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By C. R. King

Most of the acid volcanic glasses such as obsidian, perlite, pitchstone, pumice, and pumicite (volcanic ash) are susceptible to some expansion if suddenly subjected to a suitably high temperature in a properly designed furnace, and subsequently suddenly cooled. Expansion results from the action of chemically combined or dissolved water expanding as a vapor within the softened heated rock particles. This expansion forms countless minute bubbles within the pasty mass of the natural glass particles. If the particles are cooled before these bubbles can escape, the resulting products are cellular, more or less spherulitized glass froths or hollow glass spheres of many types. Chemically, they are essentially aluminum silicates containing about 70 to 75 pct silica, 10 to 16 pct alumina, and 2 to 7 pct sodium plus potassium oxides. They are relatively resistant to attack by acids or alkalies, are resistant to heat up to over 1000°F, and are completely inert to insect or fungus attack.

Jan 1, 1949

By Eugene McAuliffe

THE heavy shrinkage in the production of bituminous coal has reflected adversely in the matter of tonnage produced by stripping arid mechanical loading machinery. The purchase of stripping and underground loading equipment has likewise been circumscribed. How- .ever a growing percentage of bituminous coal is being loaded by stripping and mechanical loading machinery. This situation is due to the fact that numerous strip pits were able to operate in Illinois and Indiana when under- cover mines were subjected to labor interference, a further advantage gained by their ability to produce and market coal at a price below that of the undercover mines. The mines equipped with mechanical loading. apparatus have enjoyed more continued operation for the double reason that the companies using coal-loading machinery are, generally speaking, more substantial and in better financial condition than many of the smaller properties who maintain hand-loading methods, and the market advantage due to lower production costs also reflects to the advantage of the undercover mines using mechanical loading equipment. Where a number of mines are con- trolled by one company, those not equipped with loading machinery and suffering from higher producing costs have often been closed, with the available tonnage concentrated in the more modernly equipped mines.

Jan 1, 1933

By R. W. Smith, K. H. Lee

Bond type simulated closed-circuit grindability tests and batch grindability tests were run on six pure minerals plus a limestone and a taconite ore. The simulated closed-circuit tests were made at five different meshes of grind. The minerals tested varied widely in hardness and breakage pattern. For all simulated closed-circuit tests both Bond and Holmes work indices were calculated and compared. The Bond grindability testlm6 has been widely and quite successfully used for predictions of such items as ball mill power requirements and as an aid in plant comminution equipment selection. The test is interesting in that although run as a series of batch tests it is over-all a simulated closed-circuit test with a circulating load of 250%. The simulated closed-circuit feature is probably the primary reason for the notable success of the test. Perhaps the major criticism that can be brought against the test is that it is time consuming, since it normally takes a trained technician about an eight-hour shift to perform it.4 For many purposes this is an acceptable time requirement. However, if a grindability test is to be used for mill control purposes it should be performed in as short a time interval as possible, preferably under an hour. Sometimes in industry strictly batch tumbling mill tests are run and an attempt is made to correlate such batch tests with plant mill operation. Then an attempt is made to adjust operating tumbling mills based on data from the tests. The tests, however, frequently do not correlate well with operating data. The purpose of the present work was to explore some of the similarities and differences between a simulated closed-circui.t grindability test and a batch type test. Six different minerals plus a limestone and a taconite ore were tested in the experimentation. These materials varied widely in hardness, breakage characteristics, etc. Standard dry Bond grindability tests were mn on all materials at 48, 65, 100, 150 and 200 meshes of grind. Feed material was prepared by stage cmshing to -6 mesh. Initial feed volume was 700 cc. Care was taken to maintain the standard constant weight (about 20125 gm) and number of balls (283) during all the tests. Rotational speed was 70 rpm. Table I lists the materials studied along with pertinent data regarding the materials and Bond grindabilities obtained. In addition, dry batch tests were performed on all materials. These tests were made in the same mill as was used for the Bond tests. An identical ball charge and an identical feed volume were used. After rotating the mill for a predetermined number of revolutions at the same rotational speed as for the Bond test, the material was removed and separated from the ball charge. A screen analysis was performed on this product. Knowing the original size distribution of the feed and the size distribution of the product, it was possible to calculate the grindability or grams of a particular mesh produced per revolution of the mill. After the screen analysis of the product, the various fractions were recombined and placed back in the mill for further grinding. After grinding for additional revolutions of the mill the procedure was repeated. Thus, it was possible to obtain grindabilities for each material at a number of meshes of grind and for various revolutions of the mill. Grind-abilities obtained from batch tests are shown in Table 11. COMPARISON OF BOND AND BATCH GRINDABILITIES Figs. 1A through 1D show relationships between batch and Bond grindabilities. Figs. lA, lB, 1C and 1D show respectively graphs indicating the relationships for batch tests run for 100, 300, 500 and 700 revolutions of the mill. For a particular material on each graph, points are shown for 200, 150, 100, 65, and 48 meshes of grind except for several missing coarse meshes of grind for galena which did not fall conveniently on the figures. For each material and graph the point nearest the origin is for 200 mesh, the next for 150 mesh, the next for 100 mesh, etc. Considering Fig. lA, it is interesting to note that all relationships shown are essentially straight lines. There are, however, considerable differences

Jan 1, 1969

By R. Schuhmann

Available thermodynamic data applicable to copper smelting systems are collected and tabulated, and the important gaps are pointed out. A few examples are given of estimations which can be made from the available data. An experimental research program is proposed to supply the thermodynamic data that appear most essential to better quantitative understanding of the chemistry of copper smelting. The proposed program is designed also to shed specific light on the practical problems of slag losses and magnetite behavior. OPPER smelting, from flotation concentrates to V-/ blister copper, is conspicuous among the large scale chemical processes which are conducted with only relatively incomplete knowledge of the physical chemistry involved. For example, no common metallurgy text explains adequately why copper enters the matte phase while iron enters only to the extent that sulphur is left over after satisfying the copper. Explaining this important phenomenon as a manifestation of the greater affinity of sulphur for copper than for iron is unsound because the affinities of copper and iron for sulphur are about the same at smelting temperatures. As will be shown, other affinities are really decisive in the relatively clear-cut separation of copper in the matte. In contrast, thermodynamic studies have contributed much to our understanding of copper refining, zinc oxide reduction, magnesium production, steelmaking, etc. For each of these processes, the important reactions are clearly recognized, and fair to good quantitative values of the free-energy changes and equilibrium constants are available. Such data have proved to be of constantly increasing practical value in process development and improvement. Work in other fields has furnished much thermodynamic data applicable to copper smelting systems. In fact, several promising starts have been made in applying such data to specific smelting problems. Kelleyl made an appraisal of the possibilities of recovering elementary sulphur from low grade matte. His calculations and compilations of thermodynamic data have represented the starting point for much of the work in this field, including the present survey. Huang and Hayward2 nd Aksoy3 used thermodynamic methods in the study of copper losses in reverberatory slags. Peretti4 used thermodynamic data in explaining the chemistry of converting. The recent publications of Darken and Gurry"." and of Darken,' dealing with the iron-oxygen and iron-silicon-oxygen systems, respectively, present equilibrium data that are applicable to copper smelting systems. Also additional data were reported recently on the affinity of sulphur for copper, manganese, and iron8 and on the sulphur pressures of iron-sulphur melts." The survey presented in this paper was made as the basis for planning an experimental program on the thermodynamics of copper smelting. Few researches on the chemistry of copper smelting have been reported in recent years, so that a reappraisal and coordination of old and new data are essential if further work is to take the directions of maximum value. The experimental program is now in progress, and the plan of attack is outlined at the end of this paper. Progressive Oxidation and Desulphurization of Copper-bearing Liquid Phases: The chemical activities of sulphur and oxygen are two of the most important thermodynamic yardsticks to be applied to copper smelting processes. Virtually the entire smelting and refining sequence involves a series of systems characterized by decreasing sulphur activity and increasing oxygen activity. In this section, therefore, an attempt is made to define and explain these activities in terms of equilibrium partial pressures of SO2, s2, and O,. Also, estimates of these quantities are presented, the estimates being based largely on calculations presented in a later section of this paper. The sequence of steps from raw flotation concentrate to fully oxidized copper ready for poling involves progressive and controlled oxidation. Iron is oxidized and enters the slag. Sulphur is oxidized and leaves in the gas. Table I summarizes several important features of this oxidation and desulphurization sequence, starting at the beginning of the matte blow in the converter. The top line gives in order the principal smelting and refining stages up to fully oxidized copper, plus the additional step, not used commercially, of oxidizing all the way to Cu,O. In the second line are shown the principal copper-bearing liquid phases which characterize the process. Through most of the sequence the copper

Jan 1, 1951

By S. L. Hoyt

The writer has long been interested in seeking an explanation of the upper heat effect in the copper-tin alloys over the a + b range, first described in 1913. These notes are offered, not at all as the final explanation 'of this heat effect, but rather to indicate certain progress which has been made toward establishing what happens over this temperature interval. While working on the thermal analysis of the copper-rich kalchoids (copper-tin-zinc alloys), it was noted that those alloys containing major portions of tin and minor portions of zinc exhibited two marked heat effects, one at about 520' C. and the other at about 600" C., instead of the single effect which is generally observed in either of the two binary series. This matter was discussed with Dr. Guertler, who suggested that a heat effect at about 600" C. in the pure copper-tin alloys might be expected. This led to a more searching examination of the thermal critical points in the pure copper-tin alloys, with the result that a marked, although somewhat weak, heat effect was located at about 600. Somewhat later, this upper heat effect was discussed with Dr. Burgess, and it was requested that the Bureau of Standards make heating and cooling curves of one of these alloys for the purpose of removing any possible doubt as to the actual presence of the heat effect. Results obtained by the Bureau are given in Plate I. In an earlier paper1 differential curves were published showing that the heat effect occurred at constant temperature over the a + B range and increased in magnitude with the amount of B up to a point somewhat above 20 per cent. tin. No heat effect was noticed at this temperature in the eutectoid alloy. The existence of this heat effect seems to require a modification of the present copper-tin diagram in the a + B field, and it has been the object of the work here presented to secure the evidence upon which such a change should be based.

Jan 1, 1919

By R. D. Carnahan, J. E. White

A study of dispersion strengthening in TD-Nickel (nickel plus 2 vol pct Tho2) was conducted employing microstrain techniques at ambient room temperature. It was found that optimum strength was due primarily to the incorporation of stored energy developed by a variety of thermal-mechanical treatments. The relatively low strength of the recrys-tallized condition implies that the dispersed particles themselves offer only token resistance to deformation. The development of resistance to large-scale recovery or recrystallization at temperatures near the melting point requires a more extensive sequence of strain-anneal cycles than does the development of optimum strength. A micro-Bauschinger effect was observed which appears to be related to the lattice resistance to the movement of free dislocations. The effect was nearly identical to that in pure nickel indicating that the presence of the dispersed phase and considerably increased dislocation density (stored energy) only alters the number or effectiveness of barriers. THE early stages of deformation of engineering materials can be conveniently studied by utilizing strain-gage techniques which permit resolution of strains less than 5 X 10-7 in. per in. for testing in four-point bending (Carnahan and white1). The present investigation, part of a continuing study on the very early stages of deformation, was designed to reveal the true role of a dispersed phase in promoting high strength in a commercially available dispersion-strengthened alloy. Although this technique has been used for some time to study microdeformation in pure metals and alloys, it has just recently received attention as a means of investigating dispersion strengthening. Studying the very early stages of deformation in alloys which depend upon a finely dispersed inert phase for strength may prove to be a very important method for a better understanding of these materials. It is essential to obtain considerable clarification of actual dislocation movement and the kinds of deformation barriers which exist before optimum properties can be designed into this type of material with any degree of confidence. Considerable research on a variety of dispersion-strengthened materials has resulted in two different schools of thought regarding the strengthening mechanism. One faction2-4 favors the idea that the particles themselves resist the motion of dislocations. The criterion for yielding is the fracture of the dispersed second-phase particles due to an array of piled-up dislocations. Other invesfigators5-a have shown that particles are effective primarily by allowing a greater buildup of stored energy or dislocation density through thermal-mechanical treatments in the composite than the pure matrix material. The particles themselves, then, are not exclusive obstacles, but the complex network of particles, dislocation tangles, subboundaries, and grain boundaries are strength determining. The development of such a complex dislocation network in SAP has been studied recently in some detail by Goodrich and Ansell. The ability of dispersion-strengthened alloys to resist softening or recrystallization is also of considerable importance; however, the criteria for maximum stability may not necessarily be those for maximum strength. In this study, in addition to the evaluation of the microstrain properties of TD-Nickel, it is felt that considerable clarification of the true dependence of strength and stability on the dispersed phase is shown. I) MATERIAL AND PROCEDURE TD-Nickel is a dispersion-strengthened alloy developed by the E. I. DuPont de Nemours Co., which contains 2 vol pct thoria (Tho2) in a pure-nickel matrix. The average ThO2 particle size is approximately 0.1 p and the interparticle spacing is less than 1 u. The material was supplied by DuPont in two conditions: hot-extruded bar stock, and stress-relieved cold-rolled sheet 0.025 in. in thickness. The bar was extruded at 2200°F from a cold-pressed and sintered billet. The sheet stock was prepared from the extruded material by a process involving ten or more 50-pct cold reductions by rolling with intermediate anneals at 1800° to 2000°F. Test specimens used in this study were prepared in the form of rectangular parallelepipeds measuring 0.375 by 1.375 in. in thicknesses ranging from 0.025 to 0.040 in. Samples prepared from sheet and extruded stock were mechanically polished before heat treatment and were handled with extreme

Jan 1, 1964

By David Cornell

Back pressure test data on natural gas wells are short time test data of unsteady state nature. Performance curves from which unsteady state effects have been eliminated, called stabilized performance curves, are necessary for understanding the behavior of gas wells and for scheduling gas fields for periods up to 20 years. A calculation procedure has been developed whereby three day, seven day, 30 day, or other duration stabilized performance curves may be calculated from back pressure test data. Such curves are essential for correct gas deliverability calculations and gas field scheduling. I NTRODUCTION The manner in which a back pressure test is made will affect the slope of the back pressure curve because the radius of drainage changes with the length of time that the well is allowed to flow. The reciprocal of the slope of the back pressure curve is defined as n in Equation 1 and varies from 0.5 to 1.0. If the flow is viscous and the radius of drainage constant, n will have a value of 1.0. Because of turbulence in the formation near the wellbore, the pressure drop is usually greater than the viscous flow pressure drop and the exponent n is frequently less than 1.0. In addition, since the radius of drainage moves away from the well-bore during the test, the gas flows a greater and greater distance as the test proceeds, with a resulting increased pressure drop at the high flow rates, and, again, n for the test tends to be less than 1.O. The effect of the changes in the radius of drainage may be calculated and the results used in preparing stabilized performance curves for fixed values of the radius of drainage. Such curves can be made for a defi- nite time period, such as three day, seven day, or 30 day stabilized performance curves. These cukes will show the effect of turbulence near the wellbore and can be used to predict the performance of the gas well at any flow rate or for any production period. In order to discuss the importance of the radius of drainage quantitatively, it should be defined. Muskat" defines the radius of drainage as follows: "... the radius of drainage gives the distance from the well to which the approximately steady state condition has been established ... it being assumed that no gas is removed from any point until the radius of drainage has passed that uoint." An eauivalent definition of the radius of drainage is that radius at which the extrapolated portion of the steady state portion of the pressure gradient gives a pressure equal to the shut-in reservoir pressure. This definition is also implied in the back pressure equation. The radius of drainage is, then, the distance into the reservoir from which the gas appears to originate at any time. It is, however, only a useful concept and does not actually exist. Fig. 1 illustrates the definition of the radius of drainage. At the end of each flow period the radius of drainage may depend on three factors: (1) the duration of each flow period; (2) the rate of gas production; and (3) the rate and duration of the previous flow periods. In general, back pressure tests are conducted with various lengths of production time and at various flow rates. Each individual back pressure test, therefore, requires an individual analysis. The calculations of the change in the radius of drainage have been made, however, for the case of equal flow periods for all four production rates and several sets of increasing flow rates. Fig. 2 illustrates the results of such calculations made by the method of Cornell and Katz2 for the case of 8, = 50,000 and the flow rate increasing in the ratio 1.0:2.0:3.0:4.0 for each flow period. The increase in the radius of drainage during the test is apparent.

Jan 1, 1956

By E. P. Chartkoff, W. P. Sykes

In 1926 one of the authors published researches on the determination and description of the iron-tungsten and iron-molybdenum systems,' including the equilibrium diagrams. In 1929, further work was carried on, including the examination by X-rays, which is recorded here. Meas-urements were made of changes in lattice parameters in the solid solutions. Precipitation from the solid solution and the accompanying changes in hardness were studied as well as the formation of the intermetallic com-pound phases upon sintering a mixture of metal powders. Materials All the specimens were prepared from the same quality of metals and by the same methods as were described in the determination of the constitutional diagrams. The metal powders as mixed and pressed were sintered or fused in a hydrogen atmosphere and subsequently treated as indicated in the titles of the figures. The formation of the iron-rich solutlon in the solid was accomplished by sintering in hydrogen for a period of 20 to 30 hr. at a temperature 25' to 50' C. below the melting point of the eutectic. The tungsten-rich and molybdenum-rich solid solutions of iron were prepared by adding the iron as a solution of iron ammonium oxalate to the oxide of tungsten or molybdenum, followed by a hydrogen reduction. This method results in a homogeneous alloy after sintering the pressed metal powder for 20 to 30 hr. at a temperature slightly below that of the peritectic reaction in the system involved. For X-ray examination the specimens were variously prepared, depending on the nature of the sample and what it was desired to show. For example, the iron containing tungsten or molybdenum in solid solution was cut with a file, the chips were put through bolting cloth, and this powder of filings formed the specimens for comparative study. The

Jan 1, 1930

By L. L. Wyman

THE resultant embrittlement caused by the exposure of oxygen-bearing copper when hot and exposed to reducing gases has been the subject of many studies.1 Little attention, however, has been given to the possible embrittling effects due to atmospheres or conditions that under some circumstances might be the source of a reducing gas. At rather infrequent intervals there occur reports of copper becoming embrittled during normal annealing cycles in commercial steam-atmos-hered furnaces such as customarily are used for this operation. As might be expected, several other factors exist-such as oil, dirt on the wire, or in the furnace, or metallic surface contacts that might produce reducing gases and be the source of the trouble. However, in consider-ation of the statement made by Ruder,2 it would seem that under some conditions steam itself might prove to be the source of trouble. A consideration of the amount of the dissociation of water vapor up to temperatures of the melting point of copper shows that' the amount of hydrogen that could come from this source is far too minute to account for any embrittlement. What such information does not tell is what will happen at the surface of copper when subjected to steam at elevated temperatures, for entirely different conditions may persist, which would account for Ruder's observation. Furthermore, there are no data as to what might happen at the surfaces of other materials present, the result-ant of which might affect the condition of the copper present. For this reason, it was decided to make a series of experiments com-parable to those previously conducted by the writer,1 which would clarify the effect of the steam on copper, and in copper in the presence of steel.

Jan 1, 1940

By M. H. Sommer

MANY attempts have been made to develop a relation between the tensile properties and the deep-stamping qualities of metals com-monly used in deep drawing. These operations are generally performed cold and the metal is always stressed beyond the elastic limit. However, the problem cannot be readily solved without a proper investigation of (1) the relation between actual stress and actual strain in the plastic range and (2) the stresses that are set up in the metal during the process of deep stamping. Much work has been done in recent years to add to our knowledge on plastic deformation of metals and the shortcomings of the ordinary tensile test, particularly in the plastic range, have been sufficiently recognized. It has been widely acknowledged that the local contraction, which appears in a tensile test after the maximum load is reached, is not a general characteristic of the material but is peculiar to this form of testing. The plastic deformation of materials is explained by the slip of their crystals along certain planes and this rearrangement should be similar whether observed in a tensile, compression or torsion test, and if the results of any of these forms of testing show deviations, it must be due to other influences, as for example the local contraction in a tensile test. For this reason the tensile-test curve as obtained from the measurements taken on a tensile-test machine or registered by an autographic device has been supplemented by the so-called "actual stress-strain curve," which is constructed from the observed tensile-test data by eliminating the effect of local contraction and is in complete alignment with the stress-strain values obtained in a compression or torsion test. The actual stress-strain curve shows the increase of actual unit stress in relation to unit elongation beyond the yield point and

Jan 1, 1934

By I. Fatt

A recently developed system for measuring electrical resistivity of liquids without use of electrodes offers some interesting possibilities in electric logging technology. The equipment as supplied by the manufacturer is satisfactory for continuous mud logging on a drilling rig or for measuring mud or filtrate resistivity in the laboratory. A simple modification of the commercially available instrument makes it suitable for measuring resistivity of core samples in the laboratory. The continuous measurement of mud resistivity on a drilling rig is a convenient means for detecting mixing of formation water with the drilling mud. Such information is useful to the geologist, the mud engineer and the logging engineer. However, continuous mud resistivity logging by conventional electrode-type resistivity cells is beset with difficulties. The mud, sand and rock chips abrade the electrodes, thereby changing the cell constant and eventually destroying the cell. Also, additives and crude oil in the mud may poison the electrodes by coating them with a nonconductive material. An electrode-type resistivity cell. therefore, may give erroneous readings under certain conditions. Electric logging companies circumvent the electrode poisoning problem by using a four-electrode resistivity cell for measurement of mud resistivity. In this cell, change in electrode area does not change the cell constant. However, the four-electrode cell is difficult to adapt for continuous reading and does not solve completely the problem of electrode abrasion by the sand and cuttings in the mud. The measurement of electric logging parameters on core samples in the laboratory encounters some of the same problems discussed in connection with mud logging. Ideally, the electrical resistivity of a core sample should be measured by placing platinum black electrodes in direct contact with the plane ends of a cylindrical or rectangular sample. Platinum black electrodes however, are much too fragile and easily abraded to be brought in contact with a rock sample. Also, oil or other constituents in the fluid contained in the sample will poison platinum black. In practice, gold-plated brass electrodes, in an AC bridge circuit operating at about 1,000 cps, are used for routine core analysis. For more precise work in research studies, a four-electrode scheme is used.',' Preparation of the samples for the four-electrode method is much too involved for routine core analysis. An apparatus for measuring resistivity of liquids without use of electrodes was described by Guthrie and Boys3 in 1879. They suspended a beaker, containing the electrolyte, by a torsion wire and rotated a set of permanent bar magnets around the vessel. The eddy currents induced in the electrolyte reacted against the rotating magnetic field to develop a torque, which was measured as a deflection of the torsion wire. In 1879 this method could not be made precise or convenient because of the lack of strong permanent magnets. The writer described a very greatly improved apparatus similar to that of Guthrie and Boys, but it was not suitable for continuous measurements or core samples.' Many electrodeless resistivity devices using radio frequency current are described in the literature.5, 6 These generally are suitable only for noting the end-point in a chemical titration. They do not measure resistivity, instead measuring a complex quantity which includes the dielectric constant and the magnetic permeability. The first description of the apparatus to be discussed in this paper was given by Relis.7 Improvements and modifications are described by Fielden,s Gupta and Hills,> and Eichholz and Bettens.10 DESCRIPTION OF APPARATUS The apparatus used in this study is based on the principle that the solution under measurement can form a loop coupling two transformer coils, as shown in Fig. 1. For a fixed AC voltage applied across Coil A, the voltage appearing across Coil B is a function of the resistance of the liquid-filled loop. The details of the voltage generating and measuring circuits are given in Refs. 7, 8, 9 and 10. A block diagram of the equipment is given in Fig. 7. Special features worth mentioning are the operating frequency of 18,000 cps and the automatic temperature compensation which results in the given resistivity readings being automatically correlated to 25°C. The liquid loop supplied by the manufacturer, shown in Figs. 1 and 2, was modified for use in core analysis (Fig. 3). The core sample under test is substituted for a section of the original loop. As shown in Fig. 3, the unit accepts only plastic-mounted cylindrical core specimens. A Hassler-type sleeve easily can be designed for the unit if unmounted cores are to be measured. EXPERIMENTAL PROCEDURE MUD LOGGING A simulated mud line was set up in the laboratory.

By J. F. Martin, L. M. Melnick, R. Rapp, R. C. Takacs

Recent studies on the determination of hydrogen in steel have shown that the hot-extraction method for removing hydrogen from a solid sample is preferable to its removal from a molten sample by vacuum fusion or by fusion in vacuum with tin. A number of techniques are available, however, for determining the hydrogen so extracted. They include: thermal conductivity, gas chromatography, pressure measurement before and after catalytic oxidation of the hydrogen to water and removal of the water, and pressure measurement before and after diffusion of the hydrogen through a palladium membrane. These techniques have been evaluated on the basis of initial cost, maintenance, speed and accuracy of analysis, and applicable concentration range. The results of this study showed that the palladium-membrane technique is best suited for routine use. FOR some time investigators have been concerned with the origin, form, and effect of hydrogen in steel. In such stdies', the analysis for hydrogen constitutes one of the most important phases. It is quite apparent that the results for hydrogen concentrations in a given steel are dependent on the method of obtaining the sample, storage of the sample until analysis, preparation of the sample, and analysis of the sample, including all the facets inherent in the calibration and operation of an apparatus for gas analysis. There are a number of means available for determining hydrogen. This is a critical study of some of the more common techniques in use today. In most conventional melting and casting methods, hydrogen concentrations of 4 to 6 parts per million (ppm) in steel are quite common. Because of the undesirable effects of hydrogen on steel there has been increased use of techniques such as vacuum melting,' vacuum casting, and ladle-to-ladle stream degassing, which lower the hydrogen content to levels on the order of 1 to 2 ppm. Therefore, the method used for determining hydrogen in steel must be sensitive and precise. In any analytical procedure for gases in metals there are two distinct operations—the extraction of the gas from the metal and the analysis of the extracted gas. To extract the gas from the steel, three methods have been employed: 1) fusion of the sample with graphite at high temperature; 2) fusion with a flux, such as tin, at a lower temperature; and 3) extraction of the hydrogen from the solid sample at a temperature below the melting point of the steel. Fusion with graphite is the least-acceptable method. The blank in this method is higher and more variable than in either of the other two methods. The hydrogen fraction of the total gas composition usually is between 10 and 50 pct; thus, a larger analytical error is possible. The vacuum-tin fusion4 extraction of hydrogen is probably the most rapid method in use today; the extraction time is usually about 10 min. However, with this system a bake-out of the freshly charged tin for 2 hr is necessary and a change of crucible and a charge of fresh tin are required after each day of operation whether one or thirty samples have been analyzed. In addition, frequent checks of blank rates are required since CO and Na are continually being given up by the steel samples dissolved in the tin bath. The composition of the gas in this method lends itself readily to analysis; although the hydroge concentration may fall to as low as 50 pct, more often it is above 90 pct, thus allowing a more precise analysis (because of less interference from other gases). In 1940 ewell' published the hot-extraction method for extracting hydrogen from the solid sample, comparing analysis for hydrogen extracted at 600°C with similar analysis for the gas extracted at 1700°C by fusion with graphite. Good agreement for hydrogen was obtained between these two methods, provided sufficient time was allowed for extraction at the lower temperature. carsone obtained good results in his comparison of this hot-extraction method with vacuum-tin fusion. Subsequent work by Geller and sun7 and Hill and ohnson' has shown that steel samples should be heated to at least 800°C to effect the release not only of the diffusible hydrogen but also of the "residual" hydrogen that may be present as methane. Since the rate of evolution of hydrogene9l0 depends on such factors as sample size and composition, thermal history, and extent of cold work, a fixed extraction time is not possible. Extraction times of 30 min are normal, but 2 hr are not unusual. Induction or resistance heating may be used in the hot-extraction method. With resistance heating the

Jan 1, 1964

By C. H. Jr. Herty

ALMOST every metallurgist who has given the Howe Memorial Lecture has had a personal contact with the distinguished gentleman to whose honor this hour is devoted. Unfortunately for me, such personal contacts were not possible. However, in the preparation of a thesis on the open-hearth process, one of my earliest tasks was to make a survey of the literature, and it was from Professor Howe's Metallurgy of Iron and Steel that I drew a number of references to previous work which formed the foundation for my reading. In his volume there is such a complete exposition of the then current thought on the subject of slags and on their role in the elimination of phosphorus from steel that I feel no hesitation in discussing in this Howe Lecture the subject of "Slag Control." In the present era of close specification, the drive for uniformity of product, and the close inspection of the product and of the cost sheet, the utmost efforts must be made to control the steelmaking variables to the best advantage of the steel producer. One of the major variables is the slag in the furnace and its effect upon the composition and quality of the metal. What advantages are to be gained from slag control? In the broad sense the advantages must be tremendous, because the very foundations of good steel melting are based on "shaping up" the slag to a point where, with proper temperature, the heat is ready for the final additions. Every melter works toward these ends through his experience with innumerable heats of steel. The elimination of undesirable constituents such as phosphorus and sulphur is entirely a matter of slag composition and physical nature, a point well known for over half a century. The role played by the slag in assisting in proper heat transfer from roof and flame to the steel has been equally well known. In more recent years there has come the problem of oxygen control in the more accurate gaug-ing of additions for making high-grade rimmed steel for the new strip mills, and in the deoxidizing additions for grain-size control and cleanli-ness of forging steels, both carbon and alloy. In this problem the oxidiz-ing characteristics of the slag are of prime importance.

Jan 1, 1940

By O. W. Ellis

The question of the influence of gases upon the properties of copper has received the attention of a number of investigators, among whom Sieverts,' Iwase,2 Lobley and Jepson3 stand preeminent. Solubility of Gases in Copper Sieverts and Iwasé concerned themselves with the solubility of a variety of gases in the metal in the solid and liquid states. They determined the absorption coefficients of these gases and in all cases found a sharp change in solubility at the melting point of the metal. In this respect they disagree with Lobley and Jepson, who have based their opinions upon the appearance of small ingots of the metal which had been fused in an atmosphere of one or other of three gases and had then been rapidly cooled, while surrounded by gas, to the freezing point (rate—possibly 30" to 60" C. per sec.). The ingots that had been fused and cooled under nitrogen and carbon monoxide were free from blowholes and it was assumed that these gases were not absorbed in amounts much in excess of those which would dissolve in the solid metal; the ingots similarly treated under hydrogen were full of blowholes and it was assumed in this case that gas was ejected on solidification of the copper. The effect of varying the rate of freezing upon the character of the test ingots was not examined by these investigators; otherwise, it is felt, their views might have been subject to modification. Sieverts' most important contribution is that the solubility of a gas in any metal is proportional to the square root of its pressure or concentration. Knowing then the absorption coefficients of the various gases in copper, it should be possible to determine the analysis of the

Jan 1, 1929

By O. W. Ellis

The question of the influence of gases upon the properties of copper has received the attention of a number of investigators, among whom Sieverts,' Iwase,2 Lobley and Jepson3 stand preeminent. Solubility of Gases in Copper Sieverts and Iwasé concerned themselves with the solubility of a variety of gases in the metal in the solid and liquid states. They determined the absorption coefficients of these gases and in all cases found a sharp change in solubility at the melting point of the metal. In this respect they disagree with Lobley and Jepson, who have based their opinions upon the appearance of small ingots of the metal which had been fused in an atmosphere of one or other of three gases and had then been rapidly cooled, while surrounded by gas, to the freezing point (rate—possibly 30" to 60" C. per sec.). The ingots that had been fused and cooled under nitrogen and carbon monoxide were free from blowholes and it was assumed that these gases were not absorbed in amounts much in excess of those which would dissolve in the solid metal; the ingots similarly treated under hydrogen were full of blowholes and it was assumed in this case that gas was ejected on solidification of the copper. The effect of varying the rate of freezing upon the character of the test ingots was not examined by these investigators; otherwise, it is felt, their views might have been subject to modification. Sieverts' most important contribution is that the solubility of a gas in any metal is proportional to the square root of its pressure or concentration. Knowing then the absorption coefficients of the various gases in copper, it should be possible to determine the analysis of the

Jan 1, 1929

By H. C. Heard

The review by Professor J. C. Jaeger (Chapter 1) briefly summarizes and discusses a select group of papers by various workers dealing primarily with aspects of fracture in brittle rock materials. Professor Jaeger's treatment is primarily concerned with the correlation of phenomenological and theoretical failure criteria with empirical results from short duration tests at ambient temperatures and generally at low lithostatic and interstitial fluid pressures. As engineering rock mechanics becomes more concerned with new techniques of mineral exploration and production at increasingly greater depths in the crust, it is well to be aware of the effect of the environment -that of the superposed stress field upon the lithostatic and interstitial fluid pressure, the temperature and the duration of the loading upon the failure of rocks either by fracture or flow. All results to be discussed here are from laboratory tests on small homogeneous samples, thus caution should be used in the direct extrapolation of these results to large inhomogeneous rock masses having quite different boundary conditions in the earth. The purpose of this supplement is to briefly point out the major effects of these parameters as examined singly, with all others held constant, and to cite some recent results which apply to the main theme on the brittle failure of rocks. The total stress field imposed upon a small volume of porous and permeable rock in the earth's crust may be thought of as the sum of an applied differential stress, plus a lithostatic pressure, plus an interstitial fluid pressure. The differential stress portion may be completely specified by nine components, six shear and three normal. If the small volume element is in rotational equilibrium, by suitably choosing our coordinate axes we may resolve these nine components into the three principal com-

Jan 1, 1967

By A. A. Berk

LAGGING technology and the slow spread of information have been the chief obstacles to widespread participation in minimizing the industrial pollution load. These obstacles can be conquered by fact finding and applied research. There are three aspects to the problem of water-borne mineral waste: to minimize the amount being thrown away, to select a predisposal treatment, and to use the products or dispose of them. It is often possible to minimize the waste by making very minor changes in the process that produces it. For example, a manufacturer of automobile bumpers greatly reduced the dragout 'from a plating bath by modifying the design and position of two boltholes.' A plater of automobile hubcaps installed a drainage bar and decreased the loss of chrome-plating solution to the rinse water by about 80 pct.' The mill at a western mine found it possible to discard 60 to 70 pct of an ore with minimum treatment," so that the processing effort could be concentrated on a high-graded slime, with significant reduction in costs and improvement in recovery. The possibilities for waste reduction through process changes are limited only by the imagination. A recent patent points out the advantages of using No. 1 fuel oil instead of water in wet-process cement making;& the fuel oil presumably has better properties than water for this purpose and is said to be almost com'pletely recovered or utilized, so that there is no waterborne waste. Recycling to reduce wastes and improve process economy is very well illustrated in vanadium and uranium recoveries from relatively low grade ore. Ores containing 6 pct calcium carbonate were found to give poor vanadium recovery by the salt-roasting process because the vanadium was converted to water-insoluble calcium vanadate. Following the salt-roasting process, sulfuric acid was used to leach the uranium. Enough calcium sulfate was formed

Jan 1, 1958

A. R. Ledoux,New York City: The so-called combination method " is generally used in assaying bar copper for silver. It has been modified from time to time. Briefly outlined

Jan 1, 1901

ALABAMA Anniston.-Carrington, F. G. Auburn.-Brown, R. L. Bessemer.-Abbott, C. E. Dobbs, G. G. Ferguson, V. Salmon, H. S. Schaber, C. F. Birmingham.-Aldrich, T. H. Aldrich, T. H., Jr. Allen, A. W, Ball, E. M. Bonnyman, J. Bowron, J. Bush, M. W. Crawford G. G. Crockard, F. H. Ellis, E. E. Fairbairn, C. T. Gallacher, J. Geisiner, H. S.

Jan 1, 1917

By Henry J. Welge

The approximate methods which are now in use for calculating oil displacement from reservoirs by gas-cycling or gravity-drainage at constant gas pressure, or by water flooding, make use of fundamental relationships derived by Leverett' and Buckley and Leverett.2 The mathematical equations needed are derived by applying Darcy's law to the flowing phases, and by material balance considerations. ln general, any treatment of this type gives. for any particular exploitation time considered, a plot of oil saturation against distance in the reser-voir. The oil recovery must then be obtained by integrating in some manner the area under the plot. A useful analytical method has been derived for computing the average saturation, and hence the oil recovery. Use of this method simplifies the calculations because it makes unnecessary any numerical integrations. and even the saturation distribution plots are not needed. A further advantage of the method is that knowledge of the relative permeabilities is required only for a limited and intermediate saturation range. In both the Buckley and Leverett method and the method discussed here, a linear sand section is assumed, and in the case of gas drive the gas pressure is assumed sufficiently constant both with respect to reservoir position and time so that changes in gas density. solubility, or reservoir volume factor are negligiklle. Thus, the exploitation contemplates oil displacement as by an immiscible phase. Examples are given to illustrate how the new method can be used. INTRODUCTION AND THEORETICAL BACKGROUND This paper treats a simplified method for computing oil recovery when the oil is displaced, from the reservoir sand by a fluid which, within the limits of accuracy desired, can be assumed to be incompressible and immiscible with the oil. The method makes use of two basic relations originally developed for the case of water displacing oil. However, the case of gas displacing oil saturated with gas at a constant (or nearly constant) pressure may also be considered a displacement by an immiscible fluid. This is possible for the reason that the concentration of the gas in the oil never changes if tile pressure is fixed. consequently, any additional free gas must remain undissolved in the oil, and so must act essentially as an immiscible phase. For convenience, the cape of gas drive will be considered first. Both of the two basic relations needed refer to a linear reservoir, or one which may be somewhat idealized so that a constant cross-section is exposed to fluid flow. Further, the displacing phase is injected at one end, or face; of the reservoir, while the produced fluids are understood to emerge at one point only. which is the opposite face of the reservoir. As indicated in Fig. 1, the reservoir may he inclined by some angle 8. The first of the required equations may be derived by applying Darcy's law to both displacing and displaced phases, and subtracting the two equations. The result for water drive has been given previously, as Equation (13) of the reference by

Jan 1, 1952