of many ingots split at Homestead and at Duquesne Works, United States Steel CO., as well as those published by the British Iron and Steel Institute,' have been studied and analyzed. In the interest of brevity, only typical ingots of each type or classification from the above sources have been reproduced. Segregation in Ingots Segregation in ingots falls into three principal classifications: 1—lamellar segregation, as revealed in sulphur prints (Figs. 2 and 3); 2—zone segregation, or broad variations in composition; and 3— interdendritic, or microsegregation. The last class, of minor importance, is not considered here. When liquid metal cools, according to the theory of differential or selective solidification,2 metal of relatively high purity selectively solidifies first. Liquid segregates (principally carbon, phosphorus,

Jan 1, 1954

By David K. Hylbert

This study investigated roof falls in room-and-pillar drift coal mines in eastern Kentucky and utilized geologic methods for Predicting roof conditions in advance of mining. In the Highsplint mine, the roof was classified in four categories or conditions: Condition A and B (Laminated Shale); Condition C (Rolling Sandstone with Shale in Pockets); and Condition D (Zone of Major Sandstone Roll(s)). Structure contour and isopach maps of the Darby coal bed and associated immediate roof rocks were used to project axial trends of the sandstone roof. Trend mapping in the mine and on outcrop provided more detailed control for roof projections.

Jan 1, 1979

By R. W. Brauchli

The author has made a statistical analysis of the relations between recovery and length of cores, diameters of cores and of drill pipe, and cost of coring under different contractual conditions. The data are presented in tabular form. The length of the core appears to play a minor part in the percentage recovered, with a tendency to lower percentages with increased core length; approximately 50 per cent of the length cored is normally recovered if the cores are more than 2 in. in diameter. The diarneter of the core has a more pronounced influence on the recovery; 1 3/8-in. cores average 29.1 per cent, 2 1/8 -in. core 53.4 per cent and 3 1/8-in. cores with 6 5/8-in. drill pipe 68.5 per cent. Where 31/8-in cores were taken with smaller diameter drill pipe, i. e., 4 1/2 - in. drill pipe in 8 1/4-in. hole, the recovery dropped to 49.8 per cent, indicating that the more rigid drill pipe favors good core recovery, a conclusion also borne out by the results obtained in using large drill pipe for smaller diame-ter cores. Surprisingly good recoveries were obtained from both the Johnson and Simpson sands; shale, limestone and dolomite each gave less then average recoveries. No serious fishing jobs resulted from coring operations. Attention is called to the need of a core drill which will make it possible to drill a full-sized hole while coring, and thus reduce the cost of cores. Data pertaining to core drilling should be consistently recorded, such as, diameter of drill pipe and collar, diameter of core, recovery, size of cutter heads, type of core-barrel, coring time, speeds of rotation and of pumps, weight on core-barrel, etc.

Jan 1, 1933

By Alexandre Pourcel

The phenomena of liquation in steel or iron ingots of all sizes, but naturally to greatest extent in the heaviest ingots, have been noticed ever since the commencement on a large scale of the Besse mer and open-hearth manufactures; but they have been studied with care during the last few years only. The English and the Ameri cans were the first to publish the results of investigation upon phe nomena of this clam, to which they have given the name of segregation. Historical. Passing by that which has been written concerning the segregation observed in gray pig-iron, of which instances were given by Karsten, we shall confine ourselves here to that which is known of this subject with exclusive reference to ingot steel and iron. Mr. H. M. Howe, of Boston, in his Metallurgy of Steel, the most complete and well-arranged treatise upon steel, gives a resume of observations, with the results of numerous analyses, bearing upon the phenomena of segregation. According to Tchernoff (with whom we discussed this question at length in 1878, in connection with the cast-steel plates of large dimensions designed for the Italian fleet, which we showed him at Terre-Noire), Kalakoutsky called attention in 1866 to the lack of homogeneity in Bessemer ingots, especially when cast in sand. Our own attention had been called to the phenomena of liquation in 1868 by a somewhat surprising fact which appeared in almost every one of a number of steel-rail ingots coming from the works of Messrs. Pierre and Emile Martin at Sireuil, to be rolled at TerreNoire. In the heating or in the first groove of the rolls, a slice of from 6 to 10 centimeters (2.4 to 3.9 inches) separated itself from the head of each ingot. As a general consequence, the section of

Jan 1, 1894

Edward Keller, Baltimore, Md. (communication to the Secretary*) :—The authors of this paper are to be commended for their industry and congratulated upon the many interesting results which were the fruit of their researches. While thoroughness has marked their work in general, yet on a few points in particular they have touched but lightly, for which reason, it would appear to me, they have hit wide of the mark in their respective conclusions. The work alluded to pertains chiefly to the occurrence of magnetic iron oxide (ferroseferric oxide) in copper-mattes. Because the authors find that the magnetic residue, left by the dissolved sulphides, varies largely in quantity according to the strength of nitric acid used (with potassium chlorate) in dissolving the mattes, they conclude :— "It appears, therefore, that the ferroso-ferric oxide is the result of precipitation by the oxidizing agent, rather than an original constituent of the matte." In this part of their investigation, Messrs. Gibb and Philp have ignored some well-established data,. In the first place, they have overlooked the fact that there are mattes which are strongly magnetic and others which scarcely show any magnetic property. There is nothing in their work tending to explain this variation. They Seem to have tested none of their products for magnetism. Secondly, they have overlooked the fact that magnetic iron oxide probably exists in all ore-charges in the copper-matting furnaces, and, under the given conditions, that this oxide is very difficult to reduce and to combine with silica to form slag. Thirdly, they pay no attention to the varying specific gravity of the several grades of copper-matte, which may exceed, equal, or fall below that of the magnetic oxide. These are .essential points which, I believe, clearly in-

Jan 1, 1906

By John Chipman

The concentration of a solute in a dilute ),zetallic solution may be measured by any of several parame- ters including weight percent, atom fraction, atom ratio, and lattice ratio. The ratio of filled to unfilled interstitial sites is useful for interstitial solutes. A variable 2 proportional to this ratio is used as a measuve of concentration. For component 2 irz a bitzary solution z2 = n2/Ym - nz/b) where b is the numberber of interstitial sites per lattice atom. For a t~lul-ticortzporzent solution this becomes zz = n2/(nl + Cvjnj) in which Vj = - l/b for an interstial solute and +1 for a substitulional solute. In the infinitely dilute solution the activity of an interstitial solute 2 is proportional lo z2. At finile concentration the departure from this limiting law is expressed us an activity coefficient, his coefficient is a function of concentra1io)z expressed as tevactiolz coeffcient 8; is analogous to the jark~iliar e£ bul is found to be independent of concentvation in certain solutions for which data are available. It is found that the same equations may be used to express the activity of a nonmetallic solute, sulfur, in liquid solutions of iron containing other solutes, both metallic and nonmetallic. For a nonmetallic solute or for one which strongly increases the actiuity of sulfur, it is convenient to assign arbitvarily a value vj = — 1. When this is done the derivative is found to be constant in each of the ternary solutions studied. The activity coefficient of sulfur in a complex liquid iron solution may be expressed as where nk is a second-order cross product determined in the quaternary solution Fe-S-j-k. The equation is used to calculate tlze activity of sulfur i)z three sevetl- component solutions. IN thermodynamic calculations concerning dilute solutions it is unnecessary to invoke laws and relations which extend across the concentration range to include concentrated solutions. In most binary metallic systems, as arkeen&apos; has recently pointed out, there exist two terminal composition regions of relatively simple behavior, connected by a central region of much greater complexity. When the solute is a nonmetal there is only one such region and in many systems the concentration range is extremely limited. It is the purpose of this paper to suggest a method for the calculation of activities in such a terminal region in which one or more solutes are dissolved in a single solvent of predominantly high concentration. HENRY&apos;S LAW In the usual textbook statement of Henry&apos;s law, concentration is stated in mole fraction. This has the advantage that it makes Henry&apos;s law thermodynamically consistent with Raoult&apos;s law. Since all measures of concentration at infinite dilution are related by simple proportion it follows that mole fraction, molality, atom ratio, weight percent, or any other unit of concentration can be used with the appropriate constant. At finite concentrations, however, calculations based on the law depend upon the unit employed. Deviations from Henry&apos;s law at finite concentrations depend upon the composition variable employed. They are evaluated in terms of activity and interaction coefficients2 which have become familiar features of metallurgical thermodynamics. It is the purpose of this paper to propose a measure of concentration for metallic solutions containing interstitial or nonmetallic solutes by means of which the calculation of activities in complex solutions may be simplified. The discussion will be restricted to free-energy interaction coefficients3 typified by Wagner&apos;s c|a BINARY SOLUTIONS The several measures of concentration which are to be considered are shown in line a of Table I. The corresponding activity coefficients are in line b and the deviation coefficients, sometimes called self-interaction coefficients, are in line c. Henry&apos;s law simply states that the activity coefficient approaches a constant value at infinite dilution. By adoptihg the infinitely dilute solution as the reference state and defining the "Henrian" activity as equal to the concentration in this state, the activity coefficient is always unity at infinite dilution. This convention is far sim~ler and more useful in dilute solution than emploiment of the &apos;Raoultian" activities and it will be used in the following discussion. The several definitions and equations of Table I will be referred to by means of their coordinates in the table. Early observations of deviations from Henry&apos;s law in metallic solutions were shown graphically4 rather than analytically. For the case of sulfur in liquid iron5 the slope of a plot of logfs vs (%S) was constant in the range 0 to 4.8 pct S, indicating constancy of eh2&apos; in Ic. He was proposed by wagnerz and has been widely adopted. The a function of IIIc recently employed by ~arkenl was designed specifically for dilute solutions. Darken has shown that the value of a12 remains essentially constant for many binary solutions within a substantial range of compositions. The atom ratio is directly proportional to the molalitv.<, a conventional measure of concentration. IVb and C served as the basis for smith&apos;s6 classic studies of

Jan 1, 1968

By J. W. Lacey, F. H. Brinkman, J. E. Faris

This paper presents an analysis of the high-pressure, gas-driven LPG-slug process, based on fluid flow tests in areal models. Two types of tests were made. One series was made in low-pressure models which permitted observation of fluid movement. Three completely misci-ble analog fluids were used. A second series of tests was made in high-pressure models using methane, propane and a light refined oil saturated with methane at room temperature and 1,550 psig. Under the test conditions of room temperature and a pressure level of 1,550 psig, the phase diagram for the fluids used is similar to those for many of the field systems where the process is considered for use. A method for using these laboratory data to calculate field performance of the process is outlined. As a result of this work, it is concluded that small banks of LPG (5 per cent HV or less) are not effective in increasing oil recovery in horizontal reservoirs. Znstead, where small banks are used, the driving gas quickly penetrates the LPG bank because of fingering and channeling; and from this point on, the process behaves essentially as an immiscible gas-injection project. The validity of this conclusion was substantiated by: (1) laboratory studies of the effect of rate, model size and mobility ratio on miscible displacement in areal models; and (2) calculation of field recovery, which compared closely with actual field recovery. INTRODUCTION Field applications and pilot tests of the gas-driven, LPG-bank, oil-recovery process are on the increase. Most of these tests are employing small banks (2% to 5 per cent hydrocarbon volume) of LPG, which is miscible with both the driving gas and the oil in place, in an effort to attain an effective yet economical miscible displacement of oil by gas. The expectation of miscible displacement with small banks is based on the concepts that: (1) lengths of solvent-oil mixed zones, measured during miscible displacements in long slim cores, are representative of those that will occur in the field; and (2) areal sweep efficiencies5 measured in electrolytic model studies are applicable to miscible displacement in reservoirs. Our experimental evidence indicates that the mixed-zone lengths and sweep efficiencies mentioned are not applicable to miscible displacement in reservoirs. In this paper we present an evaluation of the gas-driven, LPG-bank oil-recovery process based on fluid flow experiments in areal models. These results are used to predict the performance of a field pilot test of this process, and the results are compared with the actual test results. THE EFFECTIVENESS OF LPG BANKS The effectiveness of LPG banks of various sizes in accomplishing miscible displacement of oil by gas was determined by displacement tests in a model representing one-quarter of a confined five-spot pattern. The model, 12 X 12 X 1/4 in. in size, was packed uniformly with glass beads. It was operated at a pressure of 1,550 psig and at room temperature; the fluids used were methane, propane and refined oil saturated with methane at 1,550 psig. The saturated oil had a viscosity of 1.2 cp at room temperature. The results of these tests are shown in Fig. 1, where recovery is plotted as a function of the volume of fluid injected for: (1) an immiscible-gas drive with an oil-to-gas viscosity ratio of 85; (2) three sizes of LPG banks; and (3) two completely miscible displacements with mobility ratios of 85:1 and 10:1. (The miscible displacement data plotted are the averages of several tests.) The results show that a 2½ per cent bank of LPG does not increase oil recovery over that obtained by immiscible-gas drive. The 7 and 17 per cent banks are, respectively, about 30 and 50 per cent effective (with reference to the M = 85 miscible-displacement curve) in increasing oil recovery at the point where 2½ hydrocarbon volumes (HV) of fluid have been injected. The percentage effectiveness of the banks at a given volume of fluid injected is defined as Recovery by Bank — Recovery by Gas Drive Recovery by Miscible Recovery by Flooding Gas Drive We conclude from these results that banks of LPG smaller than about 5 per cent HV in an individual stratum will cause from little to no increase in oil recovery. This finding was substantiated by work in low-pressure models, which permitted visual observation of fluid movements. In these tests, three completely miscible fluids having the same viscosity ratios as those used in