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By Charles P. Williams

The lead-bearing area of Missouri has been subdivided, geographically, into the Southeastern, the Central, and the Southwestern

By Arthur L. Walker

In June, 1893, while I was with the Old Dominion Copper Co. at Globe, Ariz., I received an offer to take charge, as manager, of the Baltimore Electric? Refining Co. which had recently built a plant at Baltimore, Md., having a capacity of about 1200 tons of electrolytic copper per month, using the Hayden series system. This was a very large output, for in those days the plants were small and the art was in its infancy. At the beginning of 1893 there were 11 electrolytic refineries in the United States, most of them using the multiple system. The Hayden series system was used at Baltimore and Bridgeport and the Smith series system was in operation at the Electrolytic Copper Co. at Ansonia, COM., and at the Pennsylvania Salt Co. at Philadelphia. In the latter system the plates were placed in a horizontal position, but the operating difficulties were so numerous it was soon discarded. The total production of these 11 plants in 1892 was very small; I have not been able to discover reliable figures of production. There were about thirty electrolytic copper refineries in the world that year, according to Titus Ulke, and the entire production of these

Jan 1, 1932

By O. C. Ralston, William C. Hunter

DUring experimental study on the separation of a zinc concentrate from the heavy sulfide ores of Jerome, Ariz., a great deal of attention has been given to proper activation of the sphalerite content of the ore. The sphalerite at Jerome contains enough iron to class it as a marmatite, as picked specimens have only about 60 per cent. zinc, whereas pure zinc sulfide contains 67 per cent. zinc. This marmatite in large pieces is black in color, but in dry powdered state is brown. A flotation froth made from it has a silvery black luster in comparison with a brassy luster caused by chalcopyrite which occurs in the same ores. The sample used in most of the experiments described below consisted of about 3000 Ib. of diamond-drill core from the zinc-bearing orebodies of the United Verde mine, and had the following analysis: Per Cent. Per Cent. Oz. peR Ton Cu............... 0.695 Al2O3............ 0.83 Ag................. 1.30 Zn............... 6.17 S................ 43.35 Au................ 0.02 Fe...............36.23 CaO............. 0.46 SiO2............. 9.27 Mineralogically, this analysis is calculated to the following, which is in agreement with the microscopic examination: Per Cent. Per Cent. Chalcopyrite................... 2.0 Schist........................... 3.2 Marmatite..................... 10.32 Quartz........................... 8.2 Pyrite........................ 73.0 Calcite.......................... 0.9 All samples were ground in a laboratory ball mill in order to leave about 3 per cent. on a 200-mesh sieve, fine grinding being essential to liberate the minerals in the ore. Most of the Jerome ores are so intimately crystallized that reasonably complete unlocking by grinding does not take place until 800 mesh is approached. Therefore, the 200-mesh grind adopted contains a considerable amount of locked mineral grains, but not so much as to render impossible the preparation of commercial grades of concentrate.

Jan 1, 1930

By J. W. Freeman, E. E. Reynolds, A. E. White

Fram a study of 63 systematic alloy modifications it was found that molybdenum, tungsten, and columbium, added individually or simultaneously, and increases in chromium cause major improvements in 1200°F rupture strengths of Cr-Ni-Co-Fe base alloys. Rupture strengths were a function of the effect of composition modifications on both the inherent creep resistance and the amount of deformation the alloy would tolerate before fracture. THIS paper describes the results of an investigation of a series of alloys with systematic variations of the chemical composition of the following basic alloy: C, 0.15: Mn, 1.7; Si, 0.5; Cr, 20.0; NI, 20.0: Co, 20.0: Mo, 3.0; W, 2.0; Cb, 1.0; N, 0.12; Fe, 32.0 pct. The 62 modifications of this alloy were produced under conditions which minimized all factors influencing properties at high temperatures except composition. Melting, fabrication, and heat treatment were carefully maintained constant. Stress-rupture properties at 1200°F were used as the primary criteria of evaluation of the alloy. The objective of the study was to obtain data for determining the fundamental role of the influence of alloying elements on properties of heat-resistant alloys at high temperatures. In addition the results should be useful in determining optimum chemical compositions, the sensitivity of properties to variations in composition, and the degree to which alloy content could be reduced while retaining worthwhile properties. It is difficult or impossible to develop correlations between properties at high temperatures and systematic variations in chemical composition from published data for wrought heat-resistant alloys developed for gas turbines.' ' The main reason for this is the extreme dependence of the properties on conditions of treatment of the alloys." In most cases variation in final treatments between alloys so influences the properties that the influence of chemical composition is obscured. In addition it is recognized Table I. Basic Alloy and Some Modifications Used Basic AllOy, Variations in Element Pct Composition, Pct C 0.15 0.08. 0.40. 0.60 Mn 1.1 0.03,0.25.0.50,1.0,2.5 S1 0.50 1.2, 1.6 Cr 20.0 10, 30 Ni 20.0 0, 10,30 Co 20.0 0. 10, 30 MO 3.0 0. 1.2.3, 5, 7 W 2.0 0, 1, 5, 1 Cb 1.0 0.2,4,6 N 0.12 0.004, 0.08, 0.18 Fe 32.0 that variations exist between heats of the same alloy which are related to melting practice and that there is a strong possibility that conditions of hot working influence response to final treatments. The development of heat-resistant alloys has been based on the gradual accumulation of data roughly related to composition from extensive testing programs. There is every reason to believe that in most cases the optimum compositions have been achieved by this procedure in the alloys commercially available. There are, however, very little data showing the influence of systematic variations of composition free from the influence of other factors, particularly for alloys of the type investigated. Several investigators of cast alloys have demonstrated compositional effects, notably Grant,1-6 Epremian,t Guy,8 and Harder and Gow.9 Sykes10 eviewed the work on the wrought alloy Rex 78 and the systematic variations of carbon, copper, molybdenum, and cobalt leading to the development of the stronger Rex 337A alloy. From the papers by Wilson11 and Henry12 it is possible to deduce the beneficial effect of substituting cobalt for iron in 0.45 pct C-20 pct Cr-20 pct Ni-4 pct Mo-4 pct W- 4 pct Cb alloys. Wilson mentioned but did not present the extensive compositional studies involved in developing these alloys. Binder" showed optimum properties for 3, 2, and I pct, respectively, for molybdenum, tungsten, and columbium in 20 pct Cr-20 pct Ni-20 pct Co-30 pct Fe alloys for limited systematic variations of these

Jan 1, 1953

By W. E. Anderson, T. M. Brady

As part of a larger study to identify factors influencing the practical operating life of wire rope used on large draglines in surface coal mining, field trips to operating surface coal mines were made during late 1975. Wire rope performance information was obtained from personnel at 13 mine sites west of the Appalachians. Seventeen pieces of equipment, utilizing bucket sizes ranging from 30 to 220 cu yd (23 to 168 m), were documented. Draglines at large US surface coal mines can be represented as 120 machines having 60-cu yd (46-m3) buckets, moving 1.8 x 10[9] cu yd (1.4 X 10[9] m3) of overburden during 6650 hours of productive availability per year. Based on the limited field study, the calculated downtime resulting from rope-related causes averages 105.6 hours per year for each typical 60-cu yd (43-m3) dragline. The total loss in production from this source alone is thereby estimated at about 25 X 10[6] cu yd (19 X 10[6] m3) annually.

Jan 11, 1979

By E. F. Loiseau

In a paper on the manufacture of artificial fuel, read at the Philadelphia meeting of February, 1878, I enumerated the difficulties which I had to overcome before succeeding in the mixing of coal-dust and clay, the compressing of the same mixture, and the water-proofing of the lumps. The drying of the lumps, after leaving the press, was the remaining difficulty, and it mas expected that a plan devised by Dr. Charles N. Cresson, of Philadelphia, would enable us to dry the fuel as rapidly as it was moulded, and that a continuous production could in that way be obtained. The company was reorganized. The works were purchased by the new company at an assignee's sale, and the oven was modified, according to Dr. Cresson's plan. Anticipating a possible failure, I had prepared a plan by which I expected to be able to demonstrate that anthracite coal dust nixed with pitch, could be manufactured with our present machinery slightly modified ; so that after all, if we were compelled to give up the attempt to make fuel for domestic use, there was a possibility of succeeding in the manufacture of a good steam-fuel. The plan suggested by Dr. Cresson for drying the pressed lumps of coal-dust cemented with clay, did not work as well as we expected. It enabled us to dry more fuel than we did before, but it could not be made to dry more than one half of the lumps produced by the press. The plan mas abandoned, and I was authorized to experiment with coal-dust and coal-tar pitch. The cement which is used in Europe to conglomerate coal-dust is usually dry pitch, which is prepared by separating from the tar, at a temperature of 572' Fahrenheit, the volatile matters which it contains. Some manufacturers, however, employ crude tar, others, a rich tar, which has been cleared of 25 per cent. of its volatile substances, by heating it to 392' Fahrenheit. But with common tar very weak fuels are obtained, which do riot burn well, and give out a strong smell and a great deal of smoke ; it is also necessary to subject them to a baking process, in order to solidify them, and to eliminate the more volatile of the materials contained. This operation of course requires a special plant, the cost of which increases sensibly the price of manufacture, without counting the products

Jan 1, 1880

By AIME AIME

HENRY YONGE WALKER is one of Canada's numerous gifts to the American mining and metallurgical industry, having been born it1 New Brunswick 59 years ago. At eighteen he came to the United States and has since been continuously identified with what are known as the Guggenheim interests. His first position was in the capacity of clerk at the Philadelphia Smelting & Refining Co. plant of M. Guggenheim Sons at Pueblo, Colo. In 1905 he was transferred to the plant of the American Smelting & Refining Co. at Everett, Wash., as assistant manager, two years later going to the Tacoma plant in the same capacity though with added

Jan 1, 1938

CONTENTS [The Nature of Strain Markings in Alpha Brass (paper by J. E. BURKE and C. S. BARRETT, Met. Tech. Feb. 1948. TP 2327). ......................... 2 X Ray Studies of Twinning and Untwinning in Magnesium Alloys (paper by J. B. HESS and R. L. DIETRICH, Met. Tech. Feb. 1948. TP 2328) ................ 11 ]

Jan 1, 1948

By W. J. Leas, L. A. Rapoport

As a preliminary, consicleration is given to the conventional definition of relative permeability and to the conditions governing the simultaneous flow of oil and gas through porous media. For the conditions of flow prevailing throughout most of a gas drive reservoir, the oil and gas can reasonably be supposed to be in capillary equilibrium with each other. Under these conditions, and these conditions only, the relative permeability to liquid can be expressed as a function of saturation. The relative permeability to liquid in that case is dependent upon the distribution of fluids which itself is shown to be related to the capillary pressure, and, in turn, to the saturation. As a consequence, relative permeability to liquid can be expressed in terms of the volume and surface area of a network of liquid channels bounded by the rock and the gas phase. While the volume of this network can be evaluated accurately, the surface area cannot. However, for any such volume, maximum and minimum values of the corresponding surface area can be calculated from capillary pressure data. It is then possible to establish for any saturation the limits within which the value of the relative permeability to liquid must lie. As a consequence of the theoretical development, the validity of an experimental method for measuring relative permeability to liquid which utilizes a stationary gas phase is demonstrated. In this method capillary barriers are cemented to the ends of the core sample to permit the maintenance of capillary equilibrium between the two phases. At the same time, this procedure eliminates undesirable secondary phenomena such as end effects, fissure effects, etc., the presence of which adversely affect the results of other laboratory methods. The results obtained by theoretical calculations, and experimentally, are discussed. In view of the overall precision that can presently be obtained in reservoir calculations, the agreement between the calculated and measured relative permeability to liquid data can be considered satisfactory. In conclusion, for reasons of economy and simplicity, the procedure of calculating limiting relative permeability to liquid curves from capillary pressure data is indicated for general engineering purposes. It is shown that the above procedure can easily be extended to the cases where connate water is present. Its use for reservoir studies is particularly recommended in conjunction with the method for measuring relative permeability to gas' which simultaneously yields the capillary pressure data necessary for the calculations. THEORETICAL Definition of Relative Permeabilities — Basic Equations for Heterogeneous Flow The equations by which the relative permeability concept is defined and upon which the formulation of all of the gas-oil flow problems rests at the present time are expressed as: V, = — Grad PL = — Grad PL ....(la) PL µL, k k KG VG = —K - Grad PG k- Grad Pc .... (lb) Mo where ,. and G refer to liquid and gas; V is the volumetric rate of flow per unit gross area. µ the viscosity, Grad P the potential gradient. and k the specific permeability of the porous medium.* (For horizontal flow, Grad P becomes the pressure gradient; otherwise, gravity must be included.) According to these expressions, each of the constituent phases is considered similar to a homogeneous system where the volumetric rate of flow is proportional to the pressure gradient, and for each of which the constants of proportionality, k, and kG, are termed effective permeabilities. by analogy to the specific permeability as defined by Darcy's law in its original form. In order to obtain a convenient basis of comparison, the effective permeabilities are referred to the specific permeability, k, of the considered porous medium, with the help of the relations: k1. = KI. k kQ = Kn k..........(2) K,. and Kr. are defined as the relative permeabilities to the liquid and to the gas phase respectively, and frequently expressed in per cent of specific permeability. It may be seen that Equations (1); which appear to be a direct generalization of Darcy's law, correspond to the assignment at any given time of a set of "local" permeabilities to each point of the porous medium, and represent in a differential form the two fluid flow system as a simple superposition of the individual single flow systems. The above interpretation implies that the effective or relative permeabilities are independent of pressure or rate of flow,

Jan 1, 1951

By L. A. Rapoport, W. J. Leas

As a preliminary, consicleration is given to the conventional definition of relative permeability and to the conditions governing the simultaneous flow of oil and gas through porous media. For the conditions of flow prevailing throughout most of a gas drive reservoir, the oil and gas can reasonably be supposed to be in capillary equilibrium with each other. Under these conditions, and these conditions only, the relative permeability to liquid can be expressed as a function of saturation. The relative permeability to liquid in that case is dependent upon the distribution of fluids which itself is shown to be related to the capillary pressure, and, in turn, to the saturation. As a consequence, relative permeability to liquid can be expressed in terms of the volume and surface area of a network of liquid channels bounded by the rock and the gas phase. While the volume of this network can be evaluated accurately, the surface area cannot. However, for any such volume, maximum and minimum values of the corresponding surface area can be calculated from capillary pressure data. It is then possible to establish for any saturation the limits within which the value of the relative permeability to liquid must lie. As a consequence of the theoretical development, the validity of an experimental method for measuring relative permeability to liquid which utilizes a stationary gas phase is demonstrated. In this method capillary barriers are cemented to the ends of the core sample to permit the maintenance of capillary equilibrium between the two phases. At the same time, this procedure eliminates undesirable secondary phenomena such as end effects, fissure effects, etc., the presence of which adversely affect the results of other laboratory methods. The results obtained by theoretical calculations, and experimentally, are discussed. In view of the overall precision that can presently be obtained in reservoir calculations, the agreement between the calculated and measured relative permeability to liquid data can be considered satisfactory. In conclusion, for reasons of economy and simplicity, the procedure of calculating limiting relative permeability to liquid curves from capillary pressure data is indicated for general engineering purposes. It is shown that the above procedure can easily be extended to the cases where connate water is present. Its use for reservoir studies is particularly recommended in conjunction with the method for measuring relative permeability to gas' which simultaneously yields the capillary pressure data necessary for the calculations. THEORETICAL Definition of Relative Permeabilities — Basic Equations for Heterogeneous Flow The equations by which the relative permeability concept is defined and upon which the formulation of all of the gas-oil flow problems rests at the present time are expressed as: V, = — Grad PL = — Grad PL ....(la) PL µL, k k KG VG = —K - Grad PG k- Grad Pc .... (lb) Mo where ,. and G refer to liquid and gas; V is the volumetric rate of flow per unit gross area. µ the viscosity, Grad P the potential gradient. and k the specific permeability of the porous medium.* (For horizontal flow, Grad P becomes the pressure gradient; otherwise, gravity must be included.) According to these expressions, each of the constituent phases is considered similar to a homogeneous system where the volumetric rate of flow is proportional to the pressure gradient, and for each of which the constants of proportionality, k, and kG, are termed effective permeabilities. by analogy to the specific permeability as defined by Darcy's law in its original form. In order to obtain a convenient basis of comparison, the effective permeabilities are referred to the specific permeability, k, of the considered porous medium, with the help of the relations: k1. = KI. k kQ = Kn k..........(2) K,. and Kr. are defined as the relative permeabilities to the liquid and to the gas phase respectively, and frequently expressed in per cent of specific permeability. It may be seen that Equations (1); which appear to be a direct generalization of Darcy's law, correspond to the assignment at any given time of a set of "local" permeabilities to each point of the porous medium, and represent in a differential form the two fluid flow system as a simple superposition of the individual single flow systems. The above interpretation implies that the effective or relative permeabilities are independent of pressure or rate of flow,

Jan 1, 1951

By J. H. Frye, R. M. Treco

One of the chief hindrances to an understanding of the hardness of solid solutions is the sparsity of suitable hardness data. There is great need of a large body of hardness data obtained from many different alloys of high purity by identical testing methods and corrected to correspond to a single grain size. A considerable amount of such data has been obtained by means of the Meyer analysis on copper-rich and silver-rich solid solutions. There are enough of these data to permit comparison of numerous alloys at equal solute concentration in these two solvents, but only in a few cases is it possible to construct hardness-concentration curves for any given alloy. Therefore additional hardness work on most of these alloys is desirable. The primary solid solutions of silver with cadmium, indium, tin, or antimony as solute are of special interest, since all elements are from the same period of the periodic table and since, as shown previously,l the hardening effect of equal percentages of these solutes is proportional to the lattice expansion produced by them. This paper presents the relation between hardness and concentration in the silver-antimony system from very dilute to nearly saturated solutions of antimony in silver. Experimental Procedure Alloys were made from silver, 99.99 per cent pure, and antimony, 99.975 per cent pure. Silver and antimony were placed in graphite crucibles that had an ash content of less than 0.7 5 per cent. These metals were melted and allowed to solidify in a vacuum, which, after melting was corn- . plete, was usually equivalent to 3 mm. of mercury. A high-frequency furnace was used. The ingots so obtained were worked and annealed to lessen segregation and to control grain size. Annealing was done in evacuated and sealed glass tubes. Hardness measuremeuts on specimens from these ingots were by means of the Meyer analysis.394 Using a 4-mm. ball, impressions were made under seven loads from 25 to 400 kg. The diameter of impression made under each load was measured. This enabled calculation of the constants in the well-known formula of Meyer. L = adn where L = load, d = diameter of impression, a = a constant, n = a constant The Meyer hardness is defined as P = L/i(1/4pd2) or P = 4adn-2/p Meyer hardnesses corresponding to d = I and to d = 4 are of especial interest, since the first corresponds to comparatively slight 'plastic deformation and the second to the maximum plastic deformation producible by penetration of the ball. These

Jan 1, 1945

By Rex E. Cheek, Donald E. Menzie

The fluid mapper, a model relatively new to the petroleum industry, was used to study the effect of various mobility ratios on the areal sweepout efficiency for two typical spacing patterns. The experiments indicated the areal sweepout for the five-spot pattern varied from 51.8 per cent at a mobility ratio of 0.093 to 89.1 per cent for a ratio of 24.4. In the direct line-drive pattern, the areal sweepout varied from 58.7 per cent at a mobility ratio of 0.089 to 92.0 per cent at a ratio of 24.8. The fluid mapper may prove useful to determine quickly the effective areal sweepout for any well spacing. INTRODUCTION The effect of the mobility ratio on the areal sweepout efficiency during primary depletion of a water drive reservoir and during secondary recovery operations has recently become more widely recognized The mobility ratio, M, is defined as: _ kjp (displaced fluid) k/u (displacing fluid) where k = effective permeability u = viscosity When the displacing fluid is miscible with the displaced fluid, the permeabilities are equal and the mobility ratio may be expressed as a ratio of viscosities: u (displacing fluid) u (displaced fluid) The mathematical analysis for calculating the areal sweepout efficiency with mobility ratio other than unity is quite tedious.5,11 An experimental method by using a potentiometric model2 in a step-wise manner and in using an X-ray shadowgraph model3,12 with continuous fluid flow has been published. Several types of models have been used to study oil and gas reservoir performance. These models may be classified as physical, electrolytic, potentiometric, X-ray shadowgraph, and fluid mapper. The X-ray shadowgraph and fluid mapper are models relatively new to petroleum engineering and have not been used extensively for specific applications. The theory of the fluid mapper indicates it may be adapted to a study of areal sweepout efficiencies for various mobility ratios as well as other complex problems in petroleum engineering. The use of the model and results obtained when using displacing and displaced fluids of equal densities but different viscosities are discussed. FLUID MAPPER DEVELOPMENT H. S. Hele-ShawV eveloped a fluid mapper model based on the hydrodynamic theory. This theory is that in the steady flow of a viscous fluid between horizontal parallel plates spaced a very small distance apart, the effect of viscous shear is of such magnitude in the vertical plane that the motion in the horizontal plane is practically undisbrted streamline flow. Techniques developed by Hele-Shaw were not expanded and no additional developments in fluid mapper models were forthcoming until A. D. Moore, University of Michigan, published a series of papers starting in 1949, which describe the construction of a flexible and inexpensive model'h nd the fluid mapper technique for the solution of certain problems.' The essential components of the fluid mapper as developed by Moore are::.ln 1. A base slab. made of dental stone (calcium sulphate and water). which is shaped to represent the prototype. 2. Plate glass slightly larger than the slab and spaced

Jan 1, 1956

By J. Husson, R. Iffly, M. Gondouin

A systematic variation of well deliverability, as reflected from isochronal back-pressure tests performed at regular intervals, has been observed in some gas condensate wells producing at high rates. The same effects have been obtained using a numerical model of gas and condensate flow which takes into account secondary gasoline deposited in the pore space as a result of pressure reduction, and non - Darcy flow of gas in the vicinity of the wells. Matching calculated values with previous test results has been possible, and future predictions have been obtained. An application of this method to the Hassi Er R'Mel gas-condensate field in Algeria is tentatively shown. INTRODUCTION Flow capacity of gas wells is generally derived from an analysis of back-pressure tests. The empirical equation q = C (?p2)n used by Rawlins and Schellhardtl can be derived rigorously assuming that steady-state radial flow of a dry gas of constant viscosity and compressibility is established during each flow period of the well tests. Furthermore, when Darcy's law applies in the entire flow region, the theory predicts that the exponent n is equal to 1. In low-permeability reservoirs, it was soon discovered that the time required to reach a stabilized flow often exceeded the duration of the flow periods normally available for testing wells. Consequently, transient gas flow had to be considered instead of the steady-state assumption previously used. This led to the isochronal testing procedure established by Cullender2 which has largely replaced conventional back-pressure testing. For dry gas fields, this method yields definite values of C and n equivalent to those of the empirical equation. These values should remain constant for each well as long as the permeability of the formation and the characteristics of the gas (viscosity and compressibility) do not change appreciably. This is the case when reservoir pressure remains -close to the original value and when the formation near the wellbore remains free of plugging. Under those conditions, stabilized flow potential curves of gas wells can be established from a single sequence of isochronal flow and shut-in periods. An analysis of a pressure build-up following a longer production period provides additional data on the transmissivity (k h/ u) of the reservoir, and eventually on the 'drainage radius rd of the well, which can be related to the value of C so that future performance of the well can be predicted using the concepts developed by A. Houpeurt.3 At high flow rates, Darcy's law no longer applies in the vicinity of the wellbore, and inertial effects in the high velocity gas flow introduce additional pressure drops. As a consequence, exponent n of the backpressure tests becomes smaller than 1, and a slight curvature of the log-log plot of ?p2 vs q can be predicted when going from very low to high rates of flow (Elenbaas and Katz).5 The effects of variations of viscosity and compressibility with pressure on the radial flow of dry gas in an infinite reservoir were taken into account by Jenkins and Aronofsky.7 Numerical solutions of the transient flow of an ideal gas in finite radial reservoirs were presented by Bruce, Peaceman, Rachford and Rice.8 In the case of gas condensate wells, however, the presence of gasoline in the pore space as soon as reservoir pressure is reduced below the dewpoint pressure further complicates the interpretation of flow tests so that the prediction of stabilized well performance becomes very difficult. Field observation shows that both C and n derived from isochronal tests vary in time, even when reservoir pressure has not changed appreciably. Such a variation cannot be attributed to any change of the gas characteristics, and must result from the effect of a gasoline saturation on the gas flow.

By K. H. Heino

Two 200 T/da Lurgi Turbulent Layer fluid-bed roasters have been in operation at Canadian Electrolytic Zinc Limited since 1966. Zinc concentrate containing 52-54% Zn, 9-11% Fe,31-33% S is treated to produce calcine containing 60-62% Zn,10-12% Fe, .l-.3% S as sulphide and .8-1.2% S as sulphate. Each roaster train comprises a waste heat boiler, two cyclones in parallel and a two-field electrostatic precipitator. Distribution of calcine collected is 10-15 percent from bed overflow, 55-65 percent from boilers, 20-25 percent from cyclones and 2-6 percent from precipitators. A Monsanto designed contact plant produces acid at a rated capacity of 365 T/da (100% H2304 basis) from roaster gases diluted to 7.0-7.5% S02. The process steps are gas cleaning and cooling by weak acid scrubbing, acid mist removal in electrostatic precipitators, gas drying in 93.5-96.5% H2304, conversion of sulphur dioxide to sulphur trioxide in a four-pass converter containing vanadium pentoxide catalyst, and absorption of the sulphur trioxide in 98.1-98.3% H2S04. Product acid is 93.2% H2S04. Conversion efficiency is 97-98 percent and overall sulphur recovery from concentrate is 87-90 percent. The adjacent fertilizer plant has a capacity of 135 T/da of P205. The products are 54 percent phosphoric acid, run-of-pile triple superphosphate, and diammonium phosphate. The plant is of Ugine-Kuhlman design and consists of an air-cooled multiple tank reactor, a tilting pan filter, and a forced circultation vacuum evaporator. Triple superphosphate is made on a continuous belt and partially cured in a rotary dryer. Diammonium phosphate is produced by ammoniating phosphoric acid in a single stage reactor. The slurry of ammonium phosphate is granulated in a blunger and dried.

Jan 1, 1970

By Eli T. Conner

(Wilkes-Barre Meeting, June, 1911.) My connection, under a commission from the Councils and Board of School Control of the city of Scranton, Pa., with a recent investigation of mine-caves and the resultant damages to surface-improvements, has led to the preparation, at the invitation of our Secretary, of the present paper. It is notorious that there are, in the anthracite-fields, frequent subsidences of the surface, due to the removal of the coal beneath. No particular attention is paid to such occurrences, unless they happen to injure surface-improvements. Many caves have happened in Scranton and its vicinity, which have excited but little remark, since they have generally caused no serious damage. In August, 1909, a cave occurred in the Hyde Park section of the city, generally known as the West Side, which nearly destroyed school-house No. 16 and considerable adjacent property. 'Fortunately, there were no pupils in the building at the time; but the thought of the possible result, bad the usual number of pupils and teachers been present, aroused the public to the gravity of the situation; and the School Board employed engineers to investigate the case. Two reports were made by separate sets of engineers, which differed in some particulars. These differences were pointed out in the public press and magnified, and the consequent agitation of the subject was taken tip and greatly exaggerated by some of the metropolitan newspapers, giving to uninformed people the very erroneous impression that the whole city of Scranton was in danger of sinking into the bowels of the earth. All this tended to affect the credit of the city and to depress real-estate values. The matter was considered at a joint meeting of the Board of Trade, the Councils, and the School Board. The Hon. J. Ben. Dimmick, a former Mayor, suggested that it

Sep 1, 1911

By W. C. Ellis, E. S. Greiner

METALLIC titanium has been prepared in small quantities since the beginning of the century. Hunter1 reported in 1910 that he obtained a malleable product of 99.9 pct purity by the reduction of the tetrachloride by sodium in a closed container. Later Van Arkel2 and Fast3 prepared small quantities of malleable titanium by thermal decomposition of titanium iodide. Another method for producing malleable titanium from tetrachloride was reported by Kroll4 who used magnesium as the reducing agent. More recently Dean, Long, Wartman, and Anderson5 working at the U.S. Bureau of Mines have reported the preparation of the metal on a pilot plant scale by the reduction of titanium tetrachloride by magnesium in an atmosphere of helium. Their product, which is malleable, was used in the present investigation. Early in 1948 after the work of this paper: was completed Campbell, Jaffee, Blocher, Gurland, and Gonser6 described the strength and working characteristics of pure titanium which was prepared by the iodide method on a scale producing 300 to 600 g per run, in the form of 0.3- to 0.4-in. diam rods. Their product is characterized by low hardness and large capacity for cold work which they attribute to a high degree of purity with respect to oxygen, nitrogen, and carbon. Titanium has a melting point of about 1725°C5 it may be classed as a light metal since the specific gravity is 4.5 g per cc-1. The crystal structure is close-packed hexagonal from room temperature t0 885°C. Above this temperature the structure is reported7 as body-centered cubic. The change in crystal structure has been associated with discontinuities in specific heat8 electric resistance9 and thermoelectric force10 at temperatures near 890°C. It is reported11 that annealed titanium has a tensile strength 0f 78,700 psi which can be increased by cold-work to 123,000 psi. In the present investigation, the lattice constants at room temperature, the thermal expansivity between 30 and 800°C, as well as the electrical resistivity and thermoelectric force against platinum between - 200 and 1000°C have been determined. MATERIALS For the measurements, two series of specimens were prepared from titanium furnished by the U. S. Bureau of Mines. The first was lade from an annealed sintered compact, 0.38 in. thick. Sections of the compact were cold-swaged with intermediate anneals in vacuum to the sizes used. Sizes over 0.25-in. diam were annealed at 1000°C and smaller sizes at 800°C. Specimens originating from the sintered compact are designated in this paper as A. The second series of specimens was lade from a rod of titanium, 0.19 in. in dial, which was cold-swaged with the necessary intermediate anneals to the required sizes. This series of specimens is designated B. The impurities in the specimens of titanium, determined by chemical analysis, are given in Table I. Oxygen and nitrogen which were not determined by analysis, are probably present although in small quantities in view of the ductility of the material.

Jan 1, 1948

By C. Morrow

Deformation studies were performed on tuffaceous rocks fran Yucca Mountain, Nevada Test Site to determine the strengths and coefficients of friction under confining pressures from 10-50 MPa at room temperature. Frictional strengths of 30ºsawcut samples increased with pressure and reached values of around 150 MPa at the higher confining pressures. However, the failure strengths of the intact samples were quite unpredictable. The coefficients of friction ranged between 0.7 and 0.9 for all specimens. These data can be used in conjunction with in situ stress measurements at Yucca Mountain, to evaluate the potential for earthquake activity in the region.

Jan 1, 1984

CONTENTS PAGE BAIN, EDGAR C.-The Nature of Martensite. Discussed by Ancel St. John, Henry S. Rawdon, Jerome Alexander, Howard Scott 1 FEILD, ALEXANDER L.-Effect of Zirconium on Hot-rolling Properties of High-sulfur Steels and the Occurrence of Zirconium Sulfide. Discussed by Beram D. Saklatwalla, Bradley. Stoughton, Andrew M'Cance, George F. Comstock, Alexander L. Feild 12 SAUVEUR, ALBERT and KRIVOBOK, V. N.-Use of Sodium Picrate in Revealing Dendritic Segregation in Iron Alloys. Discussed by George F. Comstock, John H. Hall 17 KINNEY, C. L., JR.-Economic Significance of Metalloids in Basic Pig Iron in Basil Open-hearth Practice. Discussed by V. J. Pazzetti, George B. Waterhouse, C. L. Kinney, Jr 19 NEAD, J. H.-Absorption of Sulfur from Producer Gas in Open-hearth Furnaces.. Discussed by George B. Waterhouse, C. L. Kinney, Jr 26 PRIESTLY, WILLIAM J.-Effect on Steel of Variations in Rate of Cooling in Ingot Molds. Discussed by Emil Gathmann, Paul E. McKinney, George A. Dornin. 27 MONYPENNY, JOHN H. G.-Stainless Steel, with Particular Reference to the Milder Varieties (Stainless Iron). Discussed by P. A. E.-Armstrong, Beram D. Saklatwalla 33 ROYSTER, P. H., and JOSEPH, T. L.-Effect of Coke Combustibility on Stock Descent in Blast Furnaces. Discussed by Ralph H. Sweetser,. Richard Franchot, Sidney Cornell, T. L. Joseph 41 DAVIS, F. W., and BOLE, G. A.-Observations on Requirements of Refractories for Open Hearth. Discussed by C. L. Kinney, Jr., L. F. Reinartz, P. E. McKinney 46

Jan 5, 1924

By J. C. Fisher

Nucleation theory is applied to martensite nucleation in substitutional iron alloys. Composition fluctuations are neglected, and a steady rate of nucleation is predicted for any composition and temperature. The maximum rate of nucleation (as a function of temperature) is shown to be measurable only for on extremely narrow composition range, being too great or too small outside this range. A number of experimental observations, including completely isothermal transformation in some alloys and composition-dependence of M. temperature in others, are compared with the calculated behavior. IN a previous report,¹ nucleation theory was applied to the formation of isothermal martensite in an Fe-Ni-Mn alloy. The experimental observations of Cech and Hollomon² were accounted for quantitatively. It now is of interest to examine the predictions of nucleation theory with respect to martensite transformation in substitutional iron alloys of other compositions. Since Fe-Ni alloys have received considerable attention, both as to their transformation kinetics and their free energies, they will be treated in detail, although the results apply with equal validity to other substitutional alloys. In substitutional alloys, where composition fluctuations can be neglected in volumes of critical nuclear size, the rate of nucleation of martensite in subcooled austenite is¹ n - Nv exp (—W*/kT) [I] where the free energy of formation of the critical size nucleus is W* = 8192 p (?² s³) [2] In the expressions for n and W*, the symbols have the following meanings: N is the number of atoms per unit volume; v, the atomic vibration frequency; 8, a function of the elastic constants of austenite and the shear angle of martensite; , the austenite/mar-tensite inter facial free energy; and ?fc is the free energy change per unit volume accompanying the transformation. Jones and Pumphrey² have determined the austenite to martensite free energy change as a function of nickel content and temperature for Fe-Ni alloys. Their expression is ?F = 2500 C + 1.25 (1 —C)?FFc cal per mol [3] where C is the atom fraction of nickel, and ?Ffe is the free energy change per unit volume for pure iron as tabulated by Zener4 (or, equivalently, Fisher"). From Eqs. 1 to 3, it is possible to calculate isothermal nucleation rates as a function of temperature and composition for Fe-Ni alloys. The only unknown parameter is (?² s³). The best value of this parameter for Fe-Ni alloys, determined from M. temperatures in a manner to be described shortly, is (?² s³)= 9.92 (10)21 cgs units [4] Taking this value of (?² s³), C-curves for isothermal nucleation were calculated for Fe-Ni alloys of several compositions, and are plotted in Fig. 1. It is evident from Fig. 1 that completely isothermal nucleation of martensite in Fe-Ni alloys can be observed experimentally for only a very narrow range of compositions. Cech and Hollomon find that a nucleation rate of about 10' nuclei per cc per sec is as fast as they can follow dilatometrically, and a rate of about 10-1 nucleus per cc per sec is about the slowest that can be measured conveniently. If the nucleation rate is to lie between the limits 10-1 10 the nickel content of an Fe-Ni alloy must fall in the atomic fraction range 0.299 5 C 5 0.302. Nickel contents lower than 0.299 correspond to nucleation rates too great to follow, and those higher than 0.302 to nucleation rates too slow to measure in a reasonable time.* In view of the narrow corn- position range in which successful isothermal measurements can be made, it is not surprising that only one substitutional alloy has been described' that comes close to being in the proper range.

Jan 1, 1954

By N. F. Dyson, T. R. Scott

The iilzfluence of catalytic agents on the oxidation of ZnS has been studied under pressure leaching conditions, using a chemically prepared sample of ZnS which was substantially unreactive on heating at 113°C with dilute sulfuric acid and 250 psi oxygen. Nurnerous prospective catalysts were added at the ratio of 0.024 mole per mole ZnS in the above reaction but pvonounced catalytic activity was confined to copper, bismuth, rutheniuwl, molybdenum, and iron in order of. decreasing effectiveness. In the absence of acid, where sulfate was the sole product of oxidation, catalysis was exhibited by copper and ruthenium only. Parameters affecting the oxidation rate were catalyst concentration, temperature, time, oxygen pressure, and a7riount of acid, the first two being most important. The main product of oxidation in the acid reaction was sulfur, with trinor amounts of sulfate. An electrochemical (galvanic) mechanism has been suggested for the sulfuv-forming reaction, whereby the relatively inert ZnS is "activated" by incorporation of catalyst ions in the lattice and the same catalysts subsequently accelerate the reduction of dissolved oxygen at cathodic sites on the ZnS surface. Insufficient data was obtained to Provide a detailed mechanism for sulfate fornzation, which is favored at low acidities and probably proceeds th'rough intermediate transient species not identified in the preseni work. THE oxidation of zinc sulfide at elevated temperatures and pressures takes place according to the following simplified reactions: ZnS + io2 + H2SO4 — ZnSO4 + SG + HsO [i] ZnS + 20,-ZSO [21 In dilute acid both reactions occur but Reaction [I] is usually predominant, whereas in the absence of acid only Reaction [2] can be observed. Both proceed very slowly with chemically pure zinc sulfide but can be greatly accelerated by the addition of suitable catalysts, as suggested by jorling' in 1954. Nevertheless, an initial success in the pressure leaching of zinc concentrates was achieved by Forward and veltman2 without any deliberate addition of catalytic agents and it was only later that the catalytic role of iron, present in concentrates both as (ZnFe)S and as impurities, was recognized and eventually patented.3 It is now apparent that another catalyst, uiz., copper, may have also played a part in the successful extraction of zinc, since copper sulfate is almost universally used as an activator in the flotation of sphalerite and can be adsorbed on the mineral surface in sufficient amount The importance of catalysis in oxidation-reduction reactions such as those cited above has been emphasized by various writers and Halpern4 sums up the situation when he writes that "there is good reason to believe that such ions (e.g., Cu) may exert an important catalytic influence on the various homogeneous and heterogeneous reactions which occur during leaching, particularly of sulfides, thus affecting not only the leaching rates but also the nature of the final products." Nevertheless relatively little work has appeared on this topic, one of the main reasons being that sufficiently pure samples of sulfide minerals are difficult to prepare or obtain. When it is realized that 1 part Cu in 2000 parts of ZnS is sufficient to exert a pronounced catalytic effect, the magnitude of the purity problem is evident. An incentive to undertake the present work was that an adequate supply of "pure" zinc sulfide became available. When preliminary tests established that the material, despite its large surface area, was substantially unreactive under pressure leaching conditions, the inference was made that it was sufficiently free from catalytic impurities to be suitable for studies in which known amounts of potential catalytic agents could be added. The first objective in the following work was to identify those ions or compounds which accelerate the reaction rate and, for practical reasons, to determine the effects of parameters such as amgunt of catalyst, temperature, time, acid concentration, and oxygen pressure. The second and ultimately the more important objective was to make use of the experimental results to further our knowledge of the reaction mechanisms occurring under pressure leaching conditions. The fact that catalysts can dramatically increase the reaction rate suggests that physical factors such as absorption of gaseous oxygen, transport of reactants and products, and so forth, are not of major importance under the experimental conditions employed and an opportunity is thereby provided to concentrate on the heterogeneous reaction on the surface of the sulfide particles. As will appear in the sequel, the first of these objectives has been achieved in a semiquantitative fashion but a great deal still remains to be clarified in the field of reaction mechanisms. EXPERIMENTAL a) Materials. The white zinc sulfide used was a chemically prepared "Laboratory Reagent" material (B.D.H.) and X-ray diffraction tests showed it to contain both sphalerite and wurtzite. The specific surface area, measured by argon absorption at 77"K, varied between 3.9 and 4.6 sq m per g. Analysis gave 65.0 pct Zn (67.1 pct theory) and 31.9 pct S (32.9 pct theory). Other metallic sulfides (CdS, FeS, and so forth) used in the experiments were also chemical preparations of "Laboratory Reagent" grade. Samples of mar ma-

Jan 1, 1969