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By B. Egeberg, H. B. Smith

Britannia metal is a white alloy consisting primarily of tin and antimony, the tin greatly predominating. The alloy usually contains a small amount of copper and occasionally very small amounts of one or two other metals, such as bismuth, zinc, and lead. It is capable of being cold-rolled, it takes a high polish, and it is fairly noncorrosive; properties which make it a popular metal for many household and traveling utensils. Britannia metal is similar in many respects to pewter and has largely replaced pewter in the arts, but it should not be confused with that alloy, because pewter is essentially a tin-lead alloy, while Britannia is a tin-antimony alloy. In view of the fact that so little has been published concerning Britannia metal, the authors feel justified in presenting the results of their investigation, particularly since the behavior of this alloy under cold rolling and heat treatment differs so greatly from that of other metals and alloys. The old craftsman, engaged in the making of ornaments or tableware, heated the cold-rolled sheet metal or his finished product to a straw color corresponding to about 375" I?., claiming to produce thereby a harder and more rigid article. The fact that possibly led him to this heating was that a reheated article or sheet made from Britannia metal has a distinct metallic ring when struck a sharp blow, whereas an unheated article or sheet has a leady, dead note. No doubt he has associated the metallic ring with a greater rigidity and strength, and justly so, as will be seen later. The approximate analysis of the metal we investigated was 91 Sn, 7 Sb, 2 Cu, and the molten metal was bottom-poured into an iron mold yielding an ingot 7 3/4 in. wide by 11 in. long and % in. thick, the casting temperature being 800" F. The ingot was cold-rolled to a sheet 0.032 in. thick, sufficiently large samples for experimental purposes being cut from the sheet at intermediate stages. The samples were all tested for hardness with scleroscope and Brine11 machine, then heated to 212" F. for 30 min., and again tested after cooling to room temperature. The same samples were heated successively at 300°, 400°, and 440" F., followed

Jan 1, 1929

By H. B. Smith, B. Egeberg

Britannia metal is a white alloy consisting primarily of tin and antimony, the tin greatly predominating. The alloy usually contains a small amount of copper and occasionally very small amounts of one or two other metals, such as bismuth, zinc, and lead. It is capable of being cold-rolled, it takes a high polish, and it is fairly noncorrosive; properties which make it a popular metal for many household and traveling utensils. Britannia metal is similar in many respects to pewter and has largely replaced pewter in the arts, but it should not be confused with that alloy, because pewter is essentially a tin-lead alloy, while Britannia is a tin-antimony alloy. In view of the fact that so little has been published concerning Britannia metal, the authors feel justified in presenting the results of their investigation, particularly since the behavior of this alloy under cold rolling and heat treatment differs so greatly from that of other metals and alloys. The old craftsman, engaged in the making of ornaments or tableware, heated the cold-rolled sheet metal or his finished product to a straw color corresponding to about 375" I?., claiming to produce thereby a harder and more rigid article. The fact that possibly led him to this heating was that a reheated article or sheet made from Britannia metal has a distinct metallic ring when struck a sharp blow, whereas an unheated article or sheet has a leady, dead note. No doubt he has associated the metallic ring with a greater rigidity and strength, and justly so, as will be seen later. The approximate analysis of the metal we investigated was 91 Sn, 7 Sb, 2 Cu, and the molten metal was bottom-poured into an iron mold yielding an ingot 7 3/4 in. wide by 11 in. long and % in. thick, the casting temperature being 800" F. The ingot was cold-rolled to a sheet 0.032 in. thick, sufficiently large samples for experimental purposes being cut from the sheet at intermediate stages. The samples were all tested for hardness with scleroscope and Brine11 machine, then heated to 212" F. for 30 min., and again tested after cooling to room temperature. The same samples were heated successively at 300°, 400°, and 440" F., followed

Jan 1, 1929

By C. S. Finney, John Mitchell

The growing popularity in the United States of the vertical-flue even was emphasized when in 1905 the United States Steel Corp. chose the Koppers oven as the type which best suited their requirements. Heinrich Koppers was born on November 23. 1872. at a small farm in Walbeck near Geldern on the lower Rhine. When young Koppers was eight years old, however the family moved away from the farm to the industrial city of Bochum in the Ruhr. Here Koppers attended public school and subsequently served an apprenticeship to a tinsmith before taking a job as a lathe operator with a local steel company. He had ambitions to be much more than a machinist, however, and used his week-ends and evenings to improve his theoretical background by taking courses at a vocational-training school in Bochum. After winning the highest honor the school could bestow (the silver Staats-medaille), Koppers went on to continue his education at the Rheinisch-Westfalische Hüttenschule in Duisberg. One of his teachers there, Fritz Wüst who later became a professor at the Technische Hochschule at Aachen, recognizing Koppers' unusual abilities, predicted for him a great future. In 1894 Heinrich Koppers joined the firm of Dr. C. Otto and Co. in Dahlhausen, and in 1899 while superintendent of the Mathias Stinnes mine he built his first battery of ovens for Hugo Stinnes, the German industrialist. Two years later he started his own organization, and in 1902 he made Essen his headquarters. It was to Essen that a group of engineers from the United States Steel Corp. went in 1906 with an invitation to Koppers to design and supervise the construction of four batteries of ovens at the Joliet works of the Illinois Steel Co. Each battery was to consist of 70 ovens. Arriving in the United States in 1907, Koppers established a branch of his firm in Joliet, and construction began. The first battery was fired on July 27, 1908. Rugged and simple, these ovens incorporated basic design features which were to make the Koppers oven and its future modifications the choice of a very large segment of the by-product coking industry of America. The 280 ovens at Joliet were 35 ft long, 8 ¾ ft in height, and tapered from 21 to 17 in. The total daily capacity of the four batteries was 2240 tons of coke. The ovens were of the new cross-regenerative type; that is, instead of longitudinal regenerators serving an entire battery, as in the older Koppers ovens, cross regenerators for each separate oven were employed. Fuel gas was supplied from the side of the battery through ducts in the brickwork known as gun flues, which reached to the center of the battery under the vertical heating-flues. Removable, ceramic gas-nozzles fitted at the top of each gun flue helped to insure good control over the distribution of the fuel gas, and uniform heating conditions were also promoted by regulating the air supply to, and the suction in, each heating flue. A different refractory w& used for each battery. One was built of American silica brick, one of American quartzite, and two of imported German quartzite. The installation at Joliet proved to be very successful, and in 1911, 490 additional' Koppers ovens were built for the Illinois Steel Co. at the great new steelworks at Gary, Ind. By 1912 the H. Koppers Co. had established its headquarters in Chicago and was rapidly extending its business to include construction for such iron and steel companies as the Woodward Iron Co. at Woodward, Ma. (80 ovens in 1912); the Tennessee Coal, Iron and Rail- road Co. at Fairfield, Ala. (280 ovens in 1912); the Inland Steel Co. at Indiana Harbor, Ind. (86 ovens during 1913 and 1914) ; and the Republic Iron and Steel Co. at Youngstown, Ohio (68 ovens in 1913). In 1914 a group of men in Pittsburgh bought a major shareholding in the H. Koppers Co., and moved the headquarters of the organization from Chicago to their own city. Under its new management the company was highly successful in obtaining a large share of the contracts for by-product installations built during World War I. In 1917 the remaining German interests in the company were

Jan 1, 1961

By Chester S. Conrad

SEVERAL years ago Pittsburgh Consolidation Coal Co. intensified efforts to combat the hazard of mine fires. The program consisted of three parts in the order of likely accomplishment: 1) Purchase and installation of newer and more practical fire fighting equipment. 2) Establishment of trained fire fighting teams at every mine plant. 3) A drive to remove the causes of mine fires. Experimentation with alternating current on section equipment is a major development in this part of the program. Use of alternating current to power mining equipment had been recognized as being most practical from the standpoint of safety. A means to re- place the d-c traction motor is all that has delayed complete section mechanization with a-c power.

Jan 1, 1958

By Hans Lundberg

IN ORDER to comprehend the help and information that may be expected from electrical prospecting, it is necessary to have at least a general knowledge of the methods and principles involved in preparing and interpreting results obtained in the field. Electrical prospecting is rather complicated, both in theory and practice, and in order to make a brief description clear to the practical mining man it has been necessary to idealize and generalize the problems, at the risk of having such simplification criticized by the theoretical man. This simplification must not be misinterpreted as showing a lack of theoretical knowledge. FIG. 1.-FLOW OF CURRENT IN AND AROUND A CONDUCTING BODY. For its operation, electrical prospecting mainly, depends on the fact that most metallic ores conduct an electric current much more readily than barren rocks. If an electric current flows through a block of ground within which a body of chalcopyrite is enclosed in country rock of. schist, the current will find less resistance to its passage through the chalcopyrite than through the schist, even though the passage through the latter be much shorter. This is because the longer path through the chalcopyrite offers less resistance, owing to the superior electrical conductivity of the chalcopyrite (Fig. 1).

Jan 1, 1928

By J. H. Nead

The experiments herein described were undertaken with a view to investigating thoroughly the influence of carbon on the tensile and impact physical properties of carbon steel. The original comprehensive plan included investigation of a series of steels with varying carbon contents over a wide range of heat treatments. These were to be studied as to their static tensile qualities, and also their resistance to shock as measured by the Charpy impact bending test. A thorough metallographic examination was likewise included in the schedule. The Charpy tests and the metallographic examination have not been completed to date, and are accordingly withheld for another report. All heat treatments, however, have been made, and the static tensile tests have been completed. A description of the procedure of the experiment and the results thus far obtained are therefore reported herein. Conclusions No attempt is made to draw general conclusions from these experiments, but the curves and the data are submitted as being of general importance and wide applicability. Composition of Materials An attempt was made to secure steels increasing in carbon by increments of 0.1 per cent. from 0.1 per cent. up to 0.8 per cent., and from that composition to 1.6 per cent. by increments of 0.2 per cent. Actually, however, steels of the composition given in Table I were procured, and as the carbon contents were arranged sufficiently well so that satisfactory curves could be drawn showing the relation between carbon content and other properties, these steels were used in the experiments.

Jan 1, 1916

By Frederic Becket

IN a recent article,1 which described the softening effect of columbium in plain high-chromium steels, the authors stated that their investi-gations had shown columbium to be also a particularly valuable inhibitor of intergranular corrosion in steels of the 18 per cent chromium, 8 per cent nickel type. It is the purpose of the present paper to record some of the results obtained through the introduction of columbium to the austenitic chromium-nickel steels. The damaging effects of this type of corrosion have become so widely known as to restrict considerably the applications of the steels under consideration, and therefore there is little question of the importance of the goal to be attained. Numerous contributions concerning the susceptibility of the aus-tenitic chromium-nickel steels to intergranular corrosion have appeared during the past few years, and among others who have dealt construc-tively with the subject are such well-known authors as Strauss and Houdremont of Germany, Hatfield of England, and Bain in the United States. Different theories have been propounded as to the cause of intergranular corrosion, and various remedial measures have been proposed, the majority of which involve the use of addition agents. Titanium is the addition agent at present most generally employed, as suggested by Houdremont and modified as described by Bain, Aborn and Rutherford.2 Little has been published on the effects of holding these steels for long periods at the relatively lower temperatures in the presence of

Jan 1, 1934

By W. H. Furlonge

WHILE fulfilling professional engagements, my travels over this portion of the Transvaal have been quite extensive—always on horseback however, so that anything like a thorough investigation of the ground passed over has been necessarily impossible; still, the more minute examination of certain small areas, coupled with general observations, has enabled me to form some idea as to the prominent geological features of the country as a whole. Anything like a complete or comprehensive description is indeed out of the question, as there are no proper maps of the country and the facilities for observation are limited. A large plateau, called the "High Veldt," stretches from east to west across the Transvaal. It is generally level, or gently rolling, and has an average elevation of 6000 feet above the sea; it is destitute of timber, and in fact greatly resembles the western prairies of North America. Rock-outcrops are not common in it. It terminates very abruptly to the east and northeast, the descent of 2000 or 3000 feet into the mountainous country that occupies its borders being made in a

Jan 1, 1890

By F. N. Speller

ASIDE from the Tuesday symposium on gases in metals, the Iron and Steel Division swung into action for the first time on the third day of the meeting with a discussion of iron and steel alloys. Dr. E. S. Davenport opened the discussion on Wednesday morning by presenting the paper written by himself in association with E. C. Bain and W. S. N. wiring on the equilibrium diagram of iron-manganese-carbon alloys. A written discussion by Mr. Scott showed qualitative agree- ment, but some quantitative disagreement. Messrs. Marsh and Sisco discussed the paper at length, pointing out non- agreement of certain conclusions with the phase rule. Dr. Krivobok, although differing with the authors on some points, stated that in his opinion the information collected would be valuable in the practical use of these alloys.

Jan 1, 1932

By H. E. McKinstry

Movement on a fracture of irregular shape can cause local widening of the fissure and thereby offer freer channelways for circulation of ore-depositing solutions. This influence: coupled with large areas of wall rock available for reacting with ore solutions in brecciated and shattered ground can account for locally active deposition of metals and the resulting ore shoots. Such irregularities in the fracture system may be caused by local variations in the strength of rocks and by pre-existing lines of weakness, especially if these stand at favorable angles to certain components of the fracturing stress. Therefore correct interpretation of the mechanics of fracturing should permit deductions as to structurally favorable places on unexplored portions of the vein system. Introduction It has long been recognized that movement on a curved or irregular fault surface is capable of separating the walls in certain portions of the fault, but until very recent years the importance of this mechanism as a factor in localizing ore shoots has escaped proper recognition. A short time ago W. H. Newhouse' presented a careful analytical study of displacements and their corresponding open spaces. For reasons that will be discussed later, it frequently happens that portions of the vein which are favorably oriented are not merely wider but also richer than the average. In many cases the widening with its accompanying richness coincides with very minor changes in the dip or strike of the vein, irregularities that commonly escape notice unless the vein is mapped in detail and a careful geometrical analysis made. While the relationship between the width of the vein and the changes in dip or strike has been recognized as a matter of observation, the irregularities have been accepted as more or less the result of accident. There has been very little effort except in isolated cases to find out the causes of these changes in dip or strike. Yet it is clear that if the causes can be recognized and expressed in terms of geologic structure the geologist will know where to look for repetitions of these favorable conditions either on extensions of the same vein or on adjoining veins. Any lack of understanding of the causes is due to the limitations of our ability to interpret our observations and not to the sheer capriciousness of

Jan 1, 1941

By H. E. McKinstry

Movement on a fracture of irregular shape can cause local widening of the fissure and thereby offer freer channelways for circulation of ore-depositing solutions. This influence: coupled with large areas of wall rock available for reacting with ore solutions in brecciated and shattered ground can account for locally active deposition of metals and the resulting ore shoots. Such irregularities in the fracture system may be caused by local variations in the strength of rocks and by pre-existing lines of weakness, especially if these stand at favorable angles to certain components of the fracturing stress. Therefore correct interpretation of the mechanics of fracturing should permit deductions as to structurally favorable places on unexplored portions of the vein system. Introduction It has long been recognized that movement on a curved or irregular fault surface is capable of separating the walls in certain portions of the fault, but until very recent years the importance of this mechanism as a factor in localizing ore shoots has escaped proper recognition. A short time ago W. H. Newhouse' presented a careful analytical study of displacements and their corresponding open spaces. For reasons that will be discussed later, it frequently happens that portions of the vein which are favorably oriented are not merely wider but also richer than the average. In many cases the widening with its accompanying richness coincides with very minor changes in the dip or strike of the vein, irregularities that commonly escape notice unless the vein is mapped in detail and a careful geometrical analysis made. While the relationship between the width of the vein and the changes in dip or strike has been recognized as a matter of observation, the irregularities have been accepted as more or less the result of accident. There has been very little effort except in isolated cases to find out the causes of these changes in dip or strike. Yet it is clear that if the causes can be recognized and expressed in terms of geologic structure the geologist will know where to look for repetitions of these favorable conditions either on extensions of the same vein or on adjoining veins. Any lack of understanding of the causes is due to the limitations of our ability to interpret our observations and not to the sheer capriciousness of

Jan 1, 1941

By E. M. Wise

THe properties required of gold alloys for jewelry are not well standardized, due in part to problems peculiar to certain branches of the jewelry industry, in part to the individual preference of the fabricator and to his willingness to cope with certain difficulties in manufacture, which arise with the use of certain alloys. General Requirements In general, the properties desired may be classed as follows: 1. Color should conform to the dictates of good taste and smart style. 2. Corrosion resistance and tarnish resistance should he good. This is to a considerable extent determined by the carat. Resistance to such corrosive agents as mercuric chloride as well as certain depi1atories is unreasonable to expect and difficult to meet. 3. Strength and hardness must be adequate to maintain the delicate contours of finely modeled jewelry. 4. Wear resistance must be great enough to resist abnormal wear, such as is encountered by a wedding ring in a lifetime of wear. 5. Ductility must be sufficient to permit the fabrication of drawn shells, tubes and difficult shapes. Material having a yield point of not less than 60,000 lb. per sq. in., an ultimate strength of 100,000 Ib. per sq. in., and an elongation of 40 per cent. is desirable. 6. Melting point should be between 800" and 1200" C. Colored Golds The popular green and yellow golds are based on the gold-silver-copper alloys; in some cases modified by the introduction of zinc to improve the casting properties and to alter the color, and nickel to increase the strength. The properties of the Au-Ag-Cu system have been the subject of a very thorough investigation by Jänecke,l Sterner-Rainer12 and Carter."

Jan 1, 1929

By E. M. Wise

THe properties required of gold alloys for jewelry are not well standardized, due in part to problems peculiar to certain branches of the jewelry industry, in part to the individual preference of the fabricator and to his willingness to cope with certain difficulties in manufacture, which arise with the use of certain alloys. General Requirements In general, the properties desired may be classed as follows: 1. Color should conform to the dictates of good taste and smart style. 2. Corrosion resistance and tarnish resistance should he good. This is to a considerable extent determined by the carat. Resistance to such corrosive agents as mercuric chloride as well as certain depi1atories is unreasonable to expect and difficult to meet. 3. Strength and hardness must be adequate to maintain the delicate contours of finely modeled jewelry. 4. Wear resistance must be great enough to resist abnormal wear, such as is encountered by a wedding ring in a lifetime of wear. 5. Ductility must be sufficient to permit the fabrication of drawn shells, tubes and difficult shapes. Material having a yield point of not less than 60,000 lb. per sq. in., an ultimate strength of 100,000 Ib. per sq. in., and an elongation of 40 per cent. is desirable. 6. Melting point should be between 800" and 1200" C. Colored Golds The popular green and yellow golds are based on the gold-silver-copper alloys; in some cases modified by the introduction of zinc to improve the casting properties and to alter the color, and nickel to increase the strength. The properties of the Au-Ag-Cu system have been the subject of a very thorough investigation by Jänecke,l Sterner-Rainer12 and Carter."

Jan 1, 1929

By Henry Lloyd Smyth

In 1891-92 1 was entrusted with the geological survey of part of the large area lying between the Marquette and Menominee iron-ranges in the Upper Peninsula of Michigan, and extending from the Republic trough on the north, through portions of the valleys of the Michigamme and Fence rivers, to and including the intermediate Felch mountain range on the south. Until a few years back the larger part of this area has been very difficult of access, and much of it is difficult still. The rock-surface is for the most part covered with swamp, forest and glacial deposits of various kinds, and therefore has not invited geological study. For these reasons the district, as a whole, with the exception of the Felch mountain range, remained almost unknown from a geological standpoint until our work in 1892. Our main object was to map the pre-Cambrian rocks, particularly the iron-bearing formations of Algonkian or Huronian age, and to obtain as much information as possible with reference to their sequence and structure, In carrying out this purpose, the use of simple magnetic instruments was found to be of the greatest assistance, and indeed indispensable. In this paper the results of our experience in tracing magnetic rocks by means of the disturbances produced in these instruments, have been brought together in systematic form, with such references to the particular area as are necessary in order to illustrate general principles, with the hope that they will prove useful to other workers in the same region, or in other regions where similar conditions may be encountered. The writer was efficiently aided in the field-work by Messrs. Samuel Sanford and Charlea N. Fairchild for nearly the whole period, and E. B. Mathews and H. F. Phillips for part of it,

Jan 1, 1897

By M. E. Wadsworth, G. W. Warren

INTRODUCTION Hydrometallurgical processes for the extraction of metal values can be divided into two broad categories: (a) Processes involving the treatment of high grade material (e.g. finely divided mineral concentrates); and (b) processes which treat lower grade material (ores, waste dumps, etc.). This discussion will be directed primarily toward the first category, but in either case a fundamental knowledge of the intrinsic kinetics and thermodynamics is necessary to understand the behavior of the system. The bulk of research efforts in the last decade along these lines has been aimed at the recovery of copper (1-8). However much information has also been reported on uranium (9, 10) , zinc (11) , cobalt and nickel (12, 13). More comprehensive reviews on these areas are also available (14). As discussed by Sepulveda and Herbst (15, 16) one of the most difficult problems facing process designers is the acquisition and scale-up of reliable information concerning the intrinsic kinetics of leaching systems. The scale-up or modeling of these multiparticle systems is far more complex than that of homogeneous ones. This is due to the numerous rate determining steps which are possible with heterogeneous reactions and the broad distribution of properties of a multiparticle feed such as particle size and mineralogical composition (16). In addition, other factors must also be considered such as interactions between particles, the anisotropic nature of individual particles, the effect of solution chemistry, and electrochemical phenomena. All of these factors must be taken into account, often simultaneously. The thrust of this paper will be to more closely examine how the factors mentioned above can be treated. Some elementary examples of

Jan 1, 1980

By G. F. Dillion, A. F. Armington

THE present method for the ultrapurification of boron involves the formation, distillation, and decomposition of boron tribromide.' However, the boron tribromide prepared contains several impurities in the ppm range, even after distillation. Some of these impurities, notably carbon, can be reduced after decomposition by zone refining. In this study, a comparison of the purity of boron tribromide at various formation temperatures is presented. The apparatus employed consisted of a bromine flask connected to a 22 mm ID horizontal quartz reaction tube packed with amorphous boron powder, which was in turn connected to a receiving flask cooled with an ice bath. Argon was used as a carrier gas. The approximate rate of passage of bromine to the reaction tube was 25 g per hr. The reaction was first investigated at several temperatures in order to determine the lowest temperature necessary to produce a colorless product which was assumed to be an indication of complete reaction of the bromine. The lowest temperature found in this study was 420oC. The amount of impurities found in the boron tribromide at various formation temperatures is shown in Table I. The data presented are emission spectroscopic results of boric oxide produced by the hydrolysis of 2 to 3 g of boron tribromide in 10 ml of distilled water. After hydrolysis, the samples were dried several hours on a hot plate. Assuming equilibrium conditions in the reactor, one can make approximate thermodynamic calculations estimatling the completeness of reaction of bromine with boron and its impurities at various temperatures. Data for these calculations were taken from Rossini,3 and must be taken as approximations since the T?S factor was not included in the calculations. The results of such calculations indicate that, with the exception of carbon bromina-tion, all impurities would react almost to completeness (> 99 pet) at all temperatures between 400" and 900oC. In the case of carbon, which cannot be accurately analyzed spectroscopically, it is estimated that only about one sixth as much carbon tetrabromide would be formed at 400" than at 900°C. Since some marked reductions in impurity content were observed at the lower reaction temperature which would not be predicted by thermo-

Jan 1, 1962

By Herbert H. Kellogg

Graphs representing the standard free-energy of formation as a function of temperature for 21 fluorides are presented, along with estimated values for the standard free-energy of formation of 20 atedadditional fluorides. A few of the many possible uses of these data in metallurgical calculations are discussed, including the fluorination of oxides, sulphides, metallurgicaland chlorides, and the reduction of metal fluorides. RECENT papers which have presented free-energy data for oxides, sulphides, chlorides, carbonates, sulphates, and silicates in the form of free energy vs. temperature plots,1-5 have found important uses in teaching and metallurgical development work. This method of presentation of thermo-dynamic data serves to make available in readily usable form thermodynamic constants which are scattered throughout the literature, and to show by graphical means the stability relations which exist between the compounds of a given type. It is certainly desirable to have these free-energy-temperature diagrams for as many types of compounds as are of present or potential use in metallurgical processes. Thus, even though there are but few uses of metallic fluorides in extractive metallurgy today, the potential uses of fluorine processes are of great importance and serve as the principal justification of this paper. Recent developments in the production of fluoro-carbons have resulted in vastly improved methods for the production and handling of fluorine and corrosive fluorides, with consequent reduction in costs.".' The extractive metallurgist should no longer overlook possible fluorine processes when development of a new process for a relatively high unit-price metal is being considered. In a previous paperv he author outlined in some detail the importance and use of free-energy data in metallurgical calculations and also discussed the properties of a standard free-energy vs. temperature diagram. The same method of presentation is adopted in this paper, and the reader is referred to the earlier work for explanations of the use of free-energy data. Thermodynamic Data This paper presents standard free-energy vs. temperature diagrams, Figs. 1 and 2, for those fluorides for which the major thermodynamic constants are known. In the calculations of the standard free-energy of formation (AGO), values of the enthalpy of formation at 298°K (?Ho,) were taken from "Selected Values of Thermodynamic Constants"8 most of the values of standard entropy at 298°K (S°298) were taken from "Selected Values"," but in a few cases the values given by Kelley9 ere preferred; data for the Phase changes came from "selected Values" and several of Kellley's publics- tions;0-12 and most of the specific-heat data were taken from Kelley.l0 The appendix gives a detailed list of the sources of the data. As explained in an earlier paper,6 he accuracy of some of the standard free-energy relationships is not high. An error of +1 kcal at 1000°C is expected in most of the curves of Figs. 1 and 2. The error may be as high as +3 kcal in some of the curves. Rather than attempt to estimate the reliability of each curve, the source of the data used is reported in the appendix, and the reader may compare these data with newer values as they become available. Figs. 1 and 2 fail to show values for the fluorides of many important metals. In most cases this is because the entropy of the metallic fluoride is unknown. For preliminary calculations it is often useful to have available the best estimate of an unknown datum, rather than no information at all. With this in mind, Table I lists estimated standard free-energy values for a number of important metallic fluorides not included in Figs. 1 and 2. The values reported in Table I were, calculated by Brewer et al.13 and are based on estimated entropy values. The estimated uncertainty of the values for each fluoride were calculated from the uncertainty values given by Brewer1' for ?H°, and the entropy function.

Jan 1, 1952

By W. P. Saunders, W. R. Hibbard, G. H. Eichelman

Interest in the various products of the austenite eutectoid transformation in iron-carbon alloys, particularly as produced by the isothermal sub-critical techniques introduced by Davenport and Bain,' has resulted in the application of similar heat treatments to other eutectoid transformations. Studies o f the beta copper-aluminum alloy eutectoid transformation revealed microstructures very similar to those found in iron-carbon alloys. Investigations5t6 of the kappa phase in the copper-silicon alloy system have established the eutectoid type transformation of this phase into terminal alpha and intermediate gamma phases. This transformation has been reported5 as forming a eutectoid type structure in a very sluggish manner by a long time isothermal treatment. The purpose of the present investigation is to study the products of the kappa eutectoid transformation as affected by transformation temperatures by means of microscopic and hardness methods. Preparation of Alloys The copper-silicon alloy equilibrium diagram is shown in Fig 1. The kappa field converges to a minimum silicon solubility at the eutectoid composition and all other completely kappa alloys are hypereutec-toid. Thus, kappa decomposition involves first the proeutectoid precipitation of gamma, followed by the eutectoid transformation of a lower silicon content kappa (5.2 pct) Smith6 has indicated that alloys containing between 5.4 and 5.7 pct silicon could be hot rolled, but that the latter composition was desirable in order to permit a wider kappa temperature range. The alloy was prepared by adding Baker's commercially pure silicon to an ingot of copper-silicon alloy containing 2.34 pct silicon remaining from the investigation of Brick, Martin and Angier.' Following the casting techniques of Krynitsky, Saunders and Stern,s the ingot was melted under a heavy layer of dried charcoal in a clay-graphite crucible in a gas-fired pot furnace. Small lumps of silicon were held under thc melt surface with a graphite rod. After the silicon had dissolved, the alloy was chill-cast and then remelted without a cover, stirred thoroughly, skimmed and poured into a preheated cast iron mold. The cast microstructure is shown in Fig 2. The casting, 10 X 4 X K in., was annealed at 750°C for 21 hr and furnace cooled, About }{& in. was milled from all surfaces. The plate was cut in half longitudinally and the bottom half analyzed by A.S.T.M. and The composition by weight was as follows: copper 94.24 pct, silicon 5.56 pct, iron 0.11 pct.

Jan 1, 1949

By Ursula E. Wolff

The precipitation of carbides from an alloy containing 33 pct Ni, 21 pct Cr, balance iron, was investigated electron microscopically by means of extraction replicas and thinned metal foils. Annealing temperatures ranged from 565°to 870°C and up to several thousand hours. M23C6 precipitated in pain boundaries, incoherent and coherent twin boundaries in that sequence. The orientation relationship between carbides and austenite matrix was determined and correlated with the morphology of the carbides and with the type of boundary in which precipitation occurred. In large-angle grain boundaries, as well as in coherent twin boundaries, the carbides had the same orientation as one of the adjacent pains. These carbides formed sheets of individual flakes with shapes related to the orientation of the boundary. In incoherent twin boundaries carbides precipitated in ribbons composed of pavallel rods. An unidentified subcarbide was found to precede precipitation of M23C6 in these boundaries. The M 23 C6 rods had a kind of fiber texture with (110) parallel to the long dimension of the rods and ribbon, and with orientations of both of the adjacent twin-related austenite crystals Predominant in the texture of the carbide. A hard sphere crystal model has been used to discuss orientation and morphology of the carbides in terms of free volume and vacancies available in the boundaries. A number of papers have dealt with the morphology of chromium carbide (M23 C6) precipitated in austenitic stainless steels.1"7 In all these investigations, the carbides were examined in the electron microscope by means of extraction replicas. With this technique, the carbides retain the spatial distribution they had in the bulk sample. However, since the matrix is dissolved in the process, the particles can turn in an unpredictable way; and the orientation relationship between matrix and carbides cannot be established. In this paper the results of studies on extraction replicas and on thinned metal foils are reported. These studies were undertaken to determine the matrix-to-car bide orientation relationship, and to correlate the orientation of the carbides with their morphology. PROCEDURE The material used was an austenitic alloy with 33 pct Ni, 21 pct Cr, balance iron, containing approximately 0.05 pct C. Coupons of 1.25-mm sheet were first solution-annealed at 1050°C for 15 min and air-cooled. Then, to precipitate the carbides, samples were isothermally annealed in the range from 565" to 870°C for times up to several thousand hours. All further specimen-preparation procedures were carried out after the final anneal. Carbon extraction replicas from polished and etched surfaces were made with 10 pct bromine in methyl alcohol.' Thin foils were prepared from punched-out 3-mm-diam disksg which fit into the electron-microscope holder. The disks were prethinned by grinding to approximately 0.5 mm thickness, and then electro-polished in a polytetrafluoroethylene holder1' with a solution containing 5 pct perchloric acid in acetic acid to which 10 g per 1 Cro3 and 5 g per 1 nickel chloride were added (etchant modified from that of Briers et al."). This solution dissolves neither the carbides nor the austenite around the carbides preferentially. By using extraction replicas, electron micrographs and selected-area electron-diffraction patterns were taken from the same carbide arrays. By using thin foils, electron micrographs were made from a grain boundary area containing carbides. Electron-diffraction patterns were then taken from the same area and from each of the adjacent grains separately. In this manner, the orientation of each grain could be determined without interference by the carbide pattern. A peculiarity of extraction replicas should be pointed out. After the matrix is etched away, the carbide arrays float freely in the etching and washing solutions, and are held in place only at the anchoring points in the carbon replica. When the replica is picked up with a screen the carbide arrays tend to flip to one side. Thus, while the surface features are preserved, the original arrangement of the carbides may severely and unpredictably be disturbed whenever the specimen contains large amounts of interconnected carbides. Nevertheless, it is possible to correlate the different morphologies of the carbides with the type of boundary in which they have precipitated. RESULTS 1) Extraction Replicas. Fig. 1 shows that the grain boundaries usually are curved, multicornered surfaces of random orientation. The coherent twin boundaries (which are (111) planes) cut a grain into parallel slices. Incoherent twin boundaries occur at the ends and on the steps of twins and are often narrow, parallel-sided strips which are much longer than they are wide. Different morphologies can clearly be distinguished for the M23Ce carbides precipitated in each of these types of boundaries, and agree well with those observed by kinzel.2 The kinetics of this precipitation has been investigated." The first carbides precipitate in junctions of three grain boundaries and fan out from there into the adjoining boundary surfaces, Fig. 2(a). These carbides are oriented randomly, Fig. 2(b), and become coarser and thicker as annealing time increases. The large-angle grain boundaries are next to fill

Jan 1, 1967

By E. A. Gulbransen, W. S. Wysong

THE behavior of tungsten and its surface oxides in oxidizing and reducing atmospheres and in high vacua at elevated temperatures is a question of considerable technical importance. The use of tungsten as a metal or as an important component in alloys in high temperature oxidizing atmospheres has been limited because of the unprotective nature of its oxide film and the volatility of its oxide. This paper will present results of a microbalance study1,2 of the following problems: (I) the oxidation behavior in the temperature range of 25 to 550°C (2) the reduction with pure hydrogen of thin oxide films formed on tungsten, and (3) the volatility of thin oxide films on tungsten. Tungsten is an interesting metal to study for the following reasons: (1) although the oxide to metal volume ratio is greater than one, the oxide is not considered protective, (2) the metal readily oxidizes at temperatures from 300° to 550°C (3) the oxides W02 and WO3 are reduced at temperatures as low as 500°C. by hydrogen, and (4) the oxide W02 is volatile at temperatures from 800 to 1100°C. LITERATURE The oxidation of tungsten in its thin film range has not been studied critically. In the thick film range Dunn3 has made the only systematic study. He found the oxidation rate to obey the parabolic rate law in the temperature range of 700 to 900°C. The temperature variation of the oxidation rate constant was found to follow an exponential law of the Arrhenius type. An inflection was noticed in the temperature plot of the rate law constant at 850 to 900°C. This was attributed to a phase change in the oxides. Scheil4 has studied the oxidation rate at 500 and 700°C over long periods of time and found a linear rate law. This result was interpreted as evidence for the presence of a nonprotective film. Pilling and Bedworth5 analyses of the oxide volume to metal volume ratio would indicate that a compact protective film should form. McAdam and Geil6 have studied the oxidation of tungsten in the thin film range using the interference color method. A parabolic rate law was found. Their curves showed that tungsten oxidizes faster than nickel but more slowly than iron. The lattice structures found in the oxidation of tungsten surfaces have been studied by Hickman and Gulbransen.7 They have reported that W03 is the stable oxide in contact with the metallic substrate up to approximately 600°C while W02 forms first at 700°C. Hägg and Magneli8 have recently reported a study of the lattice structures observed in the tungsten oxides using the X-ray diffraction method. In addition to an a-phase W03 and a d-phase W02, they reported the existence of two new phases. A ß' phase, homogeneous between

Jan 1, 1947