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By A. Spilners, M. Simnad

The rates of formation of the different oxides on molybdenum in pure oxygen at 1 atm pressure have been determined in the temperature range 500° to 770°C. The rate of vaporization of MOO, is linear with time, and the energy of activation for its vaporization is 53,000 cal per mol below 650°C and 89,600 cal per mol at temperatures above 650°C. The ratio Mo03(vapor.lzing)/MoOS3(suriace) increases in a complicated manner with time and temperature. There is a maximum in the total rate of oxidation at 6W°C. At temperatures below 600°C, an activation energy of 48,900 cal per mol for the formation of total MOO, on molybdenum has been evaluated. The suboxide Moo2 does not increase beyond a very small critical thickness. At temperatures above 725°C, catastrophic oxidation of an autocatalytic nature was encountered. Pronounced pitting of the metal was found to occur in the temperature range 550° to 650°C. Marker movement experiments indicate that the oxides on molybdenum grow almost entirely by diffusion of oxygen anions. USEFUL life of molybdenum in air at elevated temperatures is limited by the unprotective nature of its oxide which begins to volatilize at moderate temperatures. Although the oxide/metal volume ratio is greater than one, the protective nature of the oxide film is very limited. Gulbransen and Hickman' have shown, by means of electron diffraction studies, that the oxides formed during the oxidation of molybdenum are MOO, and MOO,. The dioxide is the one present next to the metal surface and the trioxide is formed by the oxidation of the dioxide. Molybdenum dioxide is a brownish-black oxide which can be reduced by hydrogen at about 500°C. Molybdenum trioxide has a colorless transparent rhombic crystal structure when sublimed, but on the metal surface it has a yellowish-white fibrous structure. It is reported to be volatile at temperatures above 500" and melts at 795°C. It is soluble in ammonia, which does not affect the dioxide or the metal. In his extensive and classic investigations of the oxidation of metals, Gulbransen2 has studied the formation of thin oxide films on molybdenum in the temperature range 250" to 523°C. These experiments were carried out in a vacuum microbalance, and the effect of pressure (in the range 10-6 yo 76 mm Hg), surface preparation, concentration of inert gas in the lattice, cycling procedures in temperature, and vacuum effect were studied. The oxidation was found to follow the parabolic law from 250" to 450°C and deviations started to occur at 450 °C. The rates of evaporation of a thick oxide film were also studied at temperatures of 474" to 523°C. In vacua of the order of 10- km Hg and at elevated temperatures, an oxidation process was observed, since the oxide that formed at these low pressures consisted of MOO, which has a protective action to further reaction in vacua at temperatures up to 1000°C. Electron diffraction studies showed that, as the film thickened in the low temperature range, MOO8 became predominant on the surface. Above 400°C MOO, was no longer observed, MOO, being the only oxide detected. The failure to detect MOO, on the surface of the film formed at the higher temperatures does not militate against the formation of this oxide, since according to free energy data MOO3, is stable up to much higher temperatures. At the low pressures employed, this oxide would volatilize off as soon as it was formed. Its vapor pressure is relatively high and is given by the equations" log p(mm iig) = -16,140 T-1 -5.53 log T + 30.69 (25°C—melting point) log p(mm He) = -14,560 T-1 -7.04 log T+1 + 34.07 (melting-boiling point). Lustman4 has reported some results on the scaling of molybdenum in air which indicate a discontinuity at the melting point of MOO, (795°C). Above the melting point of MOO,, oxidation is accompanied by loss of weight, since the oxide formed flows off the surface as soon as it is formed.5,6 Qathenau and Meijering7 point out that the eutectic MOO2-MOO3 melts at 778C, and they ascribe the catastrophic oxidation of alloys of high molybdenum content to the formation of low melting point eutectics of MOO3 with the oxides of the melts present. Fontana and Leslie -explain the same phenomenon in terms of the volatility of MOO,, which leads to the formation of a porous scale. Recent unpublished work by Speiser9 n the oxidation of molybdenum in air at temperatures between 480" and 960°C shows that the rate of weight change of molybdenum is controlled by the relationship between the rates of formation and evaporation of MOO,. They have measured the rates of evaporation of Moo3 in air at different temperatures and estimated an activation energy of 46,900 cal. This compares with the value of 50,800 cal per mol obtained by Gulbransen for the rate of sublimation of MOO, into a vacuum.

Jan 1, 1956

By H. L. Armstrong

SOLID-STATE diffusion is an important technique in certain aspects of metallurgy, and especially the metallurgy of semi-conductors and semi-conductor devices. If the diffusion is carried out under constant conditions for a time, t, the concentration, C, of the diffusant at a depth, x, below the surface from which the diffusion is carried out is given by an expression of the form. C = Cof(x,Dt) [I] Co being a constant, and D the diffusion constant of the diffusant in the material and at the temperature

Jan 1, 1959

By R. Woods

INTRODUCTION Gaudin (1), considered that "the mechanism of mineral collection is the central problem of flotation theory". From their work on adsorption phenomena in flotation for more than fifty years (2), Gaudin and his co-workers have made major contributions to the elucidation of this mechanism, a fact acknowledged by their contemporaries in the field (e.g. (3)). Their investigations in a number of areas, e. g. demonstrating that submonolayer quantities of adsorbed collector species can induce flotation, or identifying the influence of substances which can activate or depress (1), have helped to provide the basis for and the development of a theory to account for the interaction between mineral and collector. It was established in the late fifties (4) that the presence of oxygen is a prerequisite for the flotation of metal sulfides with thiol collectors. This fact rendered inadequate the concept of simple ion adsorption being responsible for rendering these minerals hydrophobic. The requirement for oxygen has been explained (1) in terms of this species being a component in chemical reactions between the sulfide surface and the collector. Gaudin has been instrumental in identifying the products of chemical reactions at sulfide minerals (1, 5), a line of work which has been continued particularly by Finkelstein and co-workers in South Africa (6). In presenting a detailed mechanism of the mineral-collector- oxygen interaction, it has often been considered that the mineral surface [must] first be oxidized to a metal oxy-sulfur species which

Jan 1, 1976

By Nev A. Gokcen

DISCREPANCIES and scattering in the equilibrium data on the reactions of hydrogen, and CO with dissolved oxygen in liquid iron are un- duly large. Available experimental results on the reduction of liquid ferrous oxide, i.e., wüs-tite, with hydrogen and CO are questionable, as pointed Out by Darken and Gurry'l Direct determinations of the solubility of oxygen in liquid iron are subject to errors which cannot be easily reduced by further experimental refinements, and therefore an accurate but indirect method is highly desirable. The purpose of this investigation was, therefore, 1)

Jan 1, 1957

The authors have done a very thorough job in analyzing the factors affecting turndown sulfur performance at Inland's No. 4 B.O.F. While many of the results are not unexpected, it is helpful I am sure to have quantified many of the relationships that the operators rely upon daily. On the other hand, however, the results shown for ladle skimming are very surprising. I do not doubt the statistical relationship shown but I feel, based on our experience at Youngstown, that some other parameter has been ignored in the data on ladle skimming. It was our experience that by skimming our hot metal transfer ladle we could reduce our lime consumption by eleven percent while obtaining sulfur removal comparable to that shown by the authors. I would like the authors comment of similar adjustments on the lime charge that were made on skimmed heats at Inland. If not, it would seem that one could gain more desulfurization in the B.O.F. by raising the hot metal manganese than by installing a skimmer. The author's state that no comparisons are valid between the data sets for the two time periods involved because of the difference in the consumption of No. 2 Bundles. I feel this in fact is one of the important conclusions to be drawn from the paper, as there seems to be approximately a 10-20 percent difference in percent of heats that are under 0.020 percent sulfur for similar conditions, which is an extremely important difference with today's demands for low sulfur. I would like the author's comments on the difference in the amount of 82 bundles consumed. Along this same line I was quite surprised by the relatively low number of heats that had a first turn down of 0.020 percent sulfur or less. Also rather disconcerting are the conditions necessary to achieve a first turn of 0.020 percent sulfur, 50 - 60 percent of the time, as required by today's specifications. It is a problem which we are well aware of, but the numbers are still shocking.

Jan 1, 1972

By T. R. Graham, J. R. Long

This report is concerned with part of a series of investigations carried on by the Federal Bureau of Mines on alloys, particularly nonferrous alloys, made with electrolytic manganese. A broad general program instituted after commercial quantities of electrolytic manganese became available was necessary in order to compare the effects of electrolytic manganese with those of the ordinary commercial grades. Representative analyses of these two materials show the commercial manganese metal to contain up to 2 per cent iron, a maximum of I per cent silicon and 0.06 per cent carbon, while the electrolytic manganese rarely exceeds 0.01 iron, 0.02 sulphur, with no silicon or aluminum. In the literature, the emphasis has been largely on high-strength casting alloys containing up to 5 per cent manganese, and few data are available on wrought manganese alloys. These factors, coupled with the strategic position of copper and zinc, have given impetus to the Bureau's War Research Program for the development of alloys containing nonstrategic manganese for the purpose of supplementing or providing alternates for the more strategic metals. The alloy reported here was studied, along with several other ferrous and nonferrous alloys, as possible cartridge-case material, and was chosen after a review of the properties of the ternary alloys of copper-manganese-zinc. Preliminary Work In a cursory survey of this system, alloys ranging from 60 to 95 per cent copper, o to 50 per cent manganese, and 5 to 40 per cent zinc were investigated. The alloys containing 60 per cent copper were found to fall into the two-phase alpha plus beta region of the system, and since those containing 70 per cent would not permit a saving, only alloys containing 65 per cent copper were considered. The tensile properties of these 65 per cent alloys are plotted in Fig. I as a function of manganese content for annealed material and for four conditions of cold-work In the annealed condition the increases in strength and decreases in elongation are minor up to 15 per cent manganese; beyond this, the changes become more significant. In the cold-worked condition, the first 5 to 10 per cent of manganese appears to have the greatest strengthening effect, the rate of increase dropping off as the manganese increases beyond this amount. These effects are more pronounced with moderate than with severe cold reduction. It is also interesting to note that while the elongation of annealed material drops regularly with increasing manganese, the elongation in the cold-worked state is relatively little affected by increasing manganese content, particu-

Jan 1, 1944

By J. R. Long, T. R. Graham

This report is concerned with part of a series of investigations carried on by the Federal Bureau of Mines on alloys, particularly nonferrous alloys, made with electrolytic manganese. A broad general program instituted after commercial quantities of electrolytic manganese became available was necessary in order to compare the effects of electrolytic manganese with those of the ordinary commercial grades. Representative analyses of these two materials show the commercial manganese metal to contain up to 2 per cent iron, a maximum of I per cent silicon and 0.06 per cent carbon, while the electrolytic manganese rarely exceeds 0.01 iron, 0.02 sulphur, with no silicon or aluminum. In the literature, the emphasis has been largely on high-strength casting alloys containing up to 5 per cent manganese, and few data are available on wrought manganese alloys. These factors, coupled with the strategic position of copper and zinc, have given impetus to the Bureau's War Research Program for the development of alloys containing nonstrategic manganese for the purpose of supplementing or providing alternates for the more strategic metals. The alloy reported here was studied, along with several other ferrous and nonferrous alloys, as possible cartridge-case material, and was chosen after a review of the properties of the ternary alloys of copper-manganese-zinc. Preliminary Work In a cursory survey of this system, alloys ranging from 60 to 95 per cent copper, o to 50 per cent manganese, and 5 to 40 per cent zinc were investigated. The alloys containing 60 per cent copper were found to fall into the two-phase alpha plus beta region of the system, and since those containing 70 per cent would not permit a saving, only alloys containing 65 per cent copper were considered. The tensile properties of these 65 per cent alloys are plotted in Fig. I as a function of manganese content for annealed material and for four conditions of cold-work In the annealed condition the increases in strength and decreases in elongation are minor up to 15 per cent manganese; beyond this, the changes become more significant. In the cold-worked condition, the first 5 to 10 per cent of manganese appears to have the greatest strengthening effect, the rate of increase dropping off as the manganese increases beyond this amount. These effects are more pronounced with moderate than with severe cold reduction. It is also interesting to note that while the elongation of annealed material drops regularly with increasing manganese, the elongation in the cold-worked state is relatively little affected by increasing manganese content, particu-

Jan 1, 1944

By J. Chipman, N. J. Grant, E. C. Roberts

An equilibrium study was made of the distribution of chromium and oxygen between liquid iron, containing less than 1 pct Cr, and simple slags of the CaO(MgO)-Si02-FeO-Cr& type in the temperature range 1526' to 1734OC. The effects of slag oxidation, temperature, and basicity were observed. IN spite of the fact that chromium is one of the most important alloying elements in steel, and exists in almost all steels as a significant residual element, little research has been done to determine its behavior in basic steelmaking processes. Considerably more work has been done under silica-saturated acid slag conditions. Korber and Oelsen,' Herasymenko,' and others have generally agreed that in acid steelmaking practice the chromium in the slag behaved as if it were present as the chrom-ous ion (CrO). Work by Hilty- ir, high chromium slags also indicated that chromium may exist as CrO. In basic slag systems no equilibrium data exist. Based on individual studies of basic open hearth and electric furnace practice, Bardenheuer," Rock-rohr,% nd HauckQ oncluded that: 1—chromium recovery increased with decreasing basicity, and 2— chromium recovery increased with increasing temperature, although the effect was small. In similar studies Yavioskii and Dzemyen' concluded that: 1— slag FeO is the most important variable, 2—the basicity of the slag has no effect on chromium recovery, and 3—slag viscosity is not high even when 20 pct Cr,O, is present. Lapitskii\ oncluded that chromium recovery improved as the basicity of the slag decreased and increased with increasing manganese in the metal. Regarding the effectiveness of CrZ08 as a base or acid in basic slags, both Kristofferseno and Trojer" reported that Cr,08 was an acidic component requiring neutralization as 2CaO-Cr,O,. Experimental Procedure The experimental apparatus and procedure used for the present research were similar in most details to those used by Winkler and Chipman" and were described in detail by them. A magnesia crucible was used, holding 60 to 80 lb of Armco iron which was decarburized with hydrogen to about 0.010 pct C. Since all the metal samples solidified without gas evolution, this carbon level was assumed not to be significant. Synthetic slags made by mixing pure oxides were used throughout the study. Temperatures were measured by means of calibrated W-Mo thermocouples and were checked by Pt-Pt-Rh thermocouples. The range of temperatures covered in this study was from 1526" to 1734°C. The chromium content of the iron was in the range 0.032 to 0.82 pct, although the bulk of the tests showed 0.04 to 0.2 pct. The slags were of the CaO(MgO)-SiO,-FeO-Cr,O, type in which the Cr,O, content was from about 2 to 20 pct, although most of the slags showed from about 2 to 10 pct. The FeO range was from about 10 to 65 pct. CaO and SiO, were in the range of about 5 to 45 pct each, yielding a rather wide range of basicity values. The first 12 heats were made without a sulphur addition, and with only 30 min allowed for slag-metal equilibrium to be reached. In previous research it had been shown that less than 30 min was adequate to achieve equilibrium in slags free of Cr2O8.11,14.15 A study of the present data indicated that some of the tests may not have reached equilibrium in this time; accordingly four additional heats were made in which at least 1 hr was permitted for equilibrium to be reached. For reaching

Jan 1, 1955

By N. M. Levine, W. M. Fassell

In this laboratory study the problem of aerative conditioning to separate chalcopyrite and pyrite from cobaltite was simply effected with a sulfy-drate collector and pH by proper choice of mixing variables. It was shown that for a given impeller type and geometry, selectivity is governed by a relation between the Froude number and a modified power number multiplied by impeller tank-diameter ratio wherein the power factor is expressed as power intensity or horsepower per unit volume of contained pulp. In applying this approach to other systems, other criteria would be used in place of selectivity. The purpose of this paper is to show how solutions to problems of aerative conditioning of pulps may be enhanced by development of mixing parameters in a given system through application of a fundamental approach to agitation. The term aerative conditioning refers to a combination of processes which include mechanical gas dispersion, gas solution in the liquid phase, transport of dissolved gases and other reactants to the reaction zone, physico-chemico interaction within the liquid phase and/or at the solid surface, and, finally transport of products away from the reaction zone. Important elements of these processes are: 1) Air-Liquid Contact Area: This area limits the rate at which a given gas may dissolve in a given liquid. Thus, an aerative conditioning system should be designed for optimum gas dispersion. 2) Diffusional Factors: Such factors as concentration gradient, diffusion film thickness, and diffusivity may govern the rate at which dissolved constituents are transferred to the zone of interaction at a particle surface and the rate at which reaction products are transported therefrom. Thus, such systems would be designed for maximum turbulence to effect good mixing and to minimize diffusion film thickness. 3) Solids-Turbulent Liquid Contact Time: Sufficient time should be provided for interactions to take place at solid-liquid interfaces. The region of maximum turbulence for mechanical systems being in the impeller zone, it is important that the number of passes through this zone be optimized. This means that a proper balance should be struck be- tween flow and turbulent power to achieve optimum conditioning time. Too high a flow rate and insufficient turbulence may be improper if the reactions are diffusion limited. On the other hand, too much turbulent power and too little time in the reaction zone due to insufficient flow power may also be limiting. 4) Geometry and Impeller Design: The design of the conditioning vessel and the type of impeller employed are important factors in determining the relative distribution between flow and turbulent power and the degree of gas dispersion. Maximization of power input would be to no avail if the distribution between flow and turbulent power were improper or gas dispersion insufficient. 5. Physical Chemistry: The reactions between dissolved gases and solid surfaces may be limiting if gas solubility, activation energies and/or free energies are not favorable. J. H. Rushton, E. W. Costich, and H. J. Everett' have summarized the mechanical elements of the combination of processes listed in a fundamental mixing equation. This equation was derived by dimensional analysis and relates the physical variables for a single impeller, centered in a cylindrical, vertical axis, flat-bottomed tank. It is, where T is tank diameter in feet; H is liquid depth in feet; C is height of impeller off tank bottom in feet; S is pitch of impeller; L is length of impeller blades; W is width of impeller blades; R is number of baffles; D is impeller diameter in feet; Np is the power number, pg/dN3D5; P is power in foot-pounds per second; g is the gravitational constant, feet per second; J is width of baffles; B is number of im-

Jan 1, 1961

By Alton B. Cook, G. B. Spencer, F. P. Bobrowski

In estimating production gas/oil ratios and oil recoveries from reservoirs containing highly volatile oils it is highly important to include condensate that may be recovered from the gas produced from the reservoir. The volume of the hydrocarbon liquid condensed from the production of the solution gas that has been liberated. in some reservoirs may equal or even exceed the volume of recoverable stock-tank oil as estimated by present methods. The usual procedure1, 2, 3 in estimating future reservoir performance includes use of relative permeability data of the reservoir rock to gas and oil and includes material-balance calculations utilizing data on the volume of the reservoir fluids, oil and gas production and reservoir pressure decline, and data on the physical properties of the initial reservoir fluids. The inaccuracy in the procedure results from the false assumption that all of the free or liberated gas that enters the well bore of reservoirs containing highly volatile oils remains in the gaseous phase as it is produced. This paper presents a method for estimating future reservoir performance and oil recoveries based on special labora. tory analyses of reservoir-oil samples and recognition of the additional volume of hydrocarbon liquid that will be recovered at various stages of depletion from a solution.gas.drive reservoir. The method also includes calculations of the volume and composition of the hydrocarbon liquids that can be recovered by processing the produced gas in a natural-gasoline plant. The development of the method resulted from a study of laboratory analyses of reservoir samples and of field data obtained from two reservoirs containing oil of the highly velatile type. Relatively high pressures and temperatures prevail in oil reservoirs discovered at the greater depths of present-day drilling. The contained fluids may have high saturation -Dressures and large volumes of gas in solution. The oils and gases under these conditions may be almost identical in compositions and densities.4,5 Also, engineers have noted that, for a number of oil reservoirs and especially the deeper reservoirs, the API gravity of the stock-tank oil increaees as the production gas/oil ratios increase. They attributed this increase in API gravity of the stock-tank oil to the formation of condensate as the liberated gas in the reservoir is being produced. SOURCE OF DATA FOR CALCULATIONS Subsurface oil samples and well-test data were obtained from the E. Constantin-Lambert Well No. 1 in the Elk City Field, Okla., to demonstrate the need for and a method of calculating future reservoir performance when consideration is given to the recoverable hydrocarbon liquid from the production of solution gas that has been or will be liberated in a reservoir. The Lambert well is located in C, SW 1/4, SW 1/4, Set- 18, T-l0-N, R-20-W, Washita County, Okla. At the time of completion it was on the east edge of the development and Was producing from conglomerate through 30 perforations in the 5 1/2-in. casing at a depth of 9,859 to 9,864 ft. The well Was completed on July 9, 1949, and subsurface oil samples were obtained July 29 and August 1, 1949. Production gas/oil ratio data were obtained during the operation in series of two Separators at high and low-pressures of 314 and 44 psia, respectively, and at an average temperature of approximately 60°F. The flowing bottom-hole pressure at the time of sampling was 3,934 psis. The static bottom-hole pressure was not obtained at the time of sampling, as the well could not be shut in long enough for testing because gas produced from the well was used for fuel at an offset drilling well. However, the initial reservoir pressure was calculated to be 4,364 psia from knowledge of pressure gradients in other wells in the field and the depth of the casing perforations in the Lambert NO. 1 well.

Jan 1, 1951

By F. P. Bobrowski, G. B. Spencer, Alton B. Cook

In estimating production gas/oil ratios and oil recoveries from reservoirs containing highly volatile oils it is highly important to include condensate that may be recovered from the gas produced from the reservoir. The volume of the hydrocarbon liquid condensed from the production of the solution gas that has been liberated. in some reservoirs may equal or even exceed the volume of recoverable stock-tank oil as estimated by present methods. The usual procedure1, 2, 3 in estimating future reservoir performance includes use of relative permeability data of the reservoir rock to gas and oil and includes material-balance calculations utilizing data on the volume of the reservoir fluids, oil and gas production and reservoir pressure decline, and data on the physical properties of the initial reservoir fluids. The inaccuracy in the procedure results from the false assumption that all of the free or liberated gas that enters the well bore of reservoirs containing highly volatile oils remains in the gaseous phase as it is produced. This paper presents a method for estimating future reservoir performance and oil recoveries based on special labora. tory analyses of reservoir-oil samples and recognition of the additional volume of hydrocarbon liquid that will be recovered at various stages of depletion from a solution.gas.drive reservoir. The method also includes calculations of the volume and composition of the hydrocarbon liquids that can be recovered by processing the produced gas in a natural-gasoline plant. The development of the method resulted from a study of laboratory analyses of reservoir samples and of field data obtained from two reservoirs containing oil of the highly velatile type. Relatively high pressures and temperatures prevail in oil reservoirs discovered at the greater depths of present-day drilling. The contained fluids may have high saturation -Dressures and large volumes of gas in solution. The oils and gases under these conditions may be almost identical in compositions and densities.4,5 Also, engineers have noted that, for a number of oil reservoirs and especially the deeper reservoirs, the API gravity of the stock-tank oil increaees as the production gas/oil ratios increase. They attributed this increase in API gravity of the stock-tank oil to the formation of condensate as the liberated gas in the reservoir is being produced. SOURCE OF DATA FOR CALCULATIONS Subsurface oil samples and well-test data were obtained from the E. Constantin-Lambert Well No. 1 in the Elk City Field, Okla., to demonstrate the need for and a method of calculating future reservoir performance when consideration is given to the recoverable hydrocarbon liquid from the production of solution gas that has been or will be liberated in a reservoir. The Lambert well is located in C, SW 1/4, SW 1/4, Set- 18, T-l0-N, R-20-W, Washita County, Okla. At the time of completion it was on the east edge of the development and Was producing from conglomerate through 30 perforations in the 5 1/2-in. casing at a depth of 9,859 to 9,864 ft. The well Was completed on July 9, 1949, and subsurface oil samples were obtained July 29 and August 1, 1949. Production gas/oil ratio data were obtained during the operation in series of two Separators at high and low-pressures of 314 and 44 psia, respectively, and at an average temperature of approximately 60°F. The flowing bottom-hole pressure at the time of sampling was 3,934 psis. The static bottom-hole pressure was not obtained at the time of sampling, as the well could not be shut in long enough for testing because gas produced from the well was used for fuel at an offset drilling well. However, the initial reservoir pressure was calculated to be 4,364 psia from knowledge of pressure gradients in other wells in the field and the depth of the casing perforations in the Lambert NO. 1 well.

Jan 1, 1951

By C. G. Dunn

Identification of the kinds of orientation relationships that may exist among crystals is an important problem in the metallurgical field. As an aid to its solution standard orientations of several orders of twins would be very useful for rapid analyses to discover high-order as well as low-order twin relationships. Although data have been published that give orientations for three generations of twins, these data are not readily useful in the form presented; i.e., in a stereo-graphic projection with one pole per orientation.' However, accurate data based on calculations of the positions of all {1001 planes for such groups would be very useful when presented in tabular form. Therefore, calculations have been made for a group of four orders of twins and the data are listed in Table 3. Illustrative applications are considered briefly, with the idea of pointing out what may be done with large groups of orientations. Method of Computing Orientation OF a Twin It is common practice to describe the orientation of a crystal in terms of the positions on a stereographic net of the poles of certain planes of the crystal. A single position on a net may be given in terms of two angle variables, two sets of which appear in the following equations: Polar Net Wulff Net x = , sin ?p cos Fbp x = r COS ?w y = r sin ?p sin Fp y = r sin ?w cos Fw % = r cos ?p z = r sin ?w, sin +, The three numbers z, y and z determine a length r as well as a direction (0, 4) in an X, Y, Z coordinate system. In the present case, r will be set equal to (h2 + k2 + L2)1/2, where h, k and I are the usual Miller indices for a crystallographic plane, a restriction that facilitates determination of the positions of poles of new planes from those of old or known ones,2 as will become evident later. Furthermore, since twinned lattices have certain planes in common, it is an easy matter to determine the orientation of a twin of a crystal if the orientation of the crystal itself is known. We start therefore with a crystal of known orientation (positions of three {Ioo} poles given) and determine where the cube poles occur in first, second, third and fourth-order twins. Methods for identifying twinned lattices and for making the calculations to find the orientation of a twin have been published.3,4' Reference 4 will be illustrated in the calculation of the orientation of a twin, even though this method differs from the one used by the writer in obtaining the following data on four orders of twins. Consider a crystal S and its twin A1, A' being one of the four {112} or {III} type* first-order twills of S. The orientation of S—i.e., the positions of poles of (I00)

Jan 1, 1945

By Norris Johnston, Carrol M. Beeson

For many years the permeability of reservoir sands has been measured by flowing air through a cleaned and dried core sample. This differs from the true reservoir permeability in one important respect: the rock particles in the reservoir are surrounded by interstitial water, not air, and their physical shape and condition of hydration are greatly dependent thereon. Permeability as defined must be measured with a single-phase fluid. Since no means exist for removing the oil and gas from a core sample by simply flowing water through it, the sample must be cleaned and then resatu-rated with water before testing. The present discussion attempts to show that after the cleaning process a considerably different permeability is determined with salt or fresh water than is obtained with air. The postulate is made that the salt-water permeability is probably closer to the true reservoir permeability than is the measurement with air. This is discussed in relation to both physically possible and economically feasible measuremerits. Data On more than 1200 core samples are given to show the nature of the effects observed, and a plea is made for others to consider water permeability measurements as a routine necessity, eventually replacing air permeability in regions where the differences are great. Introduction Permeability is defined1 as a "a measure of the capacity of a porous medium to transmit fluids, when there is no interaction between the solids and the fluid." Darcy's law of liquid flow in porous media states: kA?P QµL/A?L [I] where Q represents milliliters of liquid of viscosity p centipoises passed per second through a porous medium of permeability k darcys and cross-sectional area A sq. cm. under a pressure gradient ?P/L atmospheres per centimeter, the flow being understood to be laminar or viscous, not turbulent. This equation defines the darcy. For the case of radial flow in a uniform sand, such as usually exists in the neighborhood of a well in an oil or gas sand, Darcy's law becomes:2 Here h is the net sand thickness in feet, Pe and Pw are pressures at the drainage radius4 and well radius, and re and rw are these radii, respectively. The productivity index3 is defined as the barrels of liquid produced per day per pound per square inch mean pressure differential between ferences and well bore, and is thus: By further definition, the specific productivity index is: or in terms of practical units, and allowing for shrinkage:

Jan 1, 1945

Frank H. Probert, A.R.S.M., Morenci, Arizona (communication to the Secretary): The management of mines and the system of bookkeeping employed are subjects of great interest to mine-superintendents, and such papers as that of Mr. Davis callnot fail to attract attention. The Institution of Mining and Metallurgy, London, England, has done much within the last three years to promote discussion on the many systems adopted throughout the mining world; and any papers giving individual experience will benefit that class of men who are charged with the cconomical management of mining properties. It is often said that " a good mine shows a good manager," and more often that mismanagement is the chief cause of poor returns; or, as Mr. A. G. Charleton puts it, in his able paper on " Mining Accounts and Cost-Sheets,"* " accident may, and often

Jan 1, 1902

By P. G. Shewmon, H. E. Collins

We have studied the effect of adsorbed sulfur on the surface self-diffusion of copper using eight diflerent surface orientations and the grain boundary grooving method. The eight orientations studied were the four lying near the low-index surfaces—(loo), (Ill), and two directions in the (110)-plus four higher-index surfaces. Surface-diffusion measurements were made over a range of HZS concentrations (in Hz) from 3 to 1500 ppm between 830°and 1050°C. The results can be divided into two groups—Group 1 contains the two (110) surfaces while Group 2 contains the remaining six surfaces. In Group 1, increasing the temperature increases the effect of Hz S on DS for the Hz S range 5700 ppvn. Qs and Do increase with increasing H2S concentration in this Hz S range. Beyond this range, increasing the temperature decreases this effect on D,; also Q, and Do decrease. In Group 2, increasing the telnperature decreases the effect of H2 S on D, for the H2S range studied, and Qs and Do decrease with increasing Hz S concentration. In any study of surface phenomena, there invariably arises the question of the possible presence of and effect of adsorbed impurities. Such questions are well-founded since the presence of adsorbed atoms can sometimes produce marked changes in the kinetics of surface-energy-driven processes. In the last few years, values of the surface self-diffusion coefficient, D,, have been determined on a variety of metals by studying the decay of scratches or the growth of grain boundary grooves.L~3-L0~L3 Yet there has been relatively little work done in which the concentration of an adsorbed impurity was systematically varied and the effects observed. Work of this sort would provide some basis in fact for the assertions often made about the ro1.e of adsorbed impurities in the differences between the results of different workers in different atmospheres and on different metals. It also is relevant to those cases in which surface monolayers produce profound effects in commercially important processes. The most marked example of such effects is the ability of nickel or palladium to increase the sintering rate of tungsten by many orders of magnitude.' The aim of this work was to study the effect of sulfur partial pressures on the surface self-diffusion of copper. It was felt that this in conjunction with a study of the degree of adsorption and type of active sites involvedL8 would provide a wide range of data for one system and hopefully lead to some insight into the mechanism by which sulfur adsorption influences copper diffusion. The main reasons for choosing the Cu-S system were, first, faceting was reported not to accompany the adsorption of sulfur. This is required if our experimental technique is to work. Second, Oudar has determined a high temperature adsorption isotherm for this system, an event which puts the Cu-S system almost in a class by itself.I4 EXPERIMENTAL PROCEDURE Initially, we considered studying the effect of an adsorbed impurity on surface self-diffusion of copper using isolated (or single) scratch smoothing as the technique and oxygen as the impurity. Copper was chosen as the material because the effects of orientation and anisotropy of the surface self-diffusion coefficient, D,, of copper in a dry hydrogen atmosphere had been studied extensively by Gjostein' and by Shewmon and ~hoi.~,~ The isolated scratch technique was chosen because both the effects of surface orientation and anisotropy of D, in a given surface could be easily studied with this method.~ Oxygen was tried as the impurity because Robertson and Shewmon""~ had studied its adsorption on copper at 1000°C over the range of oxygen partial pressures of 10"22 to 10-l3 atm. After several preliminary runs, it became evident that neither the scratch technique nor the impurity oxygen would be satisfactory for this work. Scratching deforms an annealed surface so that the region near the scratches recrystallizes, thereby disrupting the scratch profiles. One can avoid this by deforming the specimen sufficiently before scratching to give complete recrystallization on subsequent heating.4 However, as a result of Gjostein's success in scratching and annealing undeformed gold single crystals without local recrystallization,13 we attempted something similar with copper single crystals using a 0.7-mil diamond phonograph needle mounted in a Tukon hardness tester. All specimens recrystallized upon being annealed. Also, some copper specimens were sent to Gjostein to be scratched using his technique. The results were the same. As a result, the scratch technique was dropped in favor of the grooving of symmetric grain boundaries. Preliminary work using oxygen showed that faceting began to occur before oxygen adsorption had any measurable effect on D, at 938°C (at Pbo/P, = 0.12). Since heavy faceting would interfere with the measurement, we decided to use a sulfur-containing atmosphere (H2S/H2). Work by Oudar and Benard' and Robertson" showed that sulfur absorbed on copper and that faceting was not observed.

Jan 1, 1967

SECTION I PAGE PAGE President's Western Trip v Presentation of the' John Fritz Hoover Makes Plea to. Stop Food Medal to Henry M. Howe.... xv Waste v International Mining Convention. xxxv. American Committee of Engineers Personal xl in London vii Employment xlii Proceedings, Meeting of Board of Local Section News xliii Directors : vii Forthcoming Meetings of Societies xlvii St. Louis Meeting V... Library xlviii The Woman's Auxiliary. xi Membership liv Members of the Institute in Mili- Biographical Notice of H. T. Chen. lxxiv tary Service xiv Institute Committees lxxv Officers and Directors lxxxii

Jan 7, 1917

By Frank Van Horn

INTRODUCTION IN June, 1911, the writer spent a few days in studying the economic geology of the vicinity of Park City. During this rather hurried visit a number of specimens of ore were collected, which have since been examined. The results of these investigations show that bournonite (PbCuSbS3) is present in the ores in greater or less quantity. This fact has never before been reported, as far as can be learned. The failure to recognize this mineral is due to its similarity to tetrahedrite, with which it has probably been confused during a long period of years. Jamesonite (Pb2Sb2S5) has been reported from the region in a rather doubtful manner, but the writer has seen it in notable amounts from several mines, and can offer the first analysis of this mineral from the district. Calamine (H2Zn2SiO6) was found at one mine and has never been recognized and reported from the district.

Jan 8, 1914

By Victor A. Phillips

A series of specimens of a Cu- 3.23 pct Co alloy were prepared with particle diameters from zero to 590A. The samples were then cold-rolled 95 pct and the effects of the particle size on the behavior on annealing for hr at temperatures between 100" and 900°C were studied (by hardness, light, and electron metallography). Particles, particularly for d r 105 to 590A, greatly impeded softening and vecvystallizn-tion, and tended to give elongated grains. Particles deformed fairly homogeneously with the ,matrix, be- IN a previous study by the author,' the growth of cobalt-rich precipitates was followed electron microscopically in Cu-3.12 Co alloy as a function of aging, typically at 650°C. The coherent spherical precipitates grew to 520 + lOOA average diam before spontaneously losing coherency and developing (111) facets. Stretching a few percent after precipitation 2aused loss of coherency to occur sooner at about 220A average particle diam. The particles apparently retained their fcc structure after loss of coherency. coming lau2ellae. For d = 55 to 180A, these lamellae gave streak-contrast effects apparently due to coherency strains , and spheroidized on annealing at 600" to 650°C, forming coherent particles. Particles of d = 250 ov 320A lost coherency during t-olling, giving incoherent lamellae. Recrystallization apparently occured by growth of new grains into unrecrystallized (recovered) material at temperatures below that at which cobalt atoms had much mobility. The present study was undertaken to explore the effect of cobalt-rjch particles of various average sizes from 50 to 600A diam on the isochronal annealing behavior of copper after heavy cold rolling. The previous work' was used as a guide in preparing the two-phase series of prerolling structures. The solution-treated alloy was also rolled for comparison. A further question of interest in the present study was whether dislocation and particle hardening were additive, since the prerolling structures covered the full range unaged - peak aged — overaged, and further precipitation might occur on annealing after cold rolling. Although there have been exhaustive studies of the isothermal2"6 and is~chronal annealing behavior of

Jan 1, 1967

Secretary Membership Committee Increase of Membership Papers and Publications Committee Library Committee Treasurer Report of the Secretary TO THE BOARDOF DIRECTORASN D THE MEMBEROS F THE AMERICANIN STITUTE OF MINING AND METALLURGICAENL GINEERS GENTLEME:N As will be shown by the special reports of the Finance, Membership, Library, Papers and Publications, Increase of Membership, and other standing Committees, together with that of the Treasurer, the year 1927 was one in which the Institute made very satisfactory progress in a number of directions. In total numbers the membership is no larger but in revenue from dues there has been a marked increase. This has been due to the promotion to full membership of Junior Associates of earlier years, to the larger proportion that come in originally as members rather than juniors, and to the keener interest in the work of the Institute reflected in prompter payment of dues. The latter is important, since experience shows that of those who fall behind a large number must ultimately be dropped for non-payment. Conditions in the mining industries have been healthy though not booming. It has been much easier for members to find employment and meet their financial obligations but there has not been that flow of young men into mining, and hence in part into the Institute, that characterized certain earlier years. Rather the tendency toward centralization and larger industrial units has restricted the number, though not the scope, of opportunities for technical men in the mineral industries. The Institute is constantly receiving resignations from members crowded out of mining into other lines of activity. On the other hand, those who remain in mining and metallurgy have a greatly increased necessity for i,dormation and contacts with technology. A few years ago many superintendents and most foremen were non-technical men. Today the reverse rule obtains and shift bosses and men who occupy even lower positions in industrial units are called upon to know and to apply such an amount of technical knowledge that graduate engineers are the rule rather than the exception. The curious situation has obtained that with a much smaller enrolment of students in the schools of mining and metallurgy there has been at times an actual shortage of young engineers for beginners' jobs. The young men retort that the conditions of employment and pay offered in mining are not equal to those in other lines and, while it is undoubtedly true that the young engineer beginning in mining is able to start under conditions markedly better as to pay, living, and responsibility than did the men who are now leaders, they are required to know much more and have usually spent more in time and money to qualify for their jobs. The whole matter is one which warrants much more attention than has been given to it. For the Institute it is important since the young men

Jan 1, 1928

By H. W. Knott, M. H. Mueller, P. A. Beck, W. P. Chernock

PREFERRED orientation studies by Harris of rolled uranium rods indicated that hot rolling to a small reduction of area caused the (010) planes to become strongly oriented and the (110) planes weakly oriented perpendicular to the rolling direc- tion. The relative intensities of these two fiber texture components were reversed upon rolling to higher reductions of area. Cold rolling caused the (010) planes to become strongly aligned and the (130) planes weakly aligned perpendicularly to the rolling direction. The present investigation was undertaken to explore in more detail the effect on the rolling texture of variables, such as the penultimate condition, the final rolling temperature and reduction of area. In addition, the recrystallization texture of rolled uranium rods was also investigated.

Jan 1, 1959