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By Lars Rossemyr, Terkel Rosenqvist

The equilibrium Mn + 2 IiCl = MnCl2(g) + H2 has been studied at 1090°C for pure manganese and for Mn-Si alloys. For this reoction a standard free energy of Fo1363, = - 19,700 i 300 col ioas found. Combined with other thermal data, the standard free energy of the reaction Mn(s, ß) + Cl2 = MnCl2(g) was derived: Fo=- 56,140 + 9.78 T log T - 40.10 T For the formation of the various manganese silicides the following free energies were obtained. 5 Mn + 3 Si - M1z5Si3 ?F°1363 = -41,500 i 1500 cal Mn + Si - h.lnSi ?F°1363= -10,000 i 500 cnl Mn + 2 Si = MnSiz ?F°1363= -11,500 ± 500 cal In the search for a method suitable for the study of thermodynamic properties of certain alloy systems, it was found that the heterogeneous equilibrium between the alloy and a gas mixture consisting of hydrogen chloride, hydrogen, and volatile metal chlorides has considerable advantages. In addition to giving thermodynamic information about the alloys, such measurements may be used to derive thermodynamic data for the volatile metal chloride itself. The present paper gives some results which were obtained for manganese silicides and manganous chloride. Similar studies are presently being carried out for the iron silicides. The phase diagram of the Mn-Si system is rather well known,' but no information exists to the authors' knowledge about the thermodynamic properties of manganese silicides or about the chemical activities in molten Mn-Si alloys. At elevated temperature, manganese may react with hydrogen chloride according to the equation: Mn(s, ß ) + 2 HC1 = MnC1, (g ) + H2 [ 1] with the equilibrium constant The value of K, may be determined from measurements of the gas composition in equilibrium with pure manganese. When this value is used in connection with measurements on manganese alloys, the chemical activity of manganese in the alloy may be derived. Initial calculations showed that around 1000" to 1200°C the equilibrium constant K1 has a value of a few thousand, i.e., the reaction is shifted far to the right. In order to study this rather unbalanced gas composition, a flow method was used in two slightly different modifications. For all experiments with manganese silicides and for some experiments with pure manganese the apparatus shown on Fig. 1 was used. A bed of the metal or alloy was placed in a tube furnace. The refractory tube had an internal diameter of 14 mm and the bed was 75 mm long. Electrolytic manganese of high purity and silicon, 99.95 pct Si, were used as raw materials. All alloys were prepared by melting weighed amounts of the elements in a high frequency induction furnace in argon atmosphere. The melting was done in a silica crucible which was placed inside a graphite shell. The alloys were crushed to - 10 +40 mesh and analyzed chemically. Also, for the pure elements, the same size fraction was used. A controlled gas mixture of purified hydrogen and from 3 to 12 pct HC1 was passed through the bed where it reacted with manganese according to Eq. [I]. The volatile manganese chloride was collected in a condenser placed in the cooler part of the furnace tube. The gas mixture before and after the furnace was sampled and analyzed by absorption of

Jan 1, 1962

By Che, C. W. Spencer, C. A. Steidel, Yu Li

Grain boundary grooving as it occurs in a 5.5-deg simple-tilt nickel bicrystal immersed in a saturated Ni-S liquid has been studied. A 1/3 (t= time) dependence for the depth of the groove indicates that the rate -controlling meckanism for groove developvnent is volume diffusion in the liquid. The activation energy for the diffusive process is estimated at 15 kcal per mole. Using an extended form of W. W. Mullins&apos; analysis for grooving reactions, a computer is employed to fit the appropriate diffusion equation by a numerical method. From the analysis a possible method of measuring L.S. the solid-liquid interfacial tension is demonstrated. WHEN a polycrystalline solid is heated in equilibrium with a saturated fluid phase, grooves will form at the intersections of the grain boundaries and surface. The equilibrium root angle of these grooves is determined by the balance between the grain boundary and solid-fluid interfacial tensions. The grooves deepen and widen with time due to a difference in chemical potential between the flat interface and the curved interface of the groove. In this investigation solid-liquid interaction at a grain boundary is studied, with the object to determine the mechanism of grain boundary grooving in the presence of a saturated liquid. Extension of Mullin analysis then permits the estimation of the solid-liquid interfacial tension. Herring has demonstrated by dimensional analysis that the quasi-steady state change of the dimensions of a small particle during sintering is proportional flow, evaporation-condensation, volume-diffusion, and surface-diffusion mechanisms, respectively, if geometric similarity of consecutive configurations of the particles holds. Mullins has extended this analysis to grain boundary grooving. In the case of shallow grooves he solves the diffusion equations for evaporation-condensation, volume-diffusion, and surface-diffusion mechanisms, and obtains the same time dependence for any linear dimension of a groove as Herring found for the change in dimension of small particles. In Mullins&apos; analysis2&apos;3 grain boundary grooving of a bicrystal by volume diffusion in the presence of a saturated fluid phase was considered. Several assumptions were made prior to the analysis: 1) the solid-fluid interfacial tension is independent of crystallographic orientation; 2) the Gibbs-Thompson equation relating curvature and chemical potential is applicable at the solid-fluid interface; 3) the relaxation time of the diffusion field is small compared with the time for appreciable changes in the curvature of the groove, so that the diffusion is divergence-less; and 4) the groove has a small slope relative to the initial flat interface. Usually this last condition is fulfilled only for solid-gas systems. The solution of the diffusion equation under the above conditions produces a t1/3 dependence for any linear dimension of the groove in the case where volume diffusion is rate-controlling. The t1/3 dependence is valid because geometric similarity of the grooves exists for all time. EXPERIMENT In the experiment a 5.5-deg nickel bicrystal of <100> simple-tilt orientation was used.4 Grooving was studied in the presence of a saturated Ni-S liquid alloy as a function of time at 750°, 800°, 850°, and 900°C. A low-angle bicrystal was chosen for study to insure that 2L.S. > .b., where l.s.

Jan 1, 1964

WE the undersigned, being all persons of full age and citizens of the united States, and a majority residents of the State of New York, desiring to form a corporation pursuant to the provisions of the Membership Corporations Law for the purpose of incorporating, as provided in Section 5 of Article I. of said law, the existing unincorporated association known as American Institute of Mining Engineers, do hereby make, acknowledge and file this Certificate for that purpose, and do Certify as follows: I. That the American Institute of Mining Engineers is an unincorporated association organized and existing with the object of promoting the arts and sciences connected with the economic production of the useful minerab and metals and the welfare of those employed in these industries by means of meetings for social intercourse and the reading and discussion of professional papers, and to circulate by means of publications among its members and associates the information thus obtained. II. That the persons duly appointed or designated to manage the affairs of said association are designated by the rules thereof Members of its Council; that the undersigned are all members of said Council as the same was constituted on the 20th day of December, 1904. III. That on said last-mentioned date a regularly called meeting of said association was held at its office in the Borough of Manhattan, City of New Pork; that thirty days before such meeting notice of the intention to incorporate said association was given by mail to each member thereof whose residence or post-office address is known; that at said meeting the following resolutions were offered, seconded and duly adopted by the unanimous vote of all its members then present, to wit: "Resolved, That it is the sense of the members and associates of the American Institute of Mining Engineers in general meeting assembled that it is desirable and necessary for the well being of said association and its members and for the furtherance of the objects for which the same has been formed, that said association lncorporate under the Membership Corporations Law of the State of New york; "And Further Resolved, That the Members of the Council of this Association, or a majority thereof, be and they hereby are authorized, in accordance with the provisions of Section 5 of Article I. of the Membership Corporations Law, to incorporate this association for the same purposes for which it has been organized and conducted, in the manner provided in Article 11. of said law; "and Further Resolved, That the name of said corporation as hereby adopted by this meeting shall be American Institute of Mining Engineers; "And Further Resolved, That the said incorporators shall be named in the Certificate of Incorporation as directors of such corporation until its first annual meeting, and that such directors and their successors in office shall be and they hereby are authorized to enact and adopt a Constitution and By-Laws for the government of said corporation." IV. That the name of the proposed corporation is American Institute of Mining Engineers. V. That the purposes for which this corporation is to be formed arc: To promote the arts and sciences connected with the economic production of the useful minerals and metals, and the welfare of those employed in these industries by all lawful means; to hold meetings for social intercourse and the reading and discussion of professional papers, and to circulate by means of publications among its members the information thus obtained, and to establish and maintain a place for meeting of its members, and

Jan 1, 1929

By Charles Prasky

ABOUT five years ago the Bureau of Mines began a study, at Minneapolis, of the various methods for beneficiating the low-grade manganese deposits of the Cuyuna range. Several samples of green carbonate slate from the Cuyuna range, containing about 7 pct Mn and about 28 pct Fe, were obtained for this study. The component minerals in the carbonate slate formation were so intimately associated that mineral dressing methods were not suitable for concentrating manganese to a ferrograde product. Although upgrading of manganese and iron minerals has been effected by flotation methods, it appears that manganese cannot be separated from iron except by chemical means. Because the flotation studies at Minneapolis were carried out simultaneously with the hydrometallurgical studies, only crude slate was available for process testing. An important economic consideration in selecting any one of the several chemical methods proposed for recovering ferrograde manganese is the availability of the chemical reagent. Fortunately, large tonnages of sulfur are available on the Cuyuna range in low-grade pyrite and pyrrhotite deposits that are readily concentrated by flotation to a suitable feed for a sulfide roasting furnace as indicated by a Bureau of Mines investigation in 195 0-1951.1 The roasted residue from the sulfide concentrates is a potential source of marketable iron oxide. Therefore, if these sulfide deposits were employed in recovering manganese, utilization of two heretofore unused mineral deposits would be accomplished. Laboratory investigations of several proposed leaching processes were made as a preliminary step in the investigation of hydrometallurgical methods for the treatment of Cuyuna carbonate slate using sulfur as a chemical reagent. From results obtained in the laboratory tests, these leaching processes did not appear entirely suitable for treating Cuyuna carbonate slate. The method developed at the North Central Experiment Station and selected for a more intensive pilot-plant investigation has been termed the differential high-temperature sulfatizing process. Essentially, this sulfatizing process consists of the following steps, described in the order in which the small-scale pilot-plant investigations were made. The first and perhaps most significant step in the process consists of a sulfate roast. Carbonate slate is roasted in an atmosphere of sulfur dioxide gas and air. The overall chemical reaction for converting manganese carbonate to a sulfate at a high temperature in a sulfur dioxide atmosphere follows MnCO8 + SO2 + 1/2 0, = MnSO4 + CO2 (H077°O = —64,180 cal per g mol) .&apos; The need for concentrated sulfuric acid is avoided. Fine grinding is not essential. Removal of carbon dioxide from the slate during roasting produces a more porous structure and permits easier permeation by the sulfatizing gas mixture. The temperature limits for this conversion of manganese have been established as 600" and 850°C. Iron sulfate is unstable and is not formed at these temperatures; phosphorus is not converted to a water-soluble form; and polythionates are not formed. The second step in the process consists simply of a water leach of the sulfatized product. Manganese sulfate in the sulfatized product is dissolved in water. Iron, phosphorus, and calcium remain in the leach residue as water-insoluble products. The third and final step consists of the recovery of ferrograde manganese oxide from manganese sulfate leach solution. Water is evaporated from the leach solution, and impure monohydrate crystals of manganese sulfate are recovered. The moist crystals are formed into pellets or extrusions and thermally decomposed to produce a ferrograde manganese

Jan 1, 1958

By R. V. Lundquist

Leaching manganese-bearing materials with NaOH to remove caustic-soluble silica has been demonstrated as a method for upgrading manganese. Those materials containing opaline varieties of silica respond most readily. Spent leach liquors are regenerated by treatment with lime to precipitate calcium silicate and to reactivate the NaOH for leaching. ALL of our larger domestic deposits of manganese are very low grade, but estimated tonnages in these deposits are large enough to constitute a potential strategic reserve of manganese for emergency periods, provided these ores can be upgraded sufficiently to meet industrial specifications. Many types of processes have been suggested for upgrading these ores, several have been studied in pilot plants, and a few have attained limited commercial production for special purposes. The hydrometallurgical process to be described below proposes a leaching operation for removing caustic-soluble silica and other gangue minerals and consequently upgrading a manganese ore or flotation concentrate to a commercially acceptable moduct. It is known that some forms of silica and some silicate minerals are soluble in NaOH solutions under suitable conditions. This new process proposes to use NaOH for removing the soluble materials from manganese ores or concentrates and, as a result, upgrade the manganese content. Since spent leach liquors are not efficient leaching agents the liquor must be treated with lime to precipitate calcium silicate and reactivate the NaOH. Experimental Procedure Manganese-ore samples ground to —35 mesh were leached in iron containers into which the ore sample and appropriate NaOH solutions were placed. Flotation concentrates were already ground to —200 mesh. The slurries were then placed on a hot plate or into a pressure digester and stirred continuously during the period of digestion. Where the- digestion was performed at atmospheric pressures, water lost by evaporation was replaced at regular intervals to maintain approximately a constant volume of slurry. In the pressure digester, volume changes were not controlled. After digestion, the slurry was allowed to cool enough for easy handling, but it was filtered hot, 50" to 70°C, on a Buechner filter. Filtration under these conditions was satisfactory. The resulting filter cake was washed and dried. In most instances, a single leach would not produce maximum extraction of silica from the ore sample; consequently, the dried tailing was treated again in the same manner with a fresh solution of NaOH to obtain an additional extraction of silica. This procedure was repeated a number of times to get the maximum extraction of silica. Usually three or at most four stages of leaching were adequate for this purpose. This leaching procedure was used for obtaining the data reported in this paper on the effects of NaOH concentration, pulp dilution, temperature, and time of digestion on the efficiency of extraction of silica from the ore sample. The experimental procedure does not match industrial methods. consequently tests for counter-current leaching were set up. Data from these tests are not yet complete, but in a qualitative way they indicate that thickeners between stages of leaching will be satisfactory and that the quantity of silica in a leach liquor moving forward to a new solid has only a minor effect on the quantity of silica extracted from the new solid. A pilot plant is now being designed for operation in the near future to test and evaluate the merits of this process.

Jan 1, 1954

By E. N. Cameron

GRAPHITE has been included in U. S. lists of strategic minerals since the problem of mineral deficiencies was revealed during World War I. Since 1918 the domestic graphite industry has led a precarious existence, and there has been much uncertainty as to the amounts of usable graphite of various grades that would be available from domestic sources in time of emergency. In 1950-1951 therefore, the writer, assisted by Paul L. Weis, undertook a review of domestic graphite sources for the U. S. Geological Survey.&apos; The conclusions of this study are presented here, with a discussion of some technologic and politico-economic factors bearing upon the problem. Uses of Graphite: Natural graphite as marketed exhibits a wide range of properties, which determine the uses to which it is put. The most essential uses are in the manufacture of crucibles and related refractory articles, in lubricants and packing materials, and in the manufacture of batteries, foundry facings, pencils, and carbon brushes. Numerous specifications covering the mineral in its various applications must be met by producers and processors of graphite. The problem of supply is therefore not simply one of procuring a sufficient total tonnage, but the more difficult problem of procuring enough of each different grade to meet foreseeable needs. The amount of graphite required by American industry is not large. Ordinarily only a few thousand tons of strategic grades are consumed annually, yet the elimination of this small tonnage would have serious effects in several industries. Strategic Graphite: Since World War I, 60 to 100 pct of the country&apos;s annual supply of graphite has been furnished from imports. At present, natural amorphous graphite for use in pencils and batteries is produced largely from American-owned mines in Mexico. Graphite for foundry facings is obtained from a number of sources. Neither grade is a serious problem. High purity graphite for carbon brushes and for pencil leads, however, is imported, largely from Ceylon, in the form of amorphous lump graphite. Most of the flake graphite used for crucibles and related refractory articles is likewise imported, largely from Madagascar, and much of the lubricant and packing grade graphite used by industry is obtained from the same source. The strateg&apos;ic grades of graphite are therefore amorphous lump of the Ceylon type, crucible flake, and flake suitable for lubricants and packing. Ceylon lump and Madagascar flake have for many years been accepted as standard by domestic consumers of graphite, and various essential manufacturing processes are geared to the use of graphite from these sources. Ceylon graphite as marketed is classified into several grades based on particle size and purity. Processing methods are said to be simple, but the products marketed are carefully graded and are consistent in their characteristics, an important matter to the consumer. Nearly all the graphite produced in Ceylon is from veins. Resources are reported to be large, labor is cheap, production costs are low, and world competition is slight—factors accounting for the commercial success of the graphite mining industry in Ceylon. Madagascar is reported to have deposits of the Ceylon type, but its output consists almost entirely of flake. Madagascar graphite as received in the U. S. is further processed by importing organizations, and a large number of grades are produced to meet industry requirements, especially those for crucible flake and for lubricant and packing grade flake. Madagascar crucible flake as marketed is noted for coarseness, uniformity, toughness, clean-

Jan 1, 1957

By Joachim J. Hauser

William F. Hosford, Jr. (Massachusetts Institute of Technology)—Dr. Hauser has used a very interesting method to study the interaction of dislocations on different slip systems, but it should be pointed out that the analysis of the experiments is subject to a serious criticism. He states that "the effect of the compression can be adequately described by one slip system." The effect of frictional constraint during the compression makes this quite unlikely. When a block of metal is compressed its lateral expansion requires a sliding of the metal over the compression platens. The role of friction in the interface between the deforming metal and the platens is to increase the normal force required for the compression. Analyses1213 have shown that, in general, the additional force, p, required for the compression is a function of l/h where is the coefficient of friction, I is the length of the speci- men in contact with the platens. For a constant COefficient of friction, isho&apos; shows that P should increase exponentially with pl/h for both plane strain and axially symmetric compression. For a compression specimen, Fig. 7, whose cross section perpendicular to the compression axis is a rectangle whith one dimension L, much larger than the other W, a much larger force would be required for appreciable flow parallel to L than for flow parallel to U7. Therefore lateral strain in the W direction, EW, should be much greater than the lateral strain in the L direction EL. Since L/H = 14.5 for Dr. Hauser&apos;s crystals, and since no lubrication was used, it seems questionable that appreciable lengthening of the crystals could occur. Because the theories of frictional constraint have been derived for isotropic polycrystalline materials, it was decided to make experimental measurements on a single crystal. A section 3.590 in. long was sawed from an aluminum single crystal with a square section of 0.249 in., so that L/W= 14.4. This crystal was tested in compression between dry ground steel platens. Fig. 8 shows the orientation of the crystal and the axis of compression. The face for compression was chosen so that the operation of the single-slip system which would be predicted in the absence of friction would lead to a larger strain in the length direction than in the width direction. The dimensional changes of the width and length as well as the height were measured frequently during the compression with micrometers. Width strains were calculated from the average of readings near each end and at the center. A plot of the length strain, EL, against the width strain E w is given in Fig. 9. The slope indicates that the EL amounted to only 2.5 pct of cw. Other compression tests on similar crystals with shorter lengths also showed severely limited elongation. Even for a crystal with L/W = A.0, EL was only about 26 pct of cw. Because of the frequent interruptions of the tests for dimensional measurements should have decreased the frictional constraint by allowing a reseating of the platens, even smaller elongations under continuous testing seem probable. These tests on long narrow crystals show that essentially plane strain conditions prevailed. We may assume that Dr. Hauser&apos;s crystals deformed similarly. That the compression can be described by the

Jan 1, 1962

By W. B. Gogarty, H. R. Bailey

Methods are presented for determining molecular diffusion coefficients by using data from, capillary flow experiments. These methods are based on a numerical solution (presented in a previous paper) of the partial differential equation describing the combined mechanisms of flow and diffusion. Results from this numerical solution are given and compared with the approximate analytical solution of G. I. Taylor. The numerical solution is valid over a much larger time range. These methods are applied to experimental results for the fluid pairs water-potassium permanganate solution and amyl acetate-orthoxylene. Both of these fluid pairs have approximately equal densities and viscosities. Graphical and numerical techniques are presented for deter mining diffusion coefficients from the flow data. Values obtained by these techniques are compared with values obtained by other methods. INTRODUCTION The molecular diffusion coefficient is known to be a variable in determining the amount of mixing in a miscible displacement process. The effect of molecular diffusion on dispersion in longitudinal flow through porous media -has been examined by different investigators. These investigators concluded that at low velocities of flow, the amount of dispersion is approximate1y proportional to the molecular diffusion coefficient. The influence of diffusion on fingering, channeling, and overriding has been mentioned by other investigators.4 Recent studies5,6 have been made on the effects of molecular diffusion in connection with the problem of gravity segregation. Many different methods have been developed for the experimental determination of molecular diffusion coefficients? These methods differ mainly according to boundary conditions selected and analytical procedures used. Nevertheless, all of these methods have the condition in common that the bulk fluids in which diffusion is occurring are stationary with respect to each other. In connection with a series of papers on mixing in capillary flow,8-10 Taylor suggested the use of a flow method for determining molecular diffusion coefficients. Additional studies 11-13 have been conducted on miscible displacements in capillary tubes, but the data from these studies were not used for the specific purpose of determining diffusion coefficients. The flow method proposed by Taylor results in a single value of the diffusion coefficient for the fluid pair used in the displacement experiments. This single value represents the true value for the fluid pair when the diffusion coefficient is independent of concentration. If the diffusion coefficient is a function of concentration, the single value obtained by the flow method gives an average value for the coefficient of the fluid pair. These average values are based on diffusion taking place over the entire range of concentration, i.e., from 0 per cent of one fluid to 100 per cent of that same fluid. In field applications of the miscible displacement process, gradients occur over the same range of concentration as are found in the displacements in capillary tubes. Molecular diffusion coefficients obtained from the capillary flow method should, therefore, be especially relevant to field operations. This investigation was undertaken to evaluate the feasibility of obtaining molecular diffusion coefficients from capillary -flow experiments. In making this evaluation, diffusion coefficients were first determined for two systems from data obtained in capillary flow experiments. These values of the diffusion coefficient were then compared to values obtained by other methods. MIXING IN CAPILLARY FLOW—THEORETICAL The theoretical basis for determining molecular diffusion coefficients from capillary flow experiments is the partial differential equation relating the mechanisms of flow and diffusion. For the case of laminar flow and with a fluid pair having equal densities and viscosities, the equation is given by

By W. B. Gogarty, H. R. Bailey

Methods are presented for determining molecular diffusion coefficients by using data from, capillary flow experiments. These methods are based on a numerical solution (presented in a previous paper) of the partial differential equation describing the combined mechanisms of flow and diffusion. Results from this numerical solution are given and compared with the approximate analytical solution of G. I. Taylor. The numerical solution is valid over a much larger time range. These methods are applied to experimental results for the fluid pairs water-potassium permanganate solution and amyl acetate-orthoxylene. Both of these fluid pairs have approximately equal densities and viscosities. Graphical and numerical techniques are presented for deter mining diffusion coefficients from the flow data. Values obtained by these techniques are compared with values obtained by other methods. INTRODUCTION The molecular diffusion coefficient is known to be a variable in determining the amount of mixing in a miscible displacement process. The effect of molecular diffusion on dispersion in longitudinal flow through porous media -has been examined by different investigators. These investigators concluded that at low velocities of flow, the amount of dispersion is approximate1y proportional to the molecular diffusion coefficient. The influence of diffusion on fingering, channeling, and overriding has been mentioned by other investigators.4 Recent studies5,6 have been made on the effects of molecular diffusion in connection with the problem of gravity segregation. Many different methods have been developed for the experimental determination of molecular diffusion coefficients? These methods differ mainly according to boundary conditions selected and analytical procedures used. Nevertheless, all of these methods have the condition in common that the bulk fluids in which diffusion is occurring are stationary with respect to each other. In connection with a series of papers on mixing in capillary flow,8-10 Taylor suggested the use of a flow method for determining molecular diffusion coefficients. Additional studies 11-13 have been conducted on miscible displacements in capillary tubes, but the data from these studies were not used for the specific purpose of determining diffusion coefficients. The flow method proposed by Taylor results in a single value of the diffusion coefficient for the fluid pair used in the displacement experiments. This single value represents the true value for the fluid pair when the diffusion coefficient is independent of concentration. If the diffusion coefficient is a function of concentration, the single value obtained by the flow method gives an average value for the coefficient of the fluid pair. These average values are based on diffusion taking place over the entire range of concentration, i.e., from 0 per cent of one fluid to 100 per cent of that same fluid. In field applications of the miscible displacement process, gradients occur over the same range of concentration as are found in the displacements in capillary tubes. Molecular diffusion coefficients obtained from the capillary flow method should, therefore, be especially relevant to field operations. This investigation was undertaken to evaluate the feasibility of obtaining molecular diffusion coefficients from capillary -flow experiments. In making this evaluation, diffusion coefficients were first determined for two systems from data obtained in capillary flow experiments. These values of the diffusion coefficient were then compared to values obtained by other methods. MIXING IN CAPILLARY FLOW—THEORETICAL The theoretical basis for determining molecular diffusion coefficients from capillary flow experiments is the partial differential equation relating the mechanisms of flow and diffusion. For the case of laminar flow and with a fluid pair having equal densities and viscosities, the equation is given by

By W. B. Gogarty

With flow of non-Newtonian fluids in porous media, effective viscosities are needed for use in the Darcy equation. These viscosities depend on the rock parameters and flowing conditions. In this investigation, rheological and flow results were correlated to develop an expression for calculating effective viscosities. Surfactant-stabilized dispersions of water in hydrocarbon were used with consolidated sandstone cores of different permeabilities. The average shear rate in a core was related to the permeability and porosity of the core and the frontal velocity through the core. By using the correlation obtained for determining effective viscosity, experimental and theoretical values were compared for each fluid system by determining average and maximum errors. For the fluid system showing the largest average error, the correlation fit 38 experimental points with an average and maximum percentage error of 4.3 and 14.8, respectively. For the fluid system showing the least error, average and maximum percentage errors of 1.8 and 4.3, respectively, were calculated using 29 experimental points. INTRODUCTION Use of non-Newtonian fluids in the petroleum industry is not new. Fluids of this type have been used for many years as fracturing agents and drilling muds. Recently, attention has focused on the use of high molecular weight polymer solutions for secondary recovery. Results have been reported on studies relating to the flow behavior of polymer solutions in porous media.1-4 Each study gives the viscosity in the Darcy equation as a function of the rheological properties of the fluid, the characteristics of the porous medium and the pressure gradient. The functional forms of the reported expressions differ somewhat in each study. The first three studies used unconsolidated porous media while the fourth used a single consolidated core. Because of the limited information available on the flow of non-Newtonian fluids in porous media, further investigation was undertaken in this area. We selected non-Newtonian fluids that did not contain high molecular weight polymers in order to minimize core plugging. The over-all objective was to gain a better understanding of the flow behavior of non-Newtonian fluids in consolidated porous media. Specifically, our goal was to determine the relationship between the average shear rate in a core and the frontal velocity. Because of this goal, it was necessary to determine the effect of permeability on the shear rate-frontal velocity relationship. We wanted to replace the viscosity in the Darcy equation with an expression relating to the average shear rate in the core and the rheological properties of the non-Newtonian fluid. THEORY For a time-independent, non-Newtonian fluid, the apparent viscosity is a function of the shear rate. This relationship is given by µ = F(v&apos;)...........(1) With Eq. 1, a single value of shear rate determines the apparent viscosity at that shear rate. With flow in porous media, a spectrum of shear rates occurs at any average throughput. An average shear rate v&apos; can be used to represent the spectrum of shear rates that exists within the core. By using v&apos; and the rheological data given by Eq. 1, an effective viscosity is determined for the flowing fluid. If v&apos; is the correct average, µe becomes the appropriate viscosity for use in the Darcy equation. Under these conditions, flow rate-pressure drop relationships can be determined for non-Newtonian fluids. HOW the correct average shear rate might be related to the frontal velocity through the core and the characteristics of the porous media will now be considered. Later, the experimental data are presented that indicate the validity of these

By R. S. Wagner, R. G. Treuting, W. C. Ellis

Use of the Weisseizbevg goniometer for the study of the morphology of whisker crystals and transfer of the results to a stereograplzic projection are described. While in almost all instances a complete and rapid solution is obtained with a purely gaphical treatment, an absolute analytical treatment applicable to difficult cases is given. Examples are given for determination of growth direction and external features of a crystal, for detection of &apos;twintzittg, and for establislting the orientation relntionships in a kinked whisker crystal. We give here a method for the use of the Weissen-berg goniometerl" in the study of orientation relationships in "whisker" (micro) crystals3-8 and direct transference of the data to the stereographic projection. The operations are straightforward and require no involved calculations: in almost all cases solely graphical treatment is adequate. In a few complex instances, a more exact analytic method may be required. In the method, not only are equatorial reflections of an oscillation photograph used, but also those on higher layer lines, or those not occurring on a recognized layer line. Such reflections off the zero level are often essentialy to detect the presence of twinning. The method is particularly suitable for examination of whisker crystals since the axial or growth direction is almost always one of high symmetry, permitting a more restricted oscillation range to obtain the necessary reflections and an accordingly shorter exposure time. The method is also applicable when there is no lattice-related external symmetry, and is as well able to identify external crystal surfaces, when such exist, with the aid of an optical beam. Thus growth direction, identification of lateral faces, twinning, and orientation relationships in a kinked crystal can be established. A test for the Eshelby twist6-8 can readily be made. The method can be used for orientation, for structure analysis, and as an aid in the identification of an unknown crystal. Moving-film techniques have previously been employed variously for crystal-orientation studies.1,2,9-13 In particular, use of the Weissenberg method for orientation determination has been reported by Wooster and wooster.14 While their method derives the same data as here described, it differs in depending on the tracing of constant p streaks, a less than dependable phenomenon with small specimens, a few microns or less in cross section. The Laue method can and has been used for orientation studies of microcrystals,15 e.g., 2 p in cross section, but requires the extreme intensity and concentration from a microfocus tube to obtain reasonable exposure time. PRINCIPLES OF THE PRESENT METHOD Consider a crystal of random orientation with respect to the oscillation axis in a Weissenberg goniometer. Its diffraction pattern need not necessarily result in recognizable layer lines. In Fig. 1, a stereo-graphic projection of the reference sphere is given with the equatorial plane XZ normal to the oscillation axis Y, and the X-ray beam directed from X towards 2. The great circle ZZ is then normal to the beam, and the axes are right-handed. Thus the reflected X-ray beam lies at the intersection R of small circle ARB of radius 28 from 2, and of small circle RE of radius a from the rotation axis Y. a is the conventional semiapex angle of a cone of diffracted rays from the atoms aligned in the direction

Jan 1, 1967

By William R. Barton

Iron and steel slag represent man&apos;s most successful attempt to date to profitably utilize a solid waste. Its consumption represents a solution to a solid waste problem and also represents tonnage of natural aggregates that will not have to be mined with concomitant disturbance of the land. Slag has been produced as long as iron has been made; but until a little more than 50 years ago, it was mostly a waste product to be disposed of with as little effort and cost as possible. Huge piles of waste slag were generated over the years of iron and steelmaking. Sporadic use was found for small amounts starting with slag (from Catalan forges) used for road bases by the Roman Empire. The first recorded sustained commercial use was, as is often the case in man&apos;s history, for making war. Some profit- conscious munitions maker in the 16th century realized that he could make cannon balls of slag instead of the more precious iron. Other small-volume uses gradually developed: cast building blocks, slag-lime mortars and cements, slag wool, ballast, road base, and, finally, in concrete. But it was not until after World War II that the true potential of blast-furnace slag as a construction aggregate was really recognized. Now nearly all blast-furnace slag produced is used, and much of the earlier stock- piles in the U. S. have been reduced or entirely consumed. Steel slag for aggregate use has been in commerce for only the past 10 years, and use has increased rapidly (10-50% per year) during the past 5 years as blast-furnace slag supplies became depleted. However, much remains to be accomplished in determining character and optimum conditions of use for various types of steel slags before such slags will realize their full use potential. Although slag represents only 2% of construction aggregate materials used in the U.S., its production involves certain features that make its production record far more important than national tonnage figures would indicate. Its source is in iron and steel production and concomitantly slag availability is restricted to those areas where iron or steel is produced. In such areas, it often represents one of the principal aggregates marketed and, because of special properties that make slag a selected aggregate for certain uses, the tonnage imbalance may be overcome by the importance of its contribution to quality or special characteristics of end products. The location and number (Fig. 1) of slag plants handling this annual production is governed by the geographic makeup of the iron producing industry. Prior to the period marked by World War 11, most blast furnaces were in the Great Lakes area-Pittsburgh, Cleveland, Chicago, Gary, Buffalo, Detroit, Youngstown, and Toledo, with exceptions at Baltimore, Bethlehem, and Birmingham. Since that time, iron and steel facilities have been established in Texas, Utah, and California. Today 85 slag plants in 15 states provide employment for almost 2000 persons. The slag plants also recover almost 4 million tons of slag-encrusted iron each year for return to the blast furnaces. Much of the success in developing uses for slag can be attributed to the efforts of the National Slag Association founded in 1918. Since then, it has conducted numerous field and laboratory investigations to demonstrate the properties and uses for slag and slag products. These investigations have resulted in total recognition of blast-furnace slag as a construction material of consequence. The American Society for Testing & Materials Designation C125 recognizes blast-furnace slag as "the nonmetallic product consisting essentially of silicates and aluminosilicates of

Jan 1, 1975

By Robert A. Rapp, Jan E. Verfurth

From the measurement of internal-oxidation band widths in Ag-In and Cu-A1 alloys, products for the solubility No and the diffusivity Do of oxygen in silver and apparent NODo products in copper have been obtained over a range of temperature. The NODO products for silver are in agreement with the product of the individually determined No and Do values of Eichenauer and Müller. Although interstitial diffusion of oxygen in silver is expected, the temperature-independent factor Do of the diffusion coefficient does not agree well with the theory of Wert and Zener. For Cu-A1 alloys internal oxidation does not follow the expression derived for ideal kinetics, since the apparent NODo product calculated from internal-oxidation measurements is a function of the alloy content in the specimen. Thus, unequivocal values for No or DO or even the product NODO in copper are not available from the literature. RELIABLE values for the saturation solubility NO and diffusivity DO of oxygen in fcc metals are lacking and difficult to determine, partially because internal-friction measurements are not applicable. Permeability experiments and Sieverts7-type adsorption -desorption methods3 have met with difficulty; however, Eichenauer and Müller4 have recently reported on the solubility and diffusivity of oxygen in silver as determined by the latter technique . Rhines, Johnson, and Anderson,5 and independently Meijering and Druyvesteyn,&apos; introduced the possibility of deriving values for the product NODO in a metal from measurements of the widths of internal-oxidation zones (subscales) formed during the internal oxidation of alloys. In addition to these authors, several other investigators7-9 have made such measurements in various silver and copper alloys at various temperatures, mostly using me- chanically polished specimen surfaces. The purpose of this investigation was to determine over a range of temperature the calculated products NODO in silver and copper from systematic measurements of the widths of internally oxidized zones in Ag-In and Cu-A1 alloys, using specimens with electro-etched surfaces. Consider the internal oxidation of a dilute solid-solution alloy in which the base metal is not oxidized. If diffusion of oxygen is the rate-controlling step, then the depth 5 of the internal-oxidation zone is given by where y is a dimensionless parameter and t the oxidation time. Based on the solution of the diffusion equation, wagnerl0 has shown that under certain conditions several mathematical simplifications may be used in the evaluation of y, so that Eq. [I] may be expressed for the case that y « 1, and y(Do/DB) 1, where N(so)the is the equilibrium solubility (mole fraction) of oxygen in the solvent metal for the given oxidizing atmosphere, is the mole fraction of the solute metal in the bulk alloy, 4 is the diffusivity of the solute in the base metal, and v is the ratio of oxygen atoms to solute atoms in the precipitated oxide BO,. Rearranging Eq. [2] Maak&apos; has derived an expression analogous to Eq. [3] for the case that an external-oxide scale, in addition to an internal-oxidation zone, is formed. For this combined external and internal oxidation for the case that 5/2 where 5 is the distance of the internal-oxidation front from the original external s.urface, and X is the distance of the external oxide/metal interface from the original external interface. The function F is defined by the expression

Jan 1, 1964

By C. G. Dunn, W. W. Martin

Various X ray diffraction techniques have been developed for determining orientations of crystals. Transmission and back-reflection Laue methods1,2,3 in particular have been found to be very useful. In many applications, however, a need still exists for a simplification of the details of analysis so that orientations can be determined more rapidly, and operators with little or no training in crystallography can be easily instructed in the necessary procedures. Filling this need in part is a system of analysis that has been in use for several years in the Metals Section of the Laboratory, General Electric Co., Pittsfield, Mass. This method is an extension of the one of Majima and Togino,4 which uses fifty-five indexed standard transmission Lauemams to cover the entire range of crystal orientations. Greater rapidity in determining the orientation of a crystal is achieved by using a slightly larger set of standard Lauegrams and by systematizing the steps followed. This system of analysis in its present form constitutes the subject matter of the present paper. Although the method uses transmission X ray Laue patterns, many of the operations are applicable to the analysis of back-reflection Lauegrams. Very briefly the method is based on the fact that Bragg and azimuthal angles for two or more identified Laue diffraction spots completely determine the orientation of a crystal, and standard Laue photographs of the Majima and Togino type provide a ready means for identifying Laue spots. After a preliminary analysis, which consists of identifying the pattern in terms of one of the standard patterns, a correctly marked Lauegram is selected to carry out the final analysis. From measured Bragg and azimuthal angles, the normals (poles) of the reflecting planes for the selected Laue spots are located on a stereographic projection and the orient.at.ion of the crystal determined (in terms of the positions of cube poles for example) by a few additional operations on a \I1ulff net. The actual procedure followed will be illustrated in detail after a brief treatment or X ray problems connected with orientation determinations and a discussion of useful principles and techniques. X Ray and Plotting Problems RELATIVE ADVANTAGES OF BACK-REFLECTION AND TRANSMISSION LAUE DIFFRACTION METHODS In the back-reflection Laue method it is easy to make a direct measurement of the tilt of a zone of Laue spots. Specimen thickness also is generally no problem. In the case of thin specimens, however, the time of exposure is less for the transmission Laue method. For example, with silicon ferrite this advantage holds up to a thickness of 0.6 mm if tungsten radiation at 40 kv peak voltage is used. Furthermore, the transmission photograph represents the entire thickness of the crystal whereas the back-reflection picture represents only a surface layer (a thickness of less than 0.05 mm for silicon ferrite), the deeper layers supplying a negligible amount to the diffraction pattern. If a crystal is distorted, the transmission Laue pattern gives more information particularly with regard to the orientation of the crystal and the overall amount of spread in orientation. Finally a 3 1/4 X 4 in. film suffices for transmission photograms; a 4 X 5 in. or 5 X 7 in. film with a central hole is needed for back-reflection patterns Not only is the manipulation of film easier because of the size of film, but

Jan 1, 1950

The Joint Committee (consisting of the chairmen of the several society committees), formed under the authority of the five societies, in order to facilitate the carrying out of the organization of an engineer reserve as part of the military forces of the United States, for which work it was appointed, now begs leave to report as follows: .The Committee has been in personal communication with the Secretary of War, the officers of the General Staff, the officers of the War College, and with the Hon. George E. Chamberlain, Chairman of the Senate Committee on Military Affairs, and the Hon. James Hay, Chairman of the House Committee on Military Affairs. As the result of these interviews there has been incorporated in the draft of the legislation proposed by the Secretary of War and included also in the bills drawn by the committees of the Senate and of the House a provision for the organization of an officers reserve on broad lines, including an engineer reserve. As now drawn these bills provide that an officer shall be commissioned for a period of five years with rank up to and including that of major, after passing such requirements of character and qualifications as shall be prescribed by the President. The bill also provides that a certain amount of duty with pay shall he performed each year by the officers in the reserve. . The Committee is waiting for the Navy Department to formulate its plans for the increase in the naval forces, and as soon as a decision has been reached by that Department and the Committee is in possession of the facts, the Committee will take up the question of the organization of an engineer reserve for the navy, similar to that contemplated for the army.

Jan 2, 1916

By Sandford S. Cole

Manganese compounds occur in many mineral forms widely distributed throughout the crust of the earth. The most important of these commercially are the oxides which are usually found as irregular masses, but in some places (notably U.S.S.R.) occur as extensive beds of varying thickness and purity. The principal sources of ore have been U.S.S.R., Ghana (the Gold Coast of Africa), India, Union of South Africa, Belgian Congo, French Morocco, Cuba, Brazil, and Mexico. New developments of ore are being conducted in Brazil, British Guiana, French Equatorial Africa, and Northern Rhodesia. The production of the United States normally meets less than 10 pct of domestic manganese consumption. Manganese ore (35 pct or more Mn) is used principally by the ferrous metallurgy industry for production of manganese metal, ferromanganese, and other manganese alloys for use in production of steel ingots and castings. Some manganese is used in the nonferrous industry as an alloying element and cleanser in aluminum alloys, aluminum bronze, constantan, manganese bronze, Monel, Everdur, nickel-chromium resistance alloys, and nickel-silver. The metallurgical uses consume about 97 pct of the total manganese ore requirements of the United States. The balance goes principally for the manufacture of dry cells and for chemicals, with limited amounts for ceramic products, plastics, welding rods and varnish. The Materials Survey on Manganese, compiled in 1952 for Materials Office National Security Resources Board by the Bureau of Mines and Geological Survey, provides an excellent review of resources, reserves, specifications, uses, mining, beneficiation, metallurgical processes and deposits, and is worth referring to for greater details. Mineralogy and Geology The more common manganese minerals with typical characteristics are listed in Table 1 in order of importance. [ ]

Jan 1, 1960

By John Gillie

PRioR to the year 1902 electricity was used in the Butte district only for lighting, for the tramming of ores on the surface, and for the electrolytic refining of copper. In that year the Canyon Ferry hydro-electric plant on the Missouri river, with a transmission line to Butte and Anaconda, was completed, and enabled the mining operators to purchase electric current in large quantities at reasonable rates, and its application and use in the various mining operations and reduction works proceeded rapidly. The principal applications of electric current in metal mining may be listed as follows: Compressing air for hoisting. Compreeaing air for rock drills and pneumatic tools. Pumping. Ventilating. Lighting. Tramming. Compressing air for blast furnaces and converters Running shop and miscellaneous motors. Compressed Air for Hoisting. The Anaconda Copper Mining Co. operates 22 mine shafts and plants at Butte. Of these, 15 are large plants and hoists, through which most of its ores are hoisted. In 1912 this company commenced using compressed air in place of steam, in operating a number of its large hoists, and at this date has 10 main hoisting engines and 10 auxiliary hoists driven by compressed air. The compressed air is furnished from a central plant containing six compressors, each having a capacity of 7,500 cu. ft. of free air per minute compressed to 90 lb. pressure in large receivers, and conducted by suitable pipe lines to the various hoists, the air being reheated before passing to the engines. Each of these compressors is driven by a 1,200-h.p. synchronous motor, directly attached to the drive shaft, and takes electric current at 2,200 volts. Two additional compressors are being installed,

Jan 1, 1914

By G. H. F. Gardner

The boundary conditions F = 1.0 and 4 = 1.0 (100 per cent) are dictated by the definition of F in the equation 1/F = aFp. These conditions have physical significance as the "limiting conditions" for the observed behavior in systems of dispersed particles. The other boundary conditions, cited by Gardner in his Eq. 3 as applying to this system, have no significance in the systems we studied. Maxwell&apos;s equation (Eq. 2) cited in Gardner&apos;s comments was developed for and limited to a regular, rather than random, dispersion of spheres which are sufficiently removed from each other so that they do not interfere with current flow about their neighbors. These restrictions also apply to Rayleigh&apos;s analysis. The title of Rayleigh&apos;s paper cited by Gardner is "On the Influence of Obstacles Arrayed in Rectangular Order upon the Properties of a Medium". He is not discussing randomly dispersed spheres. It might be inferred from Gardner&apos;s comments that Rayleigh specifically considered the differential equation (Gardner&apos;s Eq. 3). This is not the case. Mathematically, Gardner&apos;s Eq. 3 is exactly true for the system to which it applies, however, as both Rayleigh and Maxwell note that their equation for F in terms of F is not for randomly dispersed spheres. At the time we wrote our paper, we were aware of the work of Wyllie and Gregory as cited by Gardner. We cited their work in Ref. 5 of our paper. Our comment on page 287 of the paper about the validity of an m value of 1.3 for spheres with a porosity of 38 per cent remains as our answer to Gardner&apos;s question on this point. Our data, at 38 per cent porosity, show that the condition a = 1 and m = 1.3 holds for spheres near 40 per cent porosity.

By E. C. Burke, W. R. Hibbard

G. B. Craig (University of Toronto, Toronto, O,nt., Canada)—The advent of pyramidal slip at room temperatures in a magnesium crystal (M2,) and the very low value reported for the critical shear stress are puzzling. Table I1 shows the calculated values (approximate) for sin x cos I in this specimen if all the (10l) planes are considered. If So is the shear stress resolved in the direction of glide, on the glide plane, and U, is the stress operative in yield point tests, then: S,, — 325 (0.169) 55gpersqmm (approximately) for 1101: S,, = 325 (0.465) = 151 gpersqmm (approximately) for (0001): S,, — 325 (0.101) - 32.8 gpersqmm (approximately) Thus, we see the pyramidal plane in which the minimum shearing component operated. Barrett"&apos; stated: "Experiments have repeatedly shown that, when there are several crystallographically equivalent slip systems in a crystal, the one having the greatest resolved shear stress will become active. ..." It does not appear to me that the measurements given are conclusive proof that pyramidal slip operated. E. C. Burke and W. R. Hibbard, Jr. (authors&apos; reply) —Although the low value for the critical resolved shear stress for pyramidal slip may be puzzling, there does not appear to be any basis for questioning the validity of the measurements. Under the influence of constraints, slip systems having decidedly lower shearing components may become operative, e.g., "cross-slip" or the "forced glide" in magnesium reported by Bakarian. Since we believe that pyramidal slip occurred in the specimen because basal slip was inhibited, it is not too surprising to find an operative plane with a lower shear stress. -7 C. S. Barrett: Structure of Metals U94jl p. 2J6. New York. McGraw-Hill Book Co.

Jan 1, 1953

By S. E. Bretherton

Discussion of the paper of S. E. BRETHERTON, presented at. the San Francisco meeting, September, 1915, and printed in Bulletin No. 104, August, 1915, pp. 1595 to1599. ANTON EILERS, Brooklyn, N. Y. (communication to the Secretary*). While the advantages in the use of high-line siliceous slags in lead smelting which Mr. Bretherton discusses in this paper are obvious under certain economical conditions, he gives me credit for the introduction of such slags when it does not belong to me. It is true I did considerable experimental work, off and on, for the purpose of finding such slags, while at the Germania in 1877 and 1878, but I did not have occasion to introduce any such slags for regular work, because I had no ores which fitted the economical conditions for using high silica and high lime, except in isolated cases for very brief periods. On the contrary, the ores I had to treat were mostly very ferruginous and very low in silica, so that, economically, I was compelled to run nearly always on slags, which allowed me to use the abundant flux I had without cost. It was August Raht who first had occasion to establish and use for long periods a slag high in silica and line, and low in iron. This was when he was confronted with the task of smelting the. Horn-Silver ores at the smelting works at Franklin, Utah, with as little expenditure for fluxing material as possible. I was at that time in Leadville, Col., where, in the new works I had built, the Billings and Eilers smelters, I had occasion to use profitably many slags, but never anything as high in the earthy bases and in silica as Mr. Raht had to use.

Jan 12, 1915