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By J. E. Hackford

IN SOME research. work carried out by the writer, certain results have bean obtained which bear on the fundamental nature and origin of coal and the relationship between coal and petroleum. Without entering into a discussion of the details of the experiments, which were conducted on petroleum and derived bitumens, there are given here, by way of definition, some of the relations that the writer has established between certain classes of bitumens of petroliferous origin. Bitumen.-A natural organic substance, gaseous, liquid, or solid, consisting of hydrocarbons and the oxy- or thionic derivatives of the same, or of a mixture of all three. Diasphaltenes.-Those portions of bitumens that are soluble, in ether or carbon disulfide, but are insoluble in a mixture of equal parts of ether and alcohol. Diasphaltenes are produced by the oxidation or thionization of petroleum oils; they have, as the name indicates, twice the molecular weight of asphaltenes, into which they are converted when subjected to moderate temperature. For example, an artificially produced diasphaltene, which was readily soluble in pentane and ether, was quite insoluble in either of these solvents after heating for three weeks at a temperature of 100° C., and was converted into an insoluble asphaltene. Asphaltenes.-Those portions of bitumen that are insoluble in ether or ether alcohol but are soluble in carbon disulfide. Asphaltites.-Those solid or semisolid natural bitumens that are composed, for the most part, of asphaltenes or diasphaltenes. A pure asphaltite1 would be composed wholly of asphaltenes and diasphaltenes, but most asphaltites contain small percentages of oil and wax, which have not yet been converted into asphaltenes; they may also contain a small percentage of kerotenes, which represent the next stage of the metamorphosis of asphaltenes. Among the naturally., occurring oxyasphaltites may be mentioned grahamite; and among the thioasphaltites, gilsonite.

Jan 8, 1920

By T. P. Floridis

It was deemed desirable to obtain an understanding of the vacuum desulfurization process. McKechnie1 has reported that the sulfur content of nickel- and cobalt-base alloys is reduced in vacuo. Keverian and Taylor2 have observed that vacuum melting causes desulfurization of iron-carbon-silicon alloys. Garnyk and samarin3 have desulfurized transformer steel by vacuum treatment. Experiments were conducted in order to investigate the desulfurization of liquid iron under reduced pressures, and to establish the effect of some alloying elements, and various crucible materials. A vacuum-induction furnace of 50-lb capacity was used. The charge was Armco iron. Silicon was added as 90 pct ferrosilicon, carbon as electrode graphite, and aluminum as high-purity aluminum metal. Magnesia and silica crucibles were used, their inside diameters were 5 1/2 and 5 3/8 in., respectively. The temperature was measured with an optical pyrometer and it was held at 1600 1 15°C. Samples were withdrawn with quartz tubes of 6 mm ID, without disturbing the furnace atmosphere. Pressures were measured with an alphatron gage. The experimental results are shown in Fig. 1. They indicate that: 1) Sulfur can be removed from liquid iron alloys by vacuum treatment; 2) The desulfurization is enhanced by the presence of silicon, carbon, and aluminum, all these elements increase the activity of sulfur dissolved in liquid iron;4 3) The pronounced effect of silicon indicates that probably a volatile silicon sulfide is formed, Alcock and Richardson5 have observed a similar phenomenon; 4) The same rate of desulfurization was obtained when the metal was contained in either magnesia or silica crucibles. Dr. J. Keverian has contributed many discussions and recommendations. M. S. Sutliff has helped in conducting the heats. The permission of General Electric Co. for this publication is gratefully acknowledged.

Jan 1, 1960

By A. S. Yue

It was deemed desirable to obtain an understanding of the vacuum desulfurization process. McKechnie1 has reported that the sulfur content of nickel- and cobalt-base alloys is reduced in vacuo. Keverian and Taylor2 have observed that vacuum melting causes desulfurization of iron-carbon-silicon alloys. Garnyk and samarin3 have desulfurized transformer steel by vacuum treatment. Experiments were conducted in order to investigate the desulfurization of liquid iron under reduced pressures, and to establish the effect of some alloying elements, and various crucible materials. A vacuum-induction furnace of 50-lb capacity was used. The charge was Armco iron. Silicon was added as 90 pct ferrosilicon, carbon as electrode graphite, and aluminum as high-purity aluminum metal. Magnesia and silica crucibles were used, their inside diameters were 5 1/2 and 5 3/8 in., respectively. The temperature was measured with an optical pyrometer and it was held at 1600 1 15°C. Samples were withdrawn with quartz tubes of 6 mm ID, without disturbing the furnace atmosphere. Pressures were measured with an alphatron gage. The experimental results are shown in Fig. 1. They indicate that: 1) Sulfur can be removed from liquid iron alloys by vacuum treatment; 2) The desulfurization is enhanced by the presence of silicon, carbon, and aluminum, all these elements increase the activity of sulfur dissolved in liquid iron;4 3) The pronounced effect of silicon indicates that probably a volatile silicon sulfide is formed, Alcock and Richardson5 have observed a similar phenomenon; 4) The same rate of desulfurization was obtained when the metal was contained in either magnesia or silica crucibles. Dr. J. Keverian has contributed many discussions and recommendations. M. S. Sutliff has helped in conducting the heats. The permission of General Electric Co. for this publication is gratefully acknowledged.

Jan 1, 1960

By Geo. H. Ashley

The following paper is intended to be suggestive only, and to open the way for discussion and further observation. Its preparation was requested only two days before the time limit set for the submission of the papers comprising this symposium. Thus no time existed for detailed studies, so it is largely a memorandum of such facts as have come incidentally to the notice of the writer in the study of coal in the field. The field study of sulfur in coal has received very little special attention or description from coal student's. The presence of sulfur concretions is noted in hundreds of descriptions, and certain benches of a coal bed may be described as "sulfury" or the presence and position of sulfur bands may be noted in coal sections in connection with sampling. It may be accepted that some sulfur is present in all coal. The amount varies greatly in different regions, in different beds, and in the same bed in different areas. The anthracite of Rhode Island comes the nearest of any coal known to the writer of being free from sulfur, several analyses of that coal showing less than 0.1 per cent. Subbitumi-nous coals in Colorado in a few places have close to 0.2 per cent. of sulfur on the dry-coal basis and in other states subbituminous coals approach this lower limit. Bituminous coals seldom run under 0.4 per cent. of sulfur on the dry basis, though in a few places dry bituminous coals in Colorado and Washington have between 0.3 and 0.4 per cent. The better known bituminous coals have almost everywhere over 0.4 per cent. The best of the Pocahontas and New River coals run close to 0.4 per cent., but there is very little commercial coal in Pennsylvania, Ohio, Indiana, Illinois, Kentucky, or the other states, that runs under 0.5 per cent. on the dry basis. From these minimum figures, the amount will range up to 5 or 6 per cent. or higher if visible sulfur is not excluded. It must be remembered that the usual analysis of a coal bed is not intended to give the total proportion of sulfur in the bed but the amount in the coal after the removal of the more obvious and larger sulfur masses. Professor Parr has already pointed out that, chemically, sulfur occurs in several forms: as pyrite, organic sulfur, sulfates, and possibly as un-combined sulfur. Sulfur in the form of sulfates is commonly the obvious result of the weathering of pyrite and may be found in the coal within .

Jan 1, 1920

By Ruder, W. E.

CONSIDERABLE interest has been shown lately in various types of furnaces for the production of high, temperatures, both for laboratory purposes and for small industrial uses. Dr. J. A. Harker1 described certain modifications of the Arsem graphite resistance helix for high-temperature work at the National Physical Laboratory. Dr. Northrup ,also has developed two interesting forms of high-temperature furnaces. In 1911, Messrs. Winne and Dantsizen2 described two forms, of resistance furnaces using ductile molybdenum or tungsten as resistors. Since the discovery, by this laboratory, of methods for producing these metals in ductile form, their use as resistance elements in the research laboratory of the General Electric Co. has grown to such an extent that they are now almost indispensable. These furnaces are used here for alloy research, annealing, heat-treating, and practically all f the thermal processes requiring temperatures above 900° C. Various types of furnaces have been developed to meet the general needs of laboratory work, and it is the purpose of this paper briefly to describe some of these furnaces. A tubular furnace wound with a metallic resistor is the simplest type to construct, and almost every laboratory has made such furnaces. The only essential difference between a furnace wound with platinum or base metal and one wound with tungsten or molybdenum is that the coils of the latter must be heated in a neutral or reducing atmosphere. It has long been our custom here to build our resistance furnaces with a metallic casing from which the tube could be easily removed for rewinding. The heat-insulating material-usually calcined magnesia, alumina, silica, or silex, depending upon the nature of the resistor-is used in powdered form so that it can he readily removed and replaced. In order to adapt this method to tungsten or molybdenum windings, it

Jan 2, 1918

IN general in making such powders, all kinds of gravel, tuff, washed river silt, and similar earths whose grain is fine and lean by nature are good for this operation of casting, either by themselves or in mixture because they are disposed to receive the metals well on account of a certain dryness which they possess. Many kinds are also compounded by means of art. Of these, I shall proceed to tell of all those that experience [119] has taught me to recognize as good. But first I desire that we return to speak of the natural ones because they are real earths and can always be had wherever one may be, and in the necessary quantity. They please me greatly because they are easy to reduce on account of their disposition. A loam is made from these and mixed by beating with wool-cloth cut- tings, spent wash ashes, and horse dung. This is made into cakes and dried. These are then put to bake in a furnace or in some other way and, in fact, are baked very well. Then it is pounded and sifted with a fine sieve, or it is ground in a potter's color mill, or by hand on a porphyry with water, to the fineness that the craftsman desires, or as fine as he can make it. When it has been ground it is again drained free from water and dried out with fire. Then as much magistery of salt is taken as will moisten it. It is dried and pounded again and passed through a sieve. When it has been made as desired in this way it is moistened again before use with water, urine, or vinegar just enough so that it holds together when it is squeezed in the fist. Then, when it has been brought to this point, it is moulded as you will hear. Powders are also made of crushed brick, tripoli, vine ashes, tiles, and glazed drainpipes, or burned emery, calcined tin, straw, and of burned paper and horse dung as well as of young ram's-horn ashes and many other things. The goodness of all these depends on three things; namely, on receiving the metal well, on being so fine as to be almost impalpable, and on their being made .with a magistery that renders them hard and strong when they are dry. In addition to these powders I have used another when I needed it, and it has succeeded well every time I made it. To make this. I have taken I two parts of pumice and one of iron scale and ground them on the por-

Jan 1, 1942

By Howard 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 forma-tion and in age-hardening systems. Most of the work has been confined to ferrous alloys1-9t although two investigations have been made on copper alloys10,11. That such work may be of considerable, practical importance has been demonstrated by Bain12, by the workers at the Kaiser Wilhelm Institut fur Eisen-forschung13,14, and by the everyday use of precipitation and age-harden-inn 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. Daven-port 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 G. M. Schwartz, G. A. Thiel

Dimension stone was first quarried in Minnesota in 1820 and a very active industry has grown up over the years. The main basis of the present industry is a wide variety of igneous rocks sold under the general trade name of "granite." Also of considerable importance is the Ordovician dolomite sold under the locality names, Man kato, Kasota and Winona. THE first record of the quarrying of dimension stone in Minnesota dates back to 1820 when limestone was quarried locally for part of old Fort Snel-ling. Limestone quarries were operated at Stillwater, Mankato, and Winona as early as 1854. Granite was quarried first at St. Cloud in 1868, and within a few years thousands of tons were shipped to widespread points. Rough dimension stone for large buildings furnished the first important market, but beginning in 1886 paving blocks were in demand. The largest shipment was in 1888, when 1925 cars were shipped from the St. Cloud area. Quartzite was quarried first at New Ulm in 1859 and somewhat later at Pipe-stone and elsewhere in southwestern Minnesota. The productive dolomite quarries at Kasota were opened first in 1868 and have continued as large producers of a variety of stone to the present time. At present, the industry is controlled by relatively few operators, and for that reason detailed figures on dimension stone are not released for publication. A general idea may be obtained from the data in the Minerals Yearbook for 1948. The figures for total stone produced in Minnesota are 1,804,000 tons valued at $5,090,652. Probably the largest item in the latter figure is received from dimension stone. A better idea of the situation in relation to the country as a whole may be gained by using the data for 1930 when more companies were operating in Minnesota, and complete figures were published. In that year Minnesota produced granite valued at $2,668,119 and ranked third among the states in value. Minnesota's production of granite was almost exclusively for dimension stone. In the same year Minnesota produced 300,000 tons of limestone (dolomite) valued at $840,860, and this likewise was mainly dimension stone. In finished limestone Minnesota ranked second among the states in 1930. Sandstone and minor amounts of quartzite are the only other dimension stones that have been produced in Minnesota, but the quarries are now inactive. The commercial stones of Minnesota have been described in two reports by Bowlesl and by Thiel and Dutton. The early history of quarrying in Minnesota and extensive notes on the various rocks are given by N. H. Winchell.8 Small limestone and dolomite quarries were numerous throughout the area of Paleozoic rocks in southeastern Minnesota. Early production was largely dimension stone. With the increased use of Portland cement, most of these ceased production, and today only those at Kasota and Winona remain in operation. In recent years many quarries have reopened and new ones started, but these are devoted to the production of crushed rock and agricultural lime. As the application of modern quarrying and finishing methods increased, small companies in the granite business have dropped out, and the remaining companies have modernized their plants, purchased old quarries, and opened up new ones, thus furnishing a wide variety of granites suitable for most of the customary uses. It is the purpose of this review to present notes on the geology and operations of each of the quarries now operating within the state. Granites and Related Igneous Rocks The term granite as used in this report includes granites, gneisses, diorites, gabbros, and other igneous rocks. The granites of greatest economic importance are found in three widely separated regions, see Fig. 1. 1—Central Minnesota in the region of the city of St. Cloud, 2—the upper Minnesota River valley region, 3—the northeastern portion of the state, commonly referred to as the Arrowhead region. The St. Cloud Region: The rocks of the St. Cloud region are mainly granites and related rock types such as monzonites and quartz diorites. The stones may be grouped into three major types, namely, pink granite, red granite and gray granite. Most of the pink granite occurs in the area to the southwest of St. Cloud. The rock is best described as stone with large pink crystals set in a finer grained black and white background. The minerals of the matrix occur in remarkably uniform sizes, and the pink crystals are sufficiently uniform in their dis-

Jan 1, 1953

By G. M. Schwartz, G. A. Thiel

Dimension stone was first quarried in Minnesota in 1820 and a very active industry has grown up over the years. The main basis of the present industry is a wide variety of igneous rocks sold under the general trade name of "granite." Also of considerable importance is the Ordovician dolomite sold under the locality names, Man kato, Kasota and Winona. THE first record of the quarrying of dimension stone in Minnesota dates back to 1820 when limestone was quarried locally for part of old Fort Snel-ling. Limestone quarries were operated at Stillwater, Mankato, and Winona as early as 1854. Granite was quarried first at St. Cloud in 1868, and within a few years thousands of tons were shipped to widespread points. Rough dimension stone for large buildings furnished the first important market, but beginning in 1886 paving blocks were in demand. The largest shipment was in 1888, when 1925 cars were shipped from the St. Cloud area. Quartzite was quarried first at New Ulm in 1859 and somewhat later at Pipe-stone and elsewhere in southwestern Minnesota. The productive dolomite quarries at Kasota were opened first in 1868 and have continued as large producers of a variety of stone to the present time. At present, the industry is controlled by relatively few operators, and for that reason detailed figures on dimension stone are not released for publication. A general idea may be obtained from the data in the Minerals Yearbook for 1948. The figures for total stone produced in Minnesota are 1,804,000 tons valued at $5,090,652. Probably the largest item in the latter figure is received from dimension stone. A better idea of the situation in relation to the country as a whole may be gained by using the data for 1930 when more companies were operating in Minnesota, and complete figures were published. In that year Minnesota produced granite valued at $2,668,119 and ranked third among the states in value. Minnesota's production of granite was almost exclusively for dimension stone. In the same year Minnesota produced 300,000 tons of limestone (dolomite) valued at $840,860, and this likewise was mainly dimension stone. In finished limestone Minnesota ranked second among the states in 1930. Sandstone and minor amounts of quartzite are the only other dimension stones that have been produced in Minnesota, but the quarries are now inactive. The commercial stones of Minnesota have been described in two reports by Bowlesl and by Thiel and Dutton. The early history of quarrying in Minnesota and extensive notes on the various rocks are given by N. H. Winchell.8 Small limestone and dolomite quarries were numerous throughout the area of Paleozoic rocks in southeastern Minnesota. Early production was largely dimension stone. With the increased use of Portland cement, most of these ceased production, and today only those at Kasota and Winona remain in operation. In recent years many quarries have reopened and new ones started, but these are devoted to the production of crushed rock and agricultural lime. As the application of modern quarrying and finishing methods increased, small companies in the granite business have dropped out, and the remaining companies have modernized their plants, purchased old quarries, and opened up new ones, thus furnishing a wide variety of granites suitable for most of the customary uses. It is the purpose of this review to present notes on the geology and operations of each of the quarries now operating within the state. Granites and Related Igneous Rocks The term granite as used in this report includes granites, gneisses, diorites, gabbros, and other igneous rocks. The granites of greatest economic importance are found in three widely separated regions, see Fig. 1. 1—Central Minnesota in the region of the city of St. Cloud, 2—the upper Minnesota River valley region, 3—the northeastern portion of the state, commonly referred to as the Arrowhead region. The St. Cloud Region: The rocks of the St. Cloud region are mainly granites and related rock types such as monzonites and quartz diorites. The stones may be grouped into three major types, namely, pink granite, red granite and gray granite. Most of the pink granite occurs in the area to the southwest of St. Cloud. The rock is best described as stone with large pink crystals set in a finer grained black and white background. The minerals of the matrix occur in remarkably uniform sizes, and the pink crystals are sufficiently uniform in their dis-

Jan 1, 1953

SINCE I have mentioned the art of alchemy in. many parts of this treatise of mine, especially when 'came to the description of the practice of various operations,* I do not here intend to argue as to whether it may be called true or not. But in case it is true, inasmuch as it is seen in operation to be a result dependent on the actions and virtues of fires, I should not pass by in silence without speaking at all of this art here, nor would I wish to do so, especially since I think that you do not really know what it is except in so far as common report is heard everywhere to the effect that whoever carries it to completion makes silver and gold with it. Because of this belief, many seek it with much time, labor, and expense, as I know you have often heard related, if not elsewhere, by me in the chapter on gold that I have written in this volume. Now do not think that I wish to teach you this art here, for I am one of those who do not know it. Therefore I shall tell you here, so that you may know more, only. that those workers who so eagerly follow after and seek it proceed by just two pathways. One is that which takes its enlightenment from the words of the wise philosophers, by means of which they think to attain it. This they call the just, holy, and good way, and they, say that in this they are but imitators and assistants of Nature, indeed, manipulators and true physicians-of .mineral bodies, purging them of superfluities and assisting them by augmenting their virtue and freeing them from their defects. In this way they sometimes proceed to corrupt these bodies in order to be able to separate the elements they contain so as to reduce them, if possible, to their primary materials, as they call them, or sometimes they convert them into new substances by means of this art or by adding another spirit different from the first one. Thus they seek in this way to bring these materials to a certain point of corruption or to a separation of elements, or to remove or add spirits to things, or to make coarse materials subtle and sometimes to make subtle materials coarse. Therefore, as you can understand, these persons, with bridle broken, run a circular track night and day, without ever having rest; and surely I do not know whether anyone has ever arrived at the desired goal. Nevertheless, even though the goal of this art were emptiness, as many

Jan 1, 1942

By Frederic Lahee

THE total production of crude oil in Texas during 1924 was said to be 133,613,985 bbl. as compared with 125,991,628 bbl. in 1923.1 Subtracting from these figures the yield of the Gulf Coast fields, there remains, for the other part. of Texas, a yield of 106,272,573 bbl. in 1924, as compared with 101,931,595 bbl. in 1923. This represents an increased, production of over 4,250,000 bbl. for all of Texas outside of the Gulf Coast or Salt Dome fields. Within this same region, in 1924, there were 3624 completions, of which 2352 were oil or oil and gas wells, 7 were gassers, and 1265 were dry holes. Thus, nearly 35 per cent. of the completions were dry holes. In 1923, there were 4134 completions, with 2853 oil or oil and gas wells, 2 gas wells, and 1279, or 31 per cent. of the total, dry holes. Outside of the Gulf Coast region, six major pools were discovered and developed in 1924.; two pools, previously discovered, were extended far beyond their limits at the end of 1923, and many smaller pools were opened. The major pools were the Big Lake field, in Reagan Co., the New Richland field, in Navarro Co., the Harmel, Carey, and Ragle pools, in south Archer County, and the Wortham field, in Freestone and Limestone Counties. Fields that were notably extended were the Panhandle producing area and the Luling field. Many wildcat wells have been drilled; most -of these were failures, but several opened .pools and several have had sufficiently favorable results to. lead to further drilling. The activity of the operators in searching for new production was very intense during 1924, and indications point to as feverish a campaign during the coming year. This will be stimulated by rising prices for crude oil. There are good reasons for believing that new pools will be discovered along the Mexia fault zone, in Archer, Young, Baylor, and Throckmorton Counties, in the great central region of Texas where we now have the Mitchell County and Reagan County pools, and very likely in the eastern Red River Counties including Cooke and Grayson. On the other hand, with the opening of the year, there is no new big pool in sight. An outstanding feature of the production end of the business is the increasing reliance placed on geological work and geological recommendations. Not in five or six years has there been such a demand for first-class geologists.

Jan 3, 1925

By E. M. Wise

THE practice of dentistry, particularly the construction of artificial dentures and "bridges," involves a unique and difficult application of the precious-metal alloys. Appliances used in the mouth are continuously exposed to corrosive agencies which can hardly be described as mild, and must remain free from tarnish and be substantially immune to corrosion. Limitations with respect to space and weight demand high physical properties, while complexity of form requires ease of working. The high corrosion resistance required necessitates the use of alloys of high precious metal content. The usual expedient of resorting to mechanical working to produce the requisite strength and stiffness cannot be utilized because of the frequency of annealing and soldering operations. To meet these difficult conditions manufacturers of dental goods were early led, unknowingly perhaps, to the production of precipitation-hardening or temperable alloys. The excellent properties of iridium-platinum may have suggested the addition of platinum metals to the conventional gold-silver-copper alloys to produce greater strength and hardness. It was found that such quarternary alloys retained their high physical properties after passing through the usual soldering process; i, e., heating to 7500 to 8000 C. and cooling naturally in the air. Later it was discovered that they could be softened and rendered more ductile by heating to the same temperature and quenching, in water. These early examples of precipitation hardening, for years the common knowledge, of dental practitioners and laboratory technicians, escaped the attention of the scientific world and discovery of the transformation which was responsible for this hardening was discovered by the Russian investigators of the system Au-Cu, Kurnakow, Schemtschushny and Zasedatelev,(1) § although the optimum conditions for securing good properties in aged alloys were not given attention.

Jan 1, 1932

By J. E. Andersen, J. Halpern, C. S. Samis

In the presence of oxygen, galena is oxidized in an aqueous medium containing sodium hydroxide, in accordance with the following reaction: PbS + 2O2 + 3OH ? HPbO2 + SO4 = + H2O A novel method was devised for following this reaction which takes place in an autoclave under oxygen pressure, by measuring the concentration of HPbO2- in the solution with a cathode ray polarograph employing stationary platinum electrodes. Using this procedure a study was made of the kinetics of the reaction, in which the effect of a number of variables, including temperature, oxygen pressure, NaOH concentration, and agitation, on the rate, were determined. The results of this study are described and discussed, in terms of possible mechanisms for the reaction. IT is known that sulphide minerals can be oxidized in aqueous media in the presence of oxygen under pressure. Reactions of this type can be classified in two categories depending upon whether the products of oxidation are insoluble or soluble in the aqueous medium. An example of the first type of reaction is the oxidation of pyrite in alkaline solutions, giving rise to an insoluble iron oxide. The kinetics of this reaction have been investigated and its mechanism established.' It has been applied in the oxidation of iron sulphides present in refractory gold ores to improve the subsequent recovery of gold by cyanida-tion.' The second type of reaction finds application where it is desired to recover the metal by leaching during oxidation. In this case a medium is selected in which the oxidized mineral is soluble. For example, nickel, copper, and cobalt sulphide ores can be treated by oxidation in the presence of a solution of ammonia dissolving the nickel, copper, and cobalt as the metal ammine sulphate salts.:' A similar treatment has also been reported to apply to zinc sulphide ores.' It is known that lead sulphate is soluble in solutions of sodium hydroxide or ammonium acetate. It should therefore be possible to dissolve the lead from galena ores by aqueous oxidation with oxygen under pressure using either of these solutions. The applicability of the ammonium acetate treatment has been investigated and confirmed in a recent study.' The present paper describes the results of a similar study in which the kinetics of the oxidation of galena in sodium hydroxide solutions have been investigated. The object of this investigation was pri- marily to obtain information of a fundamental nature relating to the kinetics and mechanism of this reaction. The use of pulps of comminuted ore in a study of this type is undesirable because of the difficulty in controlling and measuring the surface area. The measurements were therefore made using galena crystals of measured surface area and in this way absolute reaction rates were obtained. The reaction was found to proceed as follows: PbS + 2O2 + 3OH ? HPbO2 + SO4 + H2O [I] The products are sodium plumbite and sodium sulphate salts which dissolve in the aqueous solution. The reaction studies were carried out in an autoclave in which a desired pressure of oxygen was maintained. The reaction was followed by measuring the concentration of lead in the solution with a cathode ray polarograph. The results obtained in this investigation are presented and discussed in the present paper. Experimental Materials: The crystals of galena were obtained from Violamac Mines, Sandon, B. C. The following impurities were indicated by spectrographic analysis carried out by the Provincial Assay Office, Victoria, B. C.: Sn, 0.02 to 0.2 pct; Sb, 0.07 to 0.7; Zn, 0.01 to 0.1; Si, Fe, Mg, As, less than 0.05 pct; Ag, 126 oz per ton, the latter determined by standard fire-assaying procedure. After cutting a specimen measuring approximately 5x7x12 mm, the crystal surfaces were ground parallel to the 100 axes using No. 2 emery, washed with water, and the dimensions were measured with a micrometer. Oxygen gas was of commercial grade and supplied in cylinders by Canadian Liquid Air. Solutions were made up with chemicals of chemically pure grade and distilled water. Equipment: Autoclave: The autoclave used in these studies was constructed of stainless steel and

Jan 1, 1954

By John D. Gill

THIS paper assumes the incontrovertible nature of the statement that the validity of competition in the nonnatural resource industries is established firmly on the rate and extent of the economic development of the United States. It then demonstrates the nonexistence of any condition within the petroleum industry that would invalidate the principle of competition as applied to it. It points to the benefits that competition has effected in the oil industry and the reasons why the practice of the competitive principle should continue to keep the industry virile and progressive in meeting the requirements of future generations for the kind of products natural to it. Finally, it pleads for a clearer view of the affairs of the oil industry by seeing them against a background of the whole economy. INTRODUCTION Even a few years ago there would have been only an academic reason for presenting before this Institute a paper on the validity of competition in the oil industry or any other natural resource industry; today there is no more practical subject for this body to consider. In social importance it transcends attempted solutions of perplexing technical problems; and even the numerous legal and economic problems that grow out of administration of state regulatory measures appear to be of secondary importance because they would cease to exist if competition were abolished. The aspiration of certain elements of the Federal Government to acquire control of the oil industry has long been suspected The vital need for petroleum in the national defense ... confirms my belief in the urgent need of Federal legislation to safeguard our petroleum supply through prevention of waste and by establishment and maintenance of sound economic conditions in the oil industry... . But also it may be dismissed with this mere mention of it because it predicates government control and the abandonment or broad reduction of competition on a war emergency. Clearly, the fight for a nation's life may justify a government's control over men and resources that would be abhorrent and economically enervating under conditions of national security. More pertinent to the present matter, because it appears expressive neither of a personal ambition nor of an emergency condition but rather of the long-range view of a certain school of conservationists, is the pronouncement of no less an authority than the Attorney General of the United States, who has been repeatedly quoted by the press as saying that the American Petroleum Industry constituted a case "where the principle of conservation of an exhaustible and irreplaceable resource should replace the principle of competitive exploitation." The significance of this statement in the light of the commonly accepted meanings of the " principle of conservation" and of the "principle of competitive ex-

Jan 1, 1941

By C. G. Dunn

IDENTIFICATION Of the kinds of orientation relationships that may exist among crystals is an important problem in the metallurgical field. As an aid to its solution standard orientations of several orders of twins would be very useful for rapid analyses to discover high-order as well as low-order twin relationships. Although data have been published that give orientations for three generations of twins, these data are not readily useful in the form presented; i.e., in a stereographic projection with one pole per orientation.1 However, accurate data based on calculations of the positions of all {100} planes for such groups would be very useful when presented in tabular form. Therefore, calculations have been made for a group of four orders of twins and the data are listed in Table 3. Illustrative applications are considered briefly, with the idea of pointing out what may be done with large groups of orientations. METHOD OF COMPUTING ORIENTATION OF A TWIN It is common practice to describe the orientation of a crystal in terms of the positions on a stereographic net of the poles of certain planes of the crystal. A single position on a net may be given it terms of two angle variables, two sets of which appear in the following equations: [Polar NetWalff Net x=rsinOocos4pyx=rcos0. y=rsinB,sin4,ny-rsin0.cos¢,, z=rcos0,,z=rsin0.sin4,,] The three numbers x, y and z determine a length r as well as a direction [(0, 0)] in an X, Y, Z coordinate system. In the present case, r will be set equal to (h2 + k2 +12)1/3, where h, k and 1 are the usual Miller indices for a crystallographic plane, a restriction that facilitates determination of the positions of poles of new planes from those of old or known ones,2 as will become evident later. Furthermore, since twinned lattices have certain planes in common, it is an easy matter to determine the orientation of a twin of a crystal if the orientation of the crystal itself is known. We start therefore with a crystal of known orientation (positions of three {100} poles given) and determine where the cube poles occur in first, second, third and fourth-order twins. Methods for identifying twinned lattices and for making the calculations to find the orientation of a twin have been published.3 4 Reference 4 will be illustrated in the calculation of the orientation of a twin, even though this method differs from the one used by the writer in obtaining the following data on four orders of twins. Consider a crystal S and its twin A1, A1 being one of the four {112} or {III}

Jan 1, 1945

By W. M. Rust, W. D. Mounce

The almost universal acceptance of electrical logging by the petroleum industry calls for a critical examination of the physical bases of the common methods. This is particularly needed for the natural potential log. The conventional explanations are based on the phenomena of electrofiltration and electro-osmosis. However, experimental data show that they fail to give a basis that is quantitatively sound. Moreover, they lead to interpretations of details of electrical logs that are erroneous. It was found experimenlally that when a plug of shale is placed in a chain of dissimilar electrolytes, a current flow results. Experiments on oil-well cores and fluids similar to those existing in wells show that potentials are set up which are in reasonable agreement with those encountered in electrical logging. Doubtless other sources of potential are important but this explanation not only accounts for much of the potential but also clarifies some fairly familiar examples of misinterpretations. Introduction The extraordinary value of electrical well logging as a tool for petroleum engineers and geologists is now so universally recognized that it is not necessary to point out the ways in which it can be useful. It is sufficient to mention only the saving that has resulted from the elimination of much coring that would have been necessary under former practices and the considerable additions to reserves resulting from the discovery of sands missed in coring. Paradoxically, the very remarkable success that has resulted from the application of electrical logging to correlation and completion problems has cost some of its most consistent users dearly.' The fact that some operators have placed unwarranted faith in erroneous interpretatioils of electrical logs does not reduce the value of the logs. It should, however, make one pause long enough to ask why experienced users should be misled. The answer to this question is not hard to find. In nearly every case, the fault has been oversimplification. This is illustrated very aptly by the familiar interpretation and theory of the natural potential log. Recording and Interpreting Logs The natural potential log is extremely simple to record precisely enough for all present-day uses. One needs only an electrode, a cable to lower the electrode through the drilling mud, a recording meter and a surface ground connection. The electrode can be elaborate but need not be. A simple brass rod 2 in. in diameter and 2 or 3 in. long is quite satisfactory. The cable need not be particularly well insulated, nor need it have a very low resist-

Jan 1, 1946

By W. M. Rust, W. D. Mounce

The almost universal acceptance of electrical logging by the petroleum industry calls for a critical examination of the physical bases of the common methods. This is particularly needed for the natural potential log. The conventional explanations are based on the phenomena of electrofiltration and electro-osmosis. However, experimental data show that they fail to give a basis that is quantitatively sound. Moreover, they lead to interpretations of details of electrical logs that are erroneous. It was found experimenlally that when a plug of shale is placed in a chain of dissimilar electrolytes, a current flow results. Experiments on oil-well cores and fluids similar to those existing in wells show that potentials are set up which are in reasonable agreement with those encountered in electrical logging. Doubtless other sources of potential are important but this explanation not only accounts for much of the potential but also clarifies some fairly familiar examples of misinterpretations. Introduction The extraordinary value of electrical well logging as a tool for petroleum engineers and geologists is now so universally recognized that it is not necessary to point out the ways in which it can be useful. It is sufficient to mention only the saving that has resulted from the elimination of much coring that would have been necessary under former practices and the considerable additions to reserves resulting from the discovery of sands missed in coring. Paradoxically, the very remarkable success that has resulted from the application of electrical logging to correlation and completion problems has cost some of its most consistent users dearly.' The fact that some operators have placed unwarranted faith in erroneous interpretatioils of electrical logs does not reduce the value of the logs. It should, however, make one pause long enough to ask why experienced users should be misled. The answer to this question is not hard to find. In nearly every case, the fault has been oversimplification. This is illustrated very aptly by the familiar interpretation and theory of the natural potential log. Recording and Interpreting Logs The natural potential log is extremely simple to record precisely enough for all present-day uses. One needs only an electrode, a cable to lower the electrode through the drilling mud, a recording meter and a surface ground connection. The electrode can be elaborate but need not be. A simple brass rod 2 in. in diameter and 2 or 3 in. long is quite satisfactory. The cable need not be particularly well insulated, nor need it have a very low resist-

Jan 1, 1946

By P. S. Kotva

Dislocation substructures in superalloy matrices of varyzng co)npositions have been studied. In general, it has been found that the alloys can be classified into ''high", ''medium", and "low" stacking fault energy classes based on the type of dislocation substructure observed in the matrix and that the substructure can be correlated to the stacking fault energy. The effect of different types of dislocation substructure and dislocation reactions on the intragranulur precipitation of carbide phases has been studied. In a Ni-Cv-Mo-Fe matrix, precipitation of MC carbides in association with stacking faults has been observed. In most superalloys, solid-solution strengthening and precipitation hardening are the chief mechanisms employed to achieve strength. The latter contribution to strength is usually achieved by the precipitation of / in certain wrought alloys. Insufficient attention has been given to the problem of obtaining strength in su-peralloys by controlling precipitation of carbides on imperfections within the matrix. The present work was undertaken to investigate the dislocation substructure in various superalloy matrices, to study the effect of such substructure on subsequent precipitation of carbides in the matrix, and to investigate whether certain modes of precipitation of carbide phases found in austenitic stainless steels2"4'6 would occur in nickel-base alloy matrices with dislocation substructures of the same type as those found in austenitic steels. 1) EXPERIMENTAL TECHNIQUES Five-pound heats of the various alloy compositions reported here were vacuum-cast. The ingots were given light deformation by rolling to break up the as-cast structure and then homogenized for 24 hr. HASTELLOY alloy X (nominal composition: Ni-2OCr-17Fe-8Mo-0.05C) was homogenized at 2150°F and In-cone1 625 (nominal composition: Ni-20Cr-5Fe-8Mo-3.5Cb-0.05C) was homogenized at 2280°F. Fabrication of 0.004-in. sheet was achieved by cold rolling with intermediate annealing treatments being carried out at the same temperature as those used for homogeniza-tion. Each solution anneal was followed by quenching. The aim of this procedure was to redissolve as much of the primary carbide phase as possible. Samples of the 0.004-in. sheet were cut and encapsulated in quartz capsules and then heat-treated in the tube furnaces. Thin foils were prepared using an ethanol-10 pct perchloric acid bath at 32°F and at a voltage of 22 v. A "window" technique was employed. Observations were made on a JEM-7 electron microscope operating at 100 kv. 2) EXPERIMENTAL RESULTS a) Types of Dislocation Substructure. Fig. 1 shows a schematic correlation between stacking fault energy, SFE, and the type of dislocation substructure observed in various matrices of nickel- and cobalt-base alloys. A precise quantitative determination of stacking fault energy is not implied in the figure but the correlation between stacking fault energy and the type of dislocation substructure obtained allows alloys to be divided into three classes in analogy with the classification employed by Swann and ~uttin~' for binary alloys of copper. Class I alloys are associated with a "high" SFE and show a cellular substructure of dislocations as typified by the micrograph of a thin foil of pure nickel deformed 4 pct at room temperature in Fig. 2. With decreasing SFE the tendency toward cell formation is lessened and dislocations tend to be arranged in coplanar groupings. Examples of this class of alloys with "medium" SFE are provided by the mi-crostructure of solution-heat-treated, quenched, and deformed thin foils of HASTELLOY alloy X, "Waspaloy" (prior to any aging), and Inconel 625. Fig. 3 shows a thin-foil micrograph of an alloy of Inconel 625 composition, solution-heat-treated, quenched, and deformed 5 pct at room temperatures. No evidence of any cell structure can be obtained in materials of "medium" stacking fault energy, Fig. 3, even after severe deformation. The stacking fault energy of the alloy shown in Fig. 3 is, however, not low enough to make the dissociation of dislocations visually obvious. As stacking fault energy decreases further, with successive addition of solute in the matrix, there is an increased tendency toward dissociation of dislocations and cross slip becomes progressively more difficult. Eventually, when the stacking fault energy is "low" enough, complete dissociation of dislocations is seen to occur as shown in Figs.

Jan 1, 1969

By R. W. Fountain, John Chipman

The solubility of nitrogen in Fe-B alloys (0.001 to 0.91 pet B) is determined by the Sieverts' technique for temperatures of 950° to 1150°C. The activity coefficient of nitrogen is decreased by boron. The three-phase equilibrium between ? iron, BN, and gas is established and also the four-phase equilibrium between iron, BN, Fe2B, and gas. The above equilibria are calculated for a iron. The relation of these data to hardenability and strain aging of boron-treated steels is discussed. BORON additions are known to enhanbe the hardenability of heat-treatable steels and to assist in the control of strain aging in sheet steel for deep drawing. The increase in hardenability is explained by the theory that adsorption of boron on austenite grain boundaries reduces their free energy and thus retards ferrite and upper bainite nucleation.l,2 Digges and Reinhart3 have shown that the full effectiveness of boron in commercial steels is achieved only when strong nitride formers such as titanium and zirconium are also present. The influence of nitrogen on eliminating the boron contribution to hardenability was also demonstrated by Shyne and Morgan.4 These workers prepared Ni-Mo steels containing either nitrogen or boron or nitrogen plus boron. The nitrogen-plus-boron steels showed the lowest hardenability which was attributed to the presence of stable nucleating particles, presumably nitride. Morgan and Shyne5-7 have shown that boron in the amount of 0.007 pet will completely eliminate strain aging due to nitrogen in low-carbon, open-hearth steels. In addition, by proper control of the boron additions, a rimming steel can be produced. Since the effectiveness of boron on hardenability and eliminating strain aging is influenced by the amount and distribution of the nitrogen in the steel, the present study was. undertaken to determine the influence of boron on the solubility of nitrogen in iron. EXPERIMENTAL PROCEDURE The solubility of nitrogen in Fe-B alloys was measured by the method of Sieverts, which consists of determining the amount of gas dissolved by the metal in a constant volume system. The apparatus employed in this investigation and the experimental details have beendescribed previously.B AMcLeodgage was added to the apparatus to allow measurements at very low pressures. The alloys were melted at reduced pressure in a basic-lined induction furnace using electrolytic iron and ferroboron. Ferroboron was added after the primary deoxidation of the iron with carbon. Since it was difficult to attain a constant low level of oxygen by this procedure, silicon was added after the carbon deoxidation and prior to the ferr obor on addition. The alloys were castas 2-in. sq ingots, heated in argon at 1050loC, and forged to 1/4-in. plate. After forging, 1116 in. was machined from each side of the plate to remove any possible contamination, and it was then cold-rolled to 0.010-in. sheet. The sheet was cut into approximately 1/4-in. squares and pickled in an inhibited H2SO4 solution to ensure a clean surface. In the case of the boron alloys, a hydrogen treatment could not be used for surface cleaning because boron losses resulted. The composition of the alloys is given in Table I. For a solubility determination, a 75-g sample was inserted in a quartz tube and sealed in place in the apparatus. The entire system was evacuated at room temperature and leak tested for 24 hr. If no leaks were observed, the system was heated to the temperature of measurement and again leak tested for 24 hr. If no leaks were detected, the hot volume and solubility determinations were begun. The hot volume was determined at a constant temperature for each run by admitting successive amounts of argon and recording pressure vs volume, which, in all cases, resulted in a straightline relationship. The argon was then removed and the procedure repeated with nitrogen. Successive additions were made until the desired nitrogen content of the metal and equilibrium pressure of the system were obtained. The

Jan 1, 1962

By P. W. Neurath, R. E. Waite

INFORMATION is available on the effect of stress on permeability, coercive force, and hysteresis for a variety of materials' but for the technically important grain-oriented 3 pct Si-Fe' the stress effects are not adequately covered in the literature; in addition, most of the stress data do not permit estimation of what would happen to the 60 cycle watt losses of the material under stress. Direct measurement of these effects therefore has been made and appears to be of considerable theoretical as well as practical interest. Losses were measured on the central 25 cm portion of 40~3~0.035 cm samples which could be stressed in a small tensile machine built for this purpose. Under tension the following effects, illustrated in the figures by a particular example, were observed: 1—"Unstrained" material of commercially acceptable loss level shows no change or a small increase in loss at low elastic stresses. For the sample shown in the figures, this is illustrated during the initial run, where a 7 pct increase is observed (Fig. 1). 2—There is no additional change in loss when the sample is further strained up to the elastic limit (Fig. 1). Within that limit the loss-stress curve is reversible. This is not illustrated in Fig. 1. 3—Even in the plastic range only small increases in loss are observed as long as the sample is kept under stress (Fig. 2, point N); often no increase can be observed (Fig. 1). 4—A large increase in watt losses is observed after removal of the stress subsequent to plastic deformation (Figs. 1 and 2). 5—All, or nearly all, of the foregoing increase in loss due to plastic deformation can be eliminated by a reapplication of tensile stress but returns upon removal of this stress. This is illustrated in the third run (Fig. 3). This run remains within the elastic limit and shows the reversibility of the stress-loss curve under this condition. These findings have been confirmed on large Samples (approximately 200~10~0.035 cm and larger) except that under 1 no initial increase in loss was ever observed on these. The accuracy of the watt loss measurements is of the order of 1 pct. Neither bending of the sample in the tensioning device nor a redistribution of flux along the width of the sample accounts for these results. They therefore must be explained on the basis of either a change in the domain configuration due to stress or a change in the domain wall mobility. Acknowledgment The assistance of Mr. Robert L. TenBroeck with the instrumentation is gratefully acknowledged.

Jan 1, 1956