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By Howard A. Smith

OF late considerable experimental and theoretical interest has been shown in the rates of transformation from a single phase, usually a supercooled solid solution, into one or more phases. Such reactions may involve both diffusion and transformation of the major constituent, as in iron alloys, or it may simply involve diffusion, as in superstructure formation and in age-hardening systems. Most of the work has been confined to ferrous alloys1-9† although two investigations have been made on copper alloys 10-11. That such work may be of considerable practical importance has been demonstrated by Bain12, by the workers at the Kaiser Wilhelm Institut für Eisenforschung13, 14, and by the everyday use of precipitation and age-hardening principles15. Experiments in this country have generally followed Davenport and Bain's technique of rapid supercooling followed by isothermal treatment. In Germany16, 17 the work has been extended to the study of the influence of accurately controlled and measured rates of cooling. The work on steel indicates that there are two subcritical temperature ranges where reaction starts sooner after quenching and proceeds at a more rapid rate than at other temperatures. At subcritical temperatures above Ar" where reaction is dependent upon atomic migration there is a period of time of which the length depends upon the alloy content and the temperature, before which no reaction has been detected. Davenport and Bain1 find that different sorts of atoms in solid solution in gamma iron affect the length of this "prereaction" period differently, manganese

Jan 1, 1935

By N. D. Policow, J. S. Orphanos

Dewatering fine clean coal fractions, -595µm (-28 mesh), represents one of the most difficult and costly separations in typical plant circuits. Since 1969, the screen bowl centrifuge has offered an economical alternative to filtration/thermal dyer combinations. The performance of screen bowl centrifuges has been continuously modified and improved to dewater not only coarser coals, but also today's variety of ultrafine material. Test comparisons with alternative methods show the screen bowl centrifuge to be most cost effective and efficient when all factors are considered.

Jan 1, 1984

By J. S. Billheimer, B. H. Sage, W. N. Lacey

A restricted ternary system made up of n-pentane, tetralin, and a purified bitumen was investigated at 70, 160, and 220 °F. Most of the experimental observations were at atmospheric pressure or at 200 psi." However, some experimental measurements were carried out at a pressure of approximately 8000 psi. It was found that the purified bitumen was precipitated from its solution or dispersion in tetralin by the addition of n-pentane and that the separation occurred at lower weight fractions of n-pentane at the lower temperatures. The bitumen-tetralin solutions show some colloidal characteristics at temperatures below 160 °F when near compositions at which the bitumen separates as a solid phase. At states remote from the phase boundaries and at temperatures above 160 °F these characteristics become less evident. Under these latter circumstances the mixtures tend to follow the behavior of true solutions, particularly in regard to the approach to heterogeneous equilibrium. An increase in pressure appears to increase the solubility of bitumen in tet-ralin-n-pentane solutions. This effect is more pronounced at temperatures above 160 °F than at lower temperatures. INTRODUCTION Asphaltic phases of plastic or solid nature have appeared in numerous instances during the recovery of petroleum from underground reservoirs. Such depositions occurring underground appear to have caused adverse production histories for particular wells or zones. Because of this field experience, it is desirable to understand the factors which influence the formation or separation of the asphaltic phases from petroleum. The problem is unusually complex because the number of true components involved is very large and the details of the phase behavior encountered are difficult to ascertain experimentally. The literature relating to asphalts, asphaltines, and bitumen is voluminous and widespread.' Only those references which are directly pertinent to the work at hand are cited. The separation of an asphaltic phase, hereinafter called bitumen? from naturally occurring hydrocarbon mixtures has been the subject of several investigations.2'3'4'5'6 It has been found that as many as four phases4 may be produced from a crude oil by the solution of a natural gas and propane at a pressure of 1500 psi and a temperature of 70 °F. The separation of bitumen from such naturally occurring mixtures results in at least one liquid phase which is substantially free of high molecular weight components.³ The influence of the solution of lighter hydrocarbons on the separation of bitumen from a Santa Fe Springs crude oil has been investigated. The results indicate that in the case of the methane-crude oil system, the quantity of plastic or solid phase separated reaches a maximum between 0.14 and 0.19 weight fraction methane and then decreases until negligible at higher weight fractions of methane. Similiar behavior was encountered in the case of mixtures of ethane and crude oil. The decrease in the quantity of the solid phase with an increase in the weight fraction of the lighter component appears to result from the formation of an additional liquid phase6 in which the bitumen is relatively soluble. The formation of this additional phase probably occurs at a weight fraction of methane close to that at which the quantity of separated solid reaches a maximum. A comparison of the deposition of bitumen in the field with the separation of asphalts from lubrication oil has been made' and apparently the phenomena are similar. The phase behavior of bitumen also appears to be comparable to that of coal tar."' The chemical and physical characteristics of asphalts and bitumen have been the subject of extended investigations which have been reviewed in some detail by Katz.¹º The conclusion was reached that the dispersion of bitumen in a number of organic liquids was not entirely colloidal since it was impossible to isolate individual dispersed particles even with the electron microscope. However, the evidence appeared to indicate that at states close to phase boundaries the extent of the dispersion of the phases influenced the equilibrium to a greater extent than is encountered in many simpler systems. From earlier study of field samples it became apparent that the phase behavior of bitumen-hydrocarbon systems was unusually complex. It was difficult to characterize in detail the phase behavior involved in naturally occurring hydrocarbon systems, even after a relatively extended investigation. For this reason, the study of a somewhat simpler system which still behaved in a similar manner became desirable. Three major constituents were necessary as-follows: a bituminous solid, a liquid constituent which was a reasonably good solvent, and a constituent in which bitumen was largely insoluble. A sam-

Jan 1, 1949

By W. N. Lacey, B. H. Sage, J. S. Billheimer

A restricted ternary system made up of n-pentane, tetralin, and a purified bitumen was investigated at 70, 160, and 220 °F. Most of the experimental observations were at atmospheric pressure or at 200 psi." However, some experimental measurements were carried out at a pressure of approximately 8000 psi. It was found that the purified bitumen was precipitated from its solution or dispersion in tetralin by the addition of n-pentane and that the separation occurred at lower weight fractions of n-pentane at the lower temperatures. The bitumen-tetralin solutions show some colloidal characteristics at temperatures below 160 °F when near compositions at which the bitumen separates as a solid phase. At states remote from the phase boundaries and at temperatures above 160 °F these characteristics become less evident. Under these latter circumstances the mixtures tend to follow the behavior of true solutions, particularly in regard to the approach to heterogeneous equilibrium. An increase in pressure appears to increase the solubility of bitumen in tet-ralin-n-pentane solutions. This effect is more pronounced at temperatures above 160 °F than at lower temperatures. INTRODUCTION Asphaltic phases of plastic or solid nature have appeared in numerous instances during the recovery of petroleum from underground reservoirs. Such depositions occurring underground appear to have caused adverse production histories for particular wells or zones. Because of this field experience, it is desirable to understand the factors which influence the formation or separation of the asphaltic phases from petroleum. The problem is unusually complex because the number of true components involved is very large and the details of the phase behavior encountered are difficult to ascertain experimentally. The literature relating to asphalts, asphaltines, and bitumen is voluminous and widespread.' Only those references which are directly pertinent to the work at hand are cited. The separation of an asphaltic phase, hereinafter called bitumen? from naturally occurring hydrocarbon mixtures has been the subject of several investigations.2'3'4'5'6 It has been found that as many as four phases4 may be produced from a crude oil by the solution of a natural gas and propane at a pressure of 1500 psi and a temperature of 70 °F. The separation of bitumen from such naturally occurring mixtures results in at least one liquid phase which is substantially free of high molecular weight components.³ The influence of the solution of lighter hydrocarbons on the separation of bitumen from a Santa Fe Springs crude oil has been investigated. The results indicate that in the case of the methane-crude oil system, the quantity of plastic or solid phase separated reaches a maximum between 0.14 and 0.19 weight fraction methane and then decreases until negligible at higher weight fractions of methane. Similiar behavior was encountered in the case of mixtures of ethane and crude oil. The decrease in the quantity of the solid phase with an increase in the weight fraction of the lighter component appears to result from the formation of an additional liquid phase6 in which the bitumen is relatively soluble. The formation of this additional phase probably occurs at a weight fraction of methane close to that at which the quantity of separated solid reaches a maximum. A comparison of the deposition of bitumen in the field with the separation of asphalts from lubrication oil has been made' and apparently the phenomena are similar. The phase behavior of bitumen also appears to be comparable to that of coal tar."' The chemical and physical characteristics of asphalts and bitumen have been the subject of extended investigations which have been reviewed in some detail by Katz.¹º The conclusion was reached that the dispersion of bitumen in a number of organic liquids was not entirely colloidal since it was impossible to isolate individual dispersed particles even with the electron microscope. However, the evidence appeared to indicate that at states close to phase boundaries the extent of the dispersion of the phases influenced the equilibrium to a greater extent than is encountered in many simpler systems. From earlier study of field samples it became apparent that the phase behavior of bitumen-hydrocarbon systems was unusually complex. It was difficult to characterize in detail the phase behavior involved in naturally occurring hydrocarbon systems, even after a relatively extended investigation. For this reason, the study of a somewhat simpler system which still behaved in a similar manner became desirable. Three major constituents were necessary as-follows: a bituminous solid, a liquid constituent which was a reasonably good solvent, and a constituent in which bitumen was largely insoluble. A sam-

Jan 1, 1949

By Kendall E. Born

Production of crude oil in Tennessee during 5945 was slightly more than 6000 bbl., the lowest figure since 1916. Approximately 5500 bbl. was produced from the "Mississippi lime" in Scott and Morgan Counties. The remainder was from two wells each in Clay and Fentress Counties. Thirty million cubic feet of gas was marketed off the lease in Morgan County and about 10 million cubic feet was produced in the Jamestown field in Fentress County. The production of oil by counties is shown in Table 1.

Jan 1, 1946

By David T. Day

In 1897 I published a proposed explanation for the variation in color and specific gravity of Pennsylvania oils. A resume of this subject mas also presented at the First International Petroleum Congress, in Paris, in 1900. Since that time

Jan 1, 1911

By Thomas M. Drown, P. W. Shimer

THE precipitation of phosphoric with titanic acid, by boiling an iron solution which had been reduced to the ferrous condition by sulphuretted hydrogen or sulphurous acid, was first noticed by E. H. Bogardus in 1874.* Since that time, as far as we are aware, not much has been published on the relation- of these two acids to each other, and to silicic acid, in the ordinary course of analysis of iron ores. The following investigation may perhaps aid in clearing up some of the obscure points in the analysis of titaniferous ores. THE DETERMINATION OP PHOSPHORUS. From two to five grams of the finely powdered ore are weighed into a beaker and treated with about 50 c.c. of hydrochloric acid (sp. gr. 1.12), evaporated to dryness, and heated in an air-bath for * American Journal of Science, III, 8, p. 334.

Jan 1, 1882

By T. M. Drown, P. W. Shimer

The precipitation of phosphoric with titanic acid, by boiling an iron solution which had been reduced to the ferrous condition by sulpharetted hydrogen or sulphurous acid, was first noticed by E. H. Bogardus in 1874.* Since that time, as far as we are aware, not much has been published on the relation of these two acids to each other, and to silicic acid, in the ordinary course of analysis of iron ores. The following investigation may perhaps aid in clewing up some of the obscure points in the analysis of titaniferous ores. THE DETERMINATION OF PHOSPHORUS. From two to five grams of the finely powdered ore are weighed into a beaker and treated with about 50 c.c. of hydrochloric acid (sp. gr. 1.12), evaporated to dryness, and heated ih an air-bath for

Jan 1, 1882

FINANCE COMMITTEE OF THE BOARD OF DIRECTORS Erie V. Daveler, Chairman A B. Kinzel Gail F. Moulton INVESTMENTS ErIe V. Daveler, Chairman W L. Kleitz, '52 Henry Krumb, '53 Joseph E. Pogue, '51

Jan 1, 1952

By D. F. Coolbaugh

Asia, the largest and most populous continent, has had little political influence on world affairs until very recently. The picture is rapidly changing. Although the cultures of various Asian countries differ widely, today they are united in their desire to industrialize. This desire is the key for expansion of Asian mineral production. The following discussion deals primarily with the situation in the south and southeast Asian countries -India, Pakistan, Burma, Thailand, Cambodia, Laos, South Vietnam, Malaya, and Indonesia.

Jan 10, 1960

By Robert H. Richards

VERY little has been published recently on this subject in the mining journals or proceedings of societies. The attention of experts has been diverted perhaps by the demands for pan amalgamation of refractory ores. Yet free milling ores occur in many localities, and it may be interesting to have on record some data as to details of running a small test-mill, especially as details of results do not seem to be accessible to students and investigators. Küstel, in 1863, under battery amalgamation, dismisses the subject by stating that "amalgamation on copper-plated platforms, troughs, and other copper fixings" is " very imperfect, and mostly abandoned." J. Arthur Phillips says, in 1867, under placer mining : A well-amalgamated copper plate is considered as effective for

Jan 1, 1880

By R. M. Wilhelm

HIGH-TEMPERATURE thermometry,, as treated in this paper, deals with the measurement of temperature in the range 100° to 550° C. The lower limit corresponds to the temperature of boiling water at normal atmospheric pressure, the upper limit is approximately the highest temperature to which mercury in a glass thermometer may be safely subjected.1 In this range., the domains of pyrometry and thermometry overlap somewhat, for high-temperature resistance thermometers and thermocouples generally classed as pyrometers are often used below 550° C. This paper will be confined to high-temperature mercurial thermometers, and indicating and recording thermometers of the vapor pressure, liquid or gas filled, and bimetallic or graphite-metal expansion types, a classification of which is as follows: CLASSIFICATION OF THERMOMETERS GENERAL CLASSIFICATION SUBDIVISIONS Mercury in glass Laboratory- Etched or engraved stems (mercurial) Enclosed scale (Einschlus) Industrial Vapor pressure Indicating and Pressure Liquid filled recording Gas filled Bimetallic Graphite-metal expansion

Jan 9, 1919

Jan 1, 1946

By E. A. Gulbransen, K. F. Andrew

The gas-metal reactions of zirconium are very interesting. The metal is extremely stable at room temperature to reactions with the several gases present in air and the metal will stay bright indefinitely. However, at temperatures of several hundred degrees higher the metal reacts readily with oxygen, nitrogen and hydrogen. This behavior, in addition to the fact that zirconium is one of the higher melting point metals which might have high temperature applications under the proper conditions, resulted in the work reported in this communication. There are several factors which indicate that zirconium might have good oxidation resistance at elevated temperatures. These are: (1) the high melting point of approximately 1860°C, (2) the high melting point of the oxide of approximately 2675°C, (3) the high degree of thermodynamic stability of the oxide to chemical reaction and the low decomposition pressure of the oxide and (4) the possible formation of a continuous oxide film since the volume ratio of oxide to metal is greater than unity. The unfavorable factors are: (1) the metal reacts to form nitrides, hydrides and carbides, (2) the oxide is soluble at elevated temperatures in the metal and (3) the oxide ZrO2 undergoes crystal structure transformations at high temperature. The oxidation resistance of this metal is not only a question of the rate of film formation but is complicated by the fact that the oxide and other reaction products dissolve in the metal which in turn will affect the physical and mechanical properties of the metal. The protection of the metal to nitride formation must be considered separately from the oxide problem. One unfavorable factor is that the volume ratio of the nitride to the metal is about unity. This indicates that a discontinuous film might be formed. This paper will present measurements on the rates of reaction of the metal with O2, H2 and N2 over a wide temperature and pressure range. The reaction in high vacuum and the stability of the several compounds formed will be presented. The results are correlated with fundamental rate theory and with the physical and chemical structure of the metal and film. Literature Although many papers have been published on the chemical reactions of zirconium with various gases, comparatively few are concerned with the protective nature of the metal and its reactions at normal pressures. The studies in the pressure range below 0.01 mm of Hg gas pressure are largely of interest in the nature of the adsorption of gases by hot filaments in high vacuum apparatus. The reactions of zirconium in this pressure range have been reviewed by Fast8 and by RaynOr.27 In spite of certain differences of opinion as to the maximum adsorption temperatures for various gases, the low pressure range is qualitatively understood. Some of these papers will be mentioned briefly here. 1. LOW PRESSURE Ehrke and Slack' find that oxygen reacts above 885°C and hydrogen above 760°C. Nitrogen does not react up to a temperature of 1527°C. Fast9 on the other hand observes that oxygen is absorbed above 700°C and nitrogen at temperatures exceeding 1000°C. Hydrogen is absorbed from 300" to 400°C and liberated between 500" and 800°C. It is readsorbed at 862°C and released above 862°C. Hukagawa and Nambo22 find a rather complicated picture for the absorption of oxygen. A rapid initial absorption is found between 180" to 230°C. Further oxygen is not taken up until a temperature of 450°C is reached. The optimum temperature for complete absorption is 650" to 700°C. Nitrogen is found to be completely adsorbed at 600°C. However some of the gas is evolved at higher temperatures. Their data on the absorption of hydrogen indicate some of the gas is removed at 550°C. Guldner and Wooten17 in a study of the low pressure reactions of zirconium with various gases observed that the reaction with oxygen occurs at temperatures above 400°C and that the oxide is formed. The reactions with carbon monoxide and carbon dioxide occur rapidly at temperatures of about 800°C with the oxide and carbide being formed. Zirconium reacts at temperatures of 400°C slowly and at 800°C rapidly to form the nitride and with hydrogen and water at 300°C to form the hydride and a mixture of the oxide and hydride respectively. 2. NORMAL PRESSURE DeBoer and Fast3 in a study of the electrolysis of oxygen in zirconium find that the metal absorbs up to 40 at. pct of oxygen without forming a new phase. The solubility of nitrogen in the lattice has been studied by de Boer and Fast4 and Fast10 and is found to be considerable. At higher temperatures the oxide dissolves in the lattice at an appreciable rate according to Fast10 and the zirconium surface becomes active. De Boer and Fast4 and Hägg18 have studied the solubility of hydrogen and find that at room temperature the solubility corresponds to ZrH1.95 Desorption occurs on lowering the pressure. Hydrogen is stated to be more soluble in the ß-form and the

Jan 1, 1950

By C. W. Spencer, K. A. Semlak, F. N. Rhines

IN an effort to obtain a better understanding of sintering in the presence of a liquid phase, it was decided to study the rate of capillary rise of a relatively low melting liquid metal in a higher melting metal powder compact. By assuming that the metal powder compact consists of a great number of parallel capillary tubes and that the flow of liquid

Jan 1, 1958

By R. H. Terhune

THE enormous production of pig-iron, together with the many difficult and interesting problems with which its manufacture is fraught, 11as secured to this industry the exclusive attention of scientists with reference to the chemistry of iron, while some of the minor departments of its metallurgy have suffered neglect. Particularly is

By W. M. Pierce

CORRUGATED sheet zinc has been used abroad for a great many years as a roofing material. In this country it has been in use for about 10 years. From the outset it was recognized that zinc sheets required closer spacing of the supporting purlins than steel sheets. Exact data regarding safe maximum fiber stresses were not available, however, and on occasions the span used was excessive and the sheets sagged. This paper describes both service and laboratory tests to determine safe maximum fiber-stress values for various grades of zinc for use in calculating the proper purlin spacings for any gage and profile under given loading conditions. These tests consist of laboratory loading tests on full-size roof sections over extended periods of time; of actual roof installations erected in conformity with the indications of the laboratory tests and observed over a period of years; of careful determinations of the apparent elastic limit of several grades of zinc, and finally of static tests1 (so-called creep tests) to determine the rate of flow of zinc under a variety of static tensile stresses at definite temperatures. Certain of the individual tests extended over a period of more than two years.

Jan 1, 1929

By Robert L. Akre

When Marco Polo visited China in the 13th century, no one knew what black powder was except the Chinese: they knew enough to make dazzling fireworks with it. But the realization that black powder could also do useful work came much later and, like all important discoveries, it altered the course of history. It was in the 14th century that black powder was first used to break rock in a very crude way: there were no drills and the powder was simply poured into cracks and exploded by setting it afire. Because its energy value was pretty low, the need for something more powerful was felt when the industrial revolution arrived.

Jan 6, 1976

By P. D. Wilson

The Province of British Columbia covers 382,000 sq. mi., about 250,000 sq. mi. of which have not been prospected. In fact, the coast country and the islands are so heavily timbered and the surface covered with so thick a mantle of soil, muskeg, and, over broad areas, glacial drift, that prospecting and even trail breaking are extremely difficult. It is only along the coast or stream channels, or above the timber line, or where snow or rock slides have scoured the surface, that rock outcrops can be found. Glaciers nestle in many of the cirques and fill the valleys in the higher ranges. Great ice sheets and perpetual snow persist in certain localities, thus reducing the exposed areas worth prospecting. Almost the entire country has been subjected to intense glaciation, so that the conspicuous oxidized outcrops of orebodies typical of the southwestern United States and Mexico do not exist and surface bodies of enriched or oxidized ore are rare. With few exceptions, the mines1 of the Province are working primary ore. Development, have proved that some of these orebodies are large and important, although usually comparatively low in grade. Besides the few mines that have produced most of the minerals, there are many small mines, but their total output is unimportant. Considering the number of mines and prospects and the widespread mincralization, it is strange that no really great mines, comparable in sizc and richness with those in the western United States, have been found. The deposits that most closely approach the status of great mines are

Jan 1, 1923

By P. D. Wilson

The Province of British Columbia covers 382,000 sq. mi., about 250,000 sq. mi. of which have not been prospected. In fact, the coast country and the islands are so heavily timbered and the surface covered with so thick a mantle of soil, muskeg, and, over broad areas, glacial drift, that prospecting and even trail breaking are extremely difficult. It is only along the coast or stream channels, or above the timber line, or where snow or rock slides have scoured the surface, that rock outcrops can be found. Glaciers nestle in many of the cirques and fill the valleys in the higher ranges. Great ice sheets and perpetual snow persist in certain localities, thus reducing the exposed areas worth prospecting. Almost the entire country has been subjected to intense glaciation, so that the conspicuous oxidized outcrops of orebodies typical of the southwestern United States and Mexico do not exist and surface bodies of enriched or oxidized ore are rare. With few exceptions, the mines1 of the Province are working primary ore. Development, have proved that some of these orebodies are large and important, although usually comparatively low in grade. Besides the few mines that have produced most of the minerals, there are many small mines, but their total output is unimportant. Considering the number of mines and prospects and the widespread mincralization, it is strange that no really great mines, comparable in sizc and richness with those in the western United States, have been found. The deposits that most closely approach the status of great mines are

Jan 1, 1923