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By William J. McCaughey, Richard L. Barrett

FOR sixty years-in fact, ever since the inception of the basic steelmaking process -basic slags have been the subject of study by chemists, metallurgists and petrographers, with the purpose of providing a better understanding of the reactions between the slag and the metal during the refining process. The result of this work and of the researches of mineralogists and physical chemists into the chemistry of oxide systems is a considerable body of literature dealing not only with slags themselves but with equilibrium relationships in systems synthesized from pure components. Since any actual slag is a multicomponent system more complex than any yet worked out in the laboratory, a complete solution to the problem is still far away. The writers have recently published a paper1 which they believe sheds light on the role of the slag in the elimination of phosphorus and it is the purpose of the present paper to discuss the metallurgical applications of that work. Since the pioneer investigations on the constitution of basic slags carried on by Stead and Risdale, Carnot and Richards, Hilgenstock and others in the 1880's, a considerable body of literature on this subject has appeared. Many of the more important of these papers were summarized in the previous paper,' therefore they will not be reviewed here. PETROGRAPHIC STUDY The present writers have had occasion, over a period of years, to examine petrographically a great number of basic steel- making slags having a very wide range of chemical compositions and made under various conditions of operating practice. Although certain of these slags exhibit some unusual features, it is a remarkable fact that the great majority of mature slags show certain typical characteristics, which persist throughout the wide range of chemical compositions. The typical mature slag usually appears under the microscope to consist of two phases. The phase of primary crystallization is light colored and doubly refracting. If separated mechanically and subjected to chemical analysis, it is found to consist essentially of SiO2, CaO, and P2O5. Sometimes, although not usually, two such silicate-phosphate phases are found. The other conspicuous phase is dark in color and optically isotropic, and occurs as the interstitial material between the grains of the light colored phase. This dark colored interstitial phase when analyzed is found to consist essentially of FeO,Fe2O3, MnO, and MgO. In some slags high in iron oxide, particularly those from low-carbon heats, dicalcium ferrite is found. This phase is dark reddish brown in color and anisotropic.

Jan 1, 1944

By B. M. Larsen, T. E. Brower

THIS discussion is based on statistical manipulation and evaluation of operating data from several commercial blast furnaces which include rather wide variations in practice. We are concerned here mainly with the effect of manganese on sulphur elimination under operating conditions in commercial blast furnaces, but this effect can be outlined more clearly by including certain other variables such as silicon in iron and slag basicity, which are all in part interrelated. Real progress in understanding all of the smelting-zone reactions in this process requires more laboratory studies of slag-metal melts similar to those in the blast furnace, with careful control of oxygen pressure. Such experimental work is very difficult, however, and in the meantime, with the present scarcity of more fundamental data, such statistical trends and correlations as can be obtained from commercial furnace operating records may help in choosing laboratory test conditions as well as adding to our knowledge of operating procedures. We do not know just why the furnace data are apparently so irregular that statistical treatment of large numbers is needed to obtain accurate trends. It is partly caused, no doubt, by the many simultaneous variables present, but there are perhaps also such factors as: (I) the con- tinual swings up and down so characteristic of the process; (2) difficulty of accurate sampling of co-existing phases, as well as (3) the presence of both equilibrium and rate factors as a result of the fast driving of the process. In desulphurization, for example, the flow of thin layers of slag and metal over solid coke surfaces, plus the contact between droplets of iron falling through the slag layer in the hearth, would lead one to expect a close approach to equilibrium. On the other hand, most of the critical part of sulphur removal may occur in a short time and distance below the tuyeres with perhaps an accompanying decrease in oxygen pressure and the concurrent reduction of much of the silicon and manganese, so its degree of approach to equilibrium may be quite variable. Probable Chemistry of Desulphurization Since there is little evidence that sulphur atoms in the iron solution are aasociated to any appreciable extent in molecules such as MnS, the transfer from slag to metal and back again can be written:* (FeS) ? [FeS], [I] hence the following reactions seem most probable in the slag phase, (FeS) + (CaO) ? (CaS) + (FeO), [2] and, (FeS) + (MnO) ? (MnS) + (FeO). 131

Jan 1, 1949

By C. O. Ensign

Results of the application of geo1ogic knowledge to grade control have been remarkable. Grade reduction from dilution has been diminished from greater than 9% at the time of the program's beginning to about 2% at present. This has resulted in an increase of about 1.8 lb of copper per ton of ore mined and has made a substantial contribution to earnings at White Pine during the past two years. Even more improvement is expected in the future. The White Pine orebody, situated in the southwestern portion of the Keweenaw peninsula of upper Michigan, is a gently dipping stratiform or bedded deposit. Copper distribution is stratigraphi-cally controlled with higher values being confined to specific beds in the ore column. Room-and-pillar mining is practiced. Mining technique and geologic characteristics present a special array of problems in controlling the grade of ore. A routine program of grade control was started in the White Pine mine in August 1961. The program is based upon development and application of geologic knowledge to assist mine operating personnel to increase the grade of ore, primarily by accurate stratigraphic control and selection of areas for development on the basis of grade distribution trends. Geologists work closely with mine supervisors to offer the necessary geologic guidance. STRATIGRAPHIC POSITION OF COPPER The important rock series in the White Pine area is comprised of three formations of late Precambrian age. In descending order they are the Freda sandstone, Nonesuch shale, and Copper Harbor conglomerate. The Nonesuch shale is about 600 ft thick. Economic copper concentration occurs only in the lowermost 20 to 25 ft of the formation; however, within a restricted area along the southwest side of the mine the uppermost 1 to 7 ft of the Copper Harbor conglomerate (lower sandstone) contain sufficient quantities of copper to be included in the ore column. The ore consists primarily of chalcocite with subordinate native copper disseminated in shales, siltstones, and sandstones. MINE BOUNDARIES AND STRUCTURE The mine area is bounded on the west by the sub-outcrop of basal Nonesuch at bed rock surface and on the southwest by the White Pine fault (Fig. 1). The south and southeast limit of the orebody is reasonably well delineated by thinning or pinch-out of favorable host beds. Northern, northeastern, and eastern limits have not been established. The White Pine fault is actually a wide zone of shearing which strikes approximately N 40° W. It is downthrown on the southwest side and dips steeply to the northeast. Maximum vertical displacement is about 1500 ft.

Jan 1, 1964

By William J. McCaughey, Richard L. Barrett

For sixty years—in fact, ever since the inception of the basic steelmaking process —basic slags have been the subject of study by chemists, metallurgists and petrog-raphers! with the purpose of providing a better understanding of the reactions between the slag and the metal during the refining process. The result of this work and of the researches of mineralogists and physical chemists into the chemistry of oxide systems is a considerable body of literature dealing not only with slags themselves but with equilibrium relationships in systems synthesized from pure components. Since any actual slag is a multicom-ponent system more complex than any yet worked out in the laboratory, a complete solution to the problem is still far away. The writers have recently published a paper1 which they believe sheds light on the role of the slag in the elimination of phosphorus and it is the purpose of the present paper to discuss the metallurgical applications of that work. Since the pioneer investigations on the constitution of basic slags carried on by Stead and Risdale, Carnot and Richards, Hilgenstock and others in the I88o's, a considerable body of literature on this subject has appeared. Many of the more important of these papers were summarized in the previous paper,l therefore they will not be reviewed here. PetRographic Study The present writers have had occasion, over a period of years, to examine petro-graphically a great number of basic steel-making slags having a very wide range of chemical compositions and made under various conditions of operating practice. Although certain of these slags exhibit some unusual features, it is a remarkable fact that the great majority of mature slags show certain typical characteristics, which persist throughout the wide range of chemical compositions. The typical mature slag usually appears under the microscope to consist of two phases. The phase of primary crystallization is light colored and doubly refracting. If separated mechanically and subjected to chemical analysis, it is found to consist essentially of SiO2, CaO, and P2O6. Sometimes, although not usually, two such silicate-phosphate phases are found. The other conspicuous phase is dark in color and optically isotropic, and occurs as the interstitial material between the grains of the light colored phase. This dark colored interstitial phase when analyzed is found to consist essentially of FeO, Fe2O3, MnO, and MgO. In some 'lags high in iron oxide, particularly those from low-carbon heats, dicalcium ferrite is found. This phase is dark reddish brown in color and anisotropic.

Jan 1, 1944

By B. M. Larsen, T. E. Brower

INTRODUCTION THIS discussion is based on statistical manipulation and evaluation of operating data from several commercial blast furnaces which include rather wide variations in practice. We are concerned here mainly with the effect of manganese on sulphur elimination under operating conditions in commercial blast furnaces, but this effect can be outlined more clearly by including certain other variables such as silicon in iron and slag basicity, which are all in part interrelated. Real progress in understanding all of the smelting-zone reactions in this process requires more laboratory studies of slagmetal melts similar to those in the blast furnace, with careful control of oxygen pressure. Such experimental work is very difficult, however, and in the meantime, with the present scarcity of more fundamental data, such statistical trends and correlations as can be obtained from commercial furnace operating records may help in choosing laboratory test conditions as well as adding to our knowledge of operating procedures. We do not know just why the furnace data are apparently so irregular that statistical treatment of large numbers is needed to obtain accurate trends. It is .partly caused, no doubt, by the many simultaneous variables present, but there are perhaps also such factors as: (I) the continual swings up and down so characteristic of the process; (2) difficulty of accurate sampling of co-existing phases, as well as (3) the presence of both equilibrium and rate factors as a result of the fast driving of the process, In desulphurization, for example, the flow of thin layers of slag and metal over solid coke surfaces, plus the contact between droplets of iron falling through the slag layer in the hearth, would lead one to expect a close approach to equilibrium, On the other hand, most of the critical part of sulphur removal may occur in a short time and distance below the tuyeres with perhaps an accompanying decrease in oxygen pressure and the concurrent reduction of much of the silicon and manganese, so its degree of approach to equilibrium may be quite variable. PROBABLE CHEMISTRY OF DESULPHURIZATION Since there is little evidence that sulphur atoms in the iron solution are associated to any appreciable extent in molecules such as MnS, the transfer from slag to metal and back again can be written:* [(FeS) -, [FeS],[I] hence the following reactions seem most probable in the slag phase, (FeS) + (CaO) = (CaS) + (FeO), [2] and, (FeS) + (MnO) ;:2 (MnS) + (FeO). [31]

Jan 1, 1948

By S. Yukawa, M. J. Sinnott

A high resolution autoradiographic study of the diffusion of a nickel isotope (NP3) into copper in the temperature range of 650° to 925°C, with particular emphasis on grain boundary diffusion, has been made. The extent of grain boundary diffusion is a function of the grain boundary angle and the diffusion temperature. The ratios of the grain boundary diffusion coefficient to the lattice diffusion coefficient ranges from 104 to 105. The activation energy for grain boundary diffusion decreases with increasing grain boundary angle. STUDIES and reviews&apos;-8 of metallic diffusion have indicated that grain boundary diffusion is a common phenomenon but quantitative studies of the many variables involved are not numerous. The present work was concerned with determining the influence of the crystallographic orientation of the grain boundaries and the temperature on the extent of boundary diffusion of nickel into copper. The study involved essentially three steps: 1—the production of grain boundaries of known crystallographic orientation, 2—the determination of the extent of diffusion into the boundaries, and 3—the analysis of the resulting data in terms of the usual diffusion concepts. The grain boundaries investigated approximated the simple tilt variety having l° of freedom. They were produced by controlling the solidification from a melt of Cuprovac (a high purity vacuum-melted copper obtained from Vacuum Metals Corp.) of a pair of seed crystals so that the bicrystals of copper produced had a common <100> axis. By rotating one seed crystal relative to the other, a simple tilt boundary was produced. The angle of rotation between the two crystals is the grain boundary angle 8, or what is sometimes termed the misfit angle. In all, some 16 boundaries ranging from 2" to 72" in 5" to 10" steps were investigated. The crystallographic orientations were measured with the use of both X-ray and optical goniometric techniques. The <100> axes in the crystals were found to be parallel within 2" to 3" with the exception of one crystal (8 = 12") in which the axes were 6" from being parallel. All bicrystals showed evidences of sub-grain structures. Laue analyses showed that these subgrains differed in orientation up to a maximum of 2". Because of these variations, and some curvature in the boundaries, the grain boundary angles listed are actually average values and deviate from the 1 o of freedom boundaries. The stripping film technique of high resolution autoradiography was used to detect the diffusion of the nickel isotope into the grain boundaries of the bicrystals of copper. Kodak experimental permeable stripping film with an emulsion layer 5 u thick

Jan 1, 1956

By Irving M. Symonds

Compania Minera de Penoles, S. A., at its Avalos unit operates a lead-zinc concentrator having a capacity of about 600 short tons per day. Lead and zinc concentrates are made by flotation methods. The concentrator is at Terminal de Provi-dencia, in the state of Zacatecas, some 70 miles south of Saltillo, Coahuila. The Penoles-Avalos railroad operating between the plant and Estacion Avalos, a distance of 6 miles, makes connections with the Coahuila and Zacatecas railroad, which in turn connects with the Nacionales de Mexico at Saltillo. The three railroads are each of different gauge, requiring the transfer of all supplies and concentrates at each junction. The mill operates on company ores, on ores from leased mines, and as a custom mill. The custom business is very small. The lead concentrates are shipped to company smelters at Monterrey, Nuevo Leon and Torreon, Coahuila. Since the European war, all zinc concentrates have been shipped to the United States. Ore Treated The major source of ore supply is a group of four mines owned or leased by the company, some three miles south of the mill in the mountains, from which the ore is delivered to the mill by a gravity aerial tramway. Custom ore comes in by rail. The ores occur in chimneys. The upper levels contained oxidized siliceous ores of lead, copper, silver and gold, with varying amounts of zinc. These ores were direct-smelted. In the first two years of operation a good deal of the tailing loss was caused by the oxidized content of the ores milled. Much of the ore in the transition zones between the oxides and sulphides was not mined. The ores now being milled are clean, hard sulphides in a limestone gangue, with only occasional contamination of oxides. The lead and zinc sulphides are of coarse structure and are freed even above flotation sizes. The galena is usually "steel" colored, easily and quickly floated. When there is any oxidation, it is usually on the coarsest crystals. The zinc minerals vary a good deal in color; a resin sphalerite predominates but there are varying shades of brown marmatites. On an average, the zinc sulphides contain 64 per cent zinc. The only common copper mineral is chalcopy-rite. Little is known of the occurrence of gold and silver. Waste minerals are mainly limestone and pyrite, both of which are barren. The ores vary from 20 to 35 per cent pyrite. Mill heads for the year 1940 and the first eight months of 1941 are given in Table I.

Jan 1, 1943

By Carl F. Floe, Michael B. Bever

THE possibility that carbon may be soluble in copper to a limited extent has been recognized for over a century. The quantitative investigation of this problem, however, requires more sensitive techniques than have formerly been available. Three recent developments have made possible more accurate determinations: the vacuum-fusion method of analysis, the production of copper of high purity and the availability of high-purity refractories, particularly graphite. In addition to its obvious theoretical interest, the problem of carbon solubility in copper is of practical importance. In the production of copper and of high-copper alloys, carbonaceous covers are frequently used. If even minute amounts of carbon are dissolved, insoluble carbon oxide gases will be formed when such metals are poured under oxidizing conditions. A mechanism of this kind could well be one of the principal causes of gas porosity in casting copper-base products. REVIEW OF LITERATURE In 1823 Vivian1 raised the question as to whether copper by overpoling becomes "combined with a minute portion of carbon." Karsten2 asserted, in 1832, that carbon reduces the high-temperature strength of pure copper, so that when the carbon content has reached 0.2 per cent the metal will be brittle at a dark red heat. According to Karsten, carbon contents of o.05 per cent make it difficult to hot-work copper. He also reported that the specific gravity of copper is 8.8969 and that it increases to 8.92 58 if the copper is cemented with carbon and then melted. He emphasized the difficulty of determining analytically the small amounts of carbon present in copper. The metal was removed by wet methods and the residue considered as carbon. At Percy&apos;s request, Dick,3 in 1856, carried out various working tests on copper that had been in prolonged contact with carbon, and found that the working properties of the metal had not been affected. He also attempted to determine the presence of carbon analytically. In one experiment the copper was dissolved and the residue was fused with litharge, and in another essentially a combustion analysis was made on a copper sample. In a final experiment, a sample was dissolved and the residue subsequently subjected to a combustion analysis. Indications of as much as o.005 per cent carbon were found, but Dick considered his work inconclusive largely because of the possible interference of sulphur. Percy4 concluded, from Dick&apos;s experiments and from some experimental work of his own, that the solubility of carbon in copper had not been established with

Jan 1, 1945

By Irving M. Symonds

Compania Minera de Penoles, S. A., at its Avalos unit operates a lead-zinc concentrator having a capacity of about 600 short tons per day. Lead and zinc concentrates are made by flotation methods. The concentrator is at Terminal de Provi-dencia, in the state of Zacatecas, some 70 miles south of Saltillo, Coahuila. The Penoles-Avalos railroad operating between the plant and Estacion Avalos, a distance of 6 miles, makes connections with the Coahuila and Zacatecas railroad, which in turn connects with the Nacionales de Mexico at Saltillo. The three railroads are each of different gauge, requiring the transfer of all supplies and concentrates at each junction. The mill operates on company ores, on ores from leased mines, and as a custom mill. The custom business is very small. The lead concentrates are shipped to company smelters at Monterrey, Nuevo Leon and Torreon, Coahuila. Since the European war, all zinc concentrates have been shipped to the United States. Ore Treated The major source of ore supply is a group of four mines owned or leased by the company, some three miles south of the mill in the mountains, from which the ore is delivered to the mill by a gravity aerial tramway. Custom ore comes in by rail. The ores occur in chimneys. The upper levels contained oxidized siliceous ores of lead, copper, silver and gold, with varying amounts of zinc. These ores were direct-smelted. In the first two years of operation a good deal of the tailing loss was caused by the oxidized content of the ores milled. Much of the ore in the transition zones between the oxides and sulphides was not mined. The ores now being milled are clean, hard sulphides in a limestone gangue, with only occasional contamination of oxides. The lead and zinc sulphides are of coarse structure and are freed even above flotation sizes. The galena is usually "steel" colored, easily and quickly floated. When there is any oxidation, it is usually on the coarsest crystals. The zinc minerals vary a good deal in color; a resin sphalerite predominates but there are varying shades of brown marmatites. On an average, the zinc sulphides contain 64 per cent zinc. The only common copper mineral is chalcopy-rite. Little is known of the occurrence of gold and silver. Waste minerals are mainly limestone and pyrite, both of which are barren. The ores vary from 20 to 35 per cent pyrite. Mill heads for the year 1940 and the first eight months of 1941 are given in Table I.

Jan 1, 1943

By Irving M. Symonds

COMPAÑIA Minera de Peñoles, S. A., at its Avalos unit operates a lead-zinc concentrator having a capacity of about 600 short tons per day. Lead and zinc concentrates are made by flotation methods. The concentrator is at Terminal de Providencia, in the state of Zacatecas, some 70 miles south of Saltillo, Coahuila. The Peñoles-Avalos railroad operating between the plant and Estacion Avalos, a distance of 6 miles, makes connections with the Coahuila and Zacatecas railroad, which in turn connects with the Nacionales de Mexico at Saltillo. The three railroads are each of different gauge, requiring the transfer of all supplies and concentrates at each junction. The mill operates on company ores, on ores from leased mines, and as a custom mill. The custom business is very small. The lead concentrates are shipped to company smelters at Monterrey, Nuevo Leon and Torreón, Coahuila. Since the European war, all zinc concentrates have been shipped to the United States. ORE TREATED The major source of ore supply is a group of four mines owned or leased by the company, some three miles south of the mill in the mountains, from which the ore is delivered to the mill by a gravity aerial tramway. Custom ore comes in by rail. The ores occur in chimneys. The upper levels contained oxidized siliceous ores of lead, copper, silver and gold, with varying amounts of zinc. These ores were direct-smelted. In the first two years of operation a good deal of the tailing loss was caused by the oxidized content of the ores milled. Much of the ore in the transition zones between the oxides and sulphides was not mined. The ores now being milled are clean, hard sulphides in a limestone gangue, with only occasional contamination of oxides. The lead and zinc sulphides are of coarse structure and are freed even above flotation sizes. The galena is usually "steel" colored, easily and quickly floated. When there is any oxidation, it is usually on the coarsest crystals. The zinc minerals vary a good deal in color; a resin sphalerite predominates but there are varying shades of brown marmatites. On an average, the zinc sulphides contain 64 per cent zinc. The only common copper mineral is chalcopyrite. Little is known of the occurrence of gold and silver. Waste minerals are mainly limestone and pyrite, both of which are barren. The ores vary from 20 to 35 per cent pyrite. Mill heads for the year 1940 and the first eight months of 1941 are given in Table I. [ ]

Jan 1, 1942

By Irving M. Symonds

COMPA[N]IA Minera de Penoles, S. A., at its Avalos unit operates a lead-zinc concentrator having a capacity of about 600 short tons per day. Lead and zinc concentrates are made by flotation methods. The concentrator is at Terminal de Providencia, in the state of Zacatecas, some 70 miles south of Saltillo, Coahuila. The Pe[n]oles-Avalos railroad operating between the plant and Estacion Avalos, a distance of 6 miles, makes connections with the Coahuila and Zacatecas railroad, which in turn connects with the Nacionales de Mexico at Saltillo. The three railroads are each of different gauge, requiring the transfer of all supplies and concentrates at each junction. The mill operates on company ores, on ores from leased mines, and as a custom mill. The custom business is very small. The lead concentrates are shipped to company smelters at Monterrey, Nuevo Leon and Torréon, Coahuila. Since the European war, all zinc concentrates have been shipped to the United States. ORE TREATED The major source of ore supply is a group of four mines owned or leased by the company, some three miles south of the mill in the mountains, from which the ore is delivered to the mill by a gravity aerial tramway. Custom ore comes in by rail. The ores occur in chimneys. The upper levels contained oxidized siliceous ores of lead, copper, silver and gold, with varying amounts of zinc. These ores were direct-smelted. In the first two years of operation a good deal of the tailing loss was caused by the oxidized content of the ores milled. Much of the ore in the transition zones between the oxides and sulphides was not mined. The ores now being milled are clean, hard sulphides in a limestone gangue, with only occasional contamination of oxides. The lead and zinc sulphides are of coarse structure and are freed even above flotation sizes. The galena is usually "steel" colored, easily and quickly floated. When there is any oxidation, it is usually on the coarsest crystals. The zinc minerals vary a good deal in color; a resin sphalerite predominates but there are varying shades of brown marmatites. On an average, the zinc sulphides contain 64 per cent zinc. The only common copper mineral is chalcopyrite. Little is known of the occurrence of gold and silver. Waste minerals are mainly limestone and pyrite, both of which are barren. The ores vary from 20 to 35 per cent pyrite. Mill heads for the year 1940 and the first eight months of 1941 are given in Table I. [ ]

Jan 1, 1942

By S. Y. Ogawa

The effects of sulfur (up to 0.1 pet) on the deformation and fracture characteristics of iron, in cast form, were studied at strain rates up to 100 pct pcr sec and at temperatures of 1600o to -3300 oF. The effects of oxygen and manganese additions on the behavior of Fe-S alloys were studied under comparable test conditions. Brittle fracture characteristics, evident at all strain rates, resulted from the presence of the liquid iron sulfide phase at grain boundaries. Ductility could be restored in three ways: solution of the sulfide in solid y iron at higher temperatures, spheroid-zzation of the liquid sulfide, and increase. in the melting point ot the sulfide. THE literature shows that most previous studies of deformation and fracture at hot working temperatures have been based on measurements of energy absorption, reduction of height in forging upset tests, torsion tests of bar or wire samples, and so forth,&apos; but that relatively few tension tests have been used at high temperatures and strain rates. The present work was initiated to study the ef- fects of temperature, strain rate, composition, and structure on the deformation and fracture characteristics of iron, utilizing cast specimens tested in tension. As in a previous study,&apos; strain rates up to 100 pct per sec were chosen for the temperature range 1600° to 2400° to provide data which might be useful in the interpretation of the deformation and fracture behavior of steels under hot working conditions. The previous work was with Fe-P solid solution al10ys;2 this work is concerned with Fe-S alloys, and with the effects of oxygen and manganese additions. MATERIALS AND PROCEDURE Cast tes! specimens were employed throughout, since most of the difficulty during hot working occurs in the initial breakdown of the ingot. Alloy Systems. Ten 25 lb. heats containing sulphur were prepared. Of these, three had manganese additions, and two had oxygen additions. The sulfur content varied from 0.023 to 0.10 pct. Manganese contents were intended to be ten to twenty times the sulfur content of the particular alloy. Oxygen, being more difficult to control in small melts, was varied by the amount of solid deoxidizer added, but poor control of the oxygen content was experienced in most instances. Table I shows the chemical analyses of the heats. Melting and Casting. Electrolytic-iron chips were melted by high frequency induction in a prefired, clay-graphite crucible lined with rammed magnesite.

Jan 1, 1962

By Michael B. Bever, Carl F. Floe

he possibility that carbon may be soluble in copper to a limited extent has bten recognized for over a century. The quantitative investigation of this problem, however, requires more sensitive techniques than have formerly been available. Three recent developments have made possible more accurate determinations: the vacuum-fusion method of analysis, the production of copper of high purity and the availability of high-purity refractories, particularly graphite. In addition to its obvious theoretical interest, the problem of carbon solubility in copper is of practical importance. In the production of copper and of high-copper alloys, carbonaceous covers are freauerltlv used. If even minute amounts of carbon are dissolved, insoluble carbon oxide gases will be formed when such metals are poured under oxidizing conditions. A mechanism of this kind could well be one of the principal causes of gas porosity in casting copper-base products. Review of Literature In 1823 Vivian1 raised the question as to whether copper by overpoling becomes "combined with a minute portion of carbon." Karsten2 asserted, in 1832, that carbon reduces the high-temperature strength of pure copper, so that when the carbon content has reached 0.2 per cent the metal will be brittle at a dark red heat. According to Karsten, carbon contents of 0.05 per cent make it difficult to hot-work copper. He also reported that the specific gravity of copper is 8.8969 and that it increases to 8.9258 if the copper is cemented with carbon and then melted. He emphasized the difficulty of determining analytically the small amounts of carbon present in copper. The metal was removed by wet methods and the residue considered as carbon. At Percy&apos;s request, Dick,3 in 1856, carried out various working tests on copper that had been ill prolonged contact with carbon, and found that the working properties of the metal had not been affected. He also attempted to determine the presence of carbon analytically. In one experiment the copper was dissolved and the residue was fused with litharge, and in another essentially a combustion analysis was made on a copper sample. In a final experiment, a sample was dissolved and the residue subsequently subjected to a combustion analysis. Indications of as much as 0.005 per cent carbon were found, but Dick considered his work inconclusive largely because of the possible interference of sulphur. Percy4 concluded, from Dick&apos;s experiments and from some experimental work of his own, that the solubility of carbon in copper had not been established with

Jan 1, 1946

By J. T. Peters, N. Schapiro, R. J. Gray

Petrographic studies of coal have resulted in a better understanding of the origin and composition of coal and have added to the knowledge of how and why coals differ in their response to various prepamtion and utilization processes. Petrographic methods can now be used in scientific economic exploitation of coals. Because the United States Steel Corp. is one of the largest consumers of coal and coke, there is a continuing interest in the corporation in perfecting a better understanding of coal so that it can be utilized more effectively. Coal is a heterogeneous substance composed principally of plant material that has been altered by a complex geochemical process to form rock. The science of coal is anthracology. The ultimate aim of anthracology is determining the relationships and differences among coals. The fundamental aim is finding out why coals differ. The practical application is determining how the differences in coals affect their utilization properties. Coal, like other sedimentary rocks, consists of more than one material. Fig. 1, a photograph of a natural fracture and a polished surface of a lump of coal, displays heterogeneity in terms of the banded ingredients present. The earliest attempts to describe coal were based on its hardness and appearance. &apos; Thus, coal has been described as hard or soft, bright or dull, and banded or nonbanded. The variations in the hardness and physical appearance of the coal reflect differences in materials that constitute the coal. The banded nature, lustre, and texture depend upon the relative proportions of the various constituent materials. Even the earliest petrographic investigations of coal produced evidence of of the heterogeneity of the coal substance and shoul have destroyed the concept of the unit coal molecule. Coals (Fig. 2) that appear the same frequently consist of different microscopic materials and may behave differently during mining, pulverization, washing, or coking. In Fig. 3, the upper photograph shows a bright at-trital medium-volatile coal, and the micrograph at the right shows some of the materials that constitute the coal. The lower photograph shows a bright attrital low-volatile coal and the corresponding micrograph shows material of similar origin to those from the medium-volatile coal. Any petrographic description of a coal that has meaning in terms of its utilization begins with a microscopic examination. Numerous attempts have been made to describe coal on the basis of the materials that constitute the coal.2*3 Initial petrographic studies were directed towards the question of the origin of coals without any true basis for studying the metamorphic changes in the

Jan 1, 1962

By Carl F. Floe, Michael B. Bever

he possibility that carbon may be soluble in copper to a limited extent has bten recognized for over a century. The quantitative investigation of this problem, however, requires more sensitive techniques than have formerly been available. Three recent developments have made possible more accurate determinations: the vacuum-fusion method of analysis, the production of copper of high purity and the availability of high-purity refractories, particularly graphite. In addition to its obvious theoretical interest, the problem of carbon solubility in copper is of practical importance. In the production of copper and of high-copper alloys, carbonaceous covers are freauerltlv used. If even minute amounts of carbon are dissolved, insoluble carbon oxide gases will be formed when such metals are poured under oxidizing conditions. A mechanism of this kind could well be one of the principal causes of gas porosity in casting copper-base products. Review of Literature In 1823 Vivian1 raised the question as to whether copper by overpoling becomes "combined with a minute portion of carbon." Karsten2 asserted, in 1832, that carbon reduces the high-temperature strength of pure copper, so that when the carbon content has reached 0.2 per cent the metal will be brittle at a dark red heat. According to Karsten, carbon contents of 0.05 per cent make it difficult to hot-work copper. He also reported that the specific gravity of copper is 8.8969 and that it increases to 8.9258 if the copper is cemented with carbon and then melted. He emphasized the difficulty of determining analytically the small amounts of carbon present in copper. The metal was removed by wet methods and the residue considered as carbon. At Percy&apos;s request, Dick,3 in 1856, carried out various working tests on copper that had been ill prolonged contact with carbon, and found that the working properties of the metal had not been affected. He also attempted to determine the presence of carbon analytically. In one experiment the copper was dissolved and the residue was fused with litharge, and in another essentially a combustion analysis was made on a copper sample. In a final experiment, a sample was dissolved and the residue subsequently subjected to a combustion analysis. Indications of as much as 0.005 per cent carbon were found, but Dick considered his work inconclusive largely because of the possible interference of sulphur. Percy4 concluded, from Dick&apos;s experiments and from some experimental work of his own, that the solubility of carbon in copper had not been established with

Jan 1, 1946

By J. J. Taber, I. S. K. Kamath, R. L. Reed

Alcohol floods of consolidated sandstone cores have shown the process to be strongly dependent on the phase behavior of the particular alcobol-oil-water system used. This means that in many cases the mechanism does not conform to the idea of a piston-like displacement. Instead, it is found that by changing the alcohol it is possible to change the relative velocities of the oil and water and, in fact, the entire mechanism of the process. The effects of rate, viscosity, initial saturation, distance travelled and hysteresis of relative permeability on the alcohol flooding mechanism are discussed. INTRODUCTION Reasons for interest in the use of alcohol to miscibly displace oil and water from a porous medium appear in the existing literature.l-7 The mechanism of the displacement has been considered and the apparent implications formulated into a theory which presumably would enable one to predict the essential features of the process.6 Unfortunately, most of the reported experiments have been performed with unconsolidated or artificially consolidated sands. With these systems some of the noteworthy facets of the process are obscured and resulting data appear uncertain. It is the purpose of this paper to show how the use of consolidated sandstones has led to revision of the mechanism and, hence, the theory of alcohol flooding. The practical result is increased pessimism toward the possibilities of commercial application of the simplest form of the alcohol-slug process. However, elucidation of the mechanism has made it possible to define the essential characteristics of a system of slugs which will behave in a nearly piston-like fashion and, thus, yield the best possible result. EQUILIBRIUM PHASE BEHAVIOR Fig. 1 is a diagram of the ternary system isopropyl alcohol (IPA)-Soltrol-calcium chloride brine. Brine was used to prevent plugging of the core and calcium chloride was used because sodium-chloride brine exhibits a solid phase with Soltrol and IPA. If alcohol is added in increments to the immiscible mixture of water and oil represented by Point A, the path followed by the successively equilibrated samples will be on the Line ABC and pass from the immiscible region to the miscible region by crossing the binodal curve at B. Consider the intersection D of this path with the tie Line EF. The quantity of oleic phase is proportional to the Segment ED and the quantity of the aqueous phase is proportional to DF. Compositions of the two phases are specified by Points E and F. It is clear that in the case shown the oleic phase is diminishing and entirely disappears when miscibility is achieved. Such will

By A. H. Geisler, R. F. Mehl, C. S. Barrett

The mechanism by which the supersaturated solid solution of 20 per cent silver in aluminum decomposes has been reported in two previous publications.1&apos;2 The analysis of streaks in Laue photograms showed that thin platelike particles (the so-called Guinier-Preston aggregates) form upon matrix planes in the early state of decomposition.1 The size of these particles is larger, the higher the temperature at which they form in accordance with nucleation theory;³ at all temperatures they increase in size with aging.2 When they have grown thick enough to afford three-dimensional diffraction, powder X-ray photograms show that the structure is not that of the equilibrium precipitate but that of a transition lattice . Sincc this is also platelike in shape and also lies upon the (III) matrix planes with the [IIO] direction in the matrix parallel to the [II.O] direction in it seems likely that the original platelet particles are merely in an early stage of formation, and thus finely dispersed. The atomic spacing and pattern on the (00.1) plane in y&apos; are identical with those on the (111) matrix plane to which it lies parallel, and since comparable directions in the two planes are parallel, the lattices are thus coherent at the interface; an analogous coherence has been found in aluminum-copper alloys.3 The structures y&apos; and y are both close-packed hexagonal and are oriented alike; they differ only in interatomic distances. Consequently, y&apos; is regarded as y strained from its ordinary dimensions by the lattice coherency between it and the matrix.2 The lattice movements that transform the matrix to the equilibrium precipitate appear to be very simple.2 The mechanism of precipitation in this system is simpler and is more precisely known than that in any other system hence the system should be a profitable one for the difficult task of correlating property changes with structural alterations. The present report provides additional studies on powder X-ray diffraction from alloys of 10 per cent, 20 per cent and 30 per cent Ag, and presents the correlation of crystallographic changes with changes in microstructurc, Brinell hardness and electrical resistivity of the three alloys. Preparation of Samples and Experimental Procedure The preparation of the 20.2 per cent Ag alloy has been described2 Alloys containing 9.9 and 29.7 per cent Ag were prepared from 99.97 per cent A1 and 99.99+ per cent Ag using a similar procedure. Rolled

Jan 1, 1943

By R. F. Mehl, C. S. Barrett, A. H. Geisler

The mechanism by which the supersaturated solid solution of 20 per cent silver in aluminum decomposes has been reported in two previous publications.1&apos;2 The analysis of streaks in Laue photograms showed that thin platelike particles (the so-called Guinier-Preston aggregates) form upon matrix planes in the early state of decomposition.1 The size of these particles is larger, the higher the temperature at which they form in accordance with nucleation theory;³ at all temperatures they increase in size with aging.2 When they have grown thick enough to afford three-dimensional diffraction, powder X-ray photograms show that the structure is not that of the equilibrium precipitate but that of a transition lattice . Sincc this is also platelike in shape and also lies upon the (III) matrix planes with the [IIO] direction in the matrix parallel to the [II.O] direction in it seems likely that the original platelet particles are merely in an early stage of formation, and thus finely dispersed. The atomic spacing and pattern on the (00.1) plane in y&apos; are identical with those on the (111) matrix plane to which it lies parallel, and since comparable directions in the two planes are parallel, the lattices are thus coherent at the interface; an analogous coherence has been found in aluminum-copper alloys.3 The structures y&apos; and y are both close-packed hexagonal and are oriented alike; they differ only in interatomic distances. Consequently, y&apos; is regarded as y strained from its ordinary dimensions by the lattice coherency between it and the matrix.2 The lattice movements that transform the matrix to the equilibrium precipitate appear to be very simple.2 The mechanism of precipitation in this system is simpler and is more precisely known than that in any other system hence the system should be a profitable one for the difficult task of correlating property changes with structural alterations. The present report provides additional studies on powder X-ray diffraction from alloys of 10 per cent, 20 per cent and 30 per cent Ag, and presents the correlation of crystallographic changes with changes in microstructurc, Brinell hardness and electrical resistivity of the three alloys. Preparation of Samples and Experimental Procedure The preparation of the 20.2 per cent Ag alloy has been described2 Alloys containing 9.9 and 29.7 per cent Ag were prepared from 99.97 per cent A1 and 99.99+ per cent Ag using a similar procedure. Rolled

Jan 1, 1943

By R. F. Mehl, C. S. Barrett, A. H. Geisler

THE mechanism by which the super-saturated solid solution of 20 per cent silver in aluminum decomposes has been reported in two previous publications. 1,2 The analysis of streaks in Laue photograms showed that thin platelike particles (the so-called Guinier-Preston aggregates) form upon {111} matrix planes in the early state of decomposition.1 The size of these particles is larger, the higher the temperature at which they form in accordance with nucleation theory;3 at all temperatures they increase in size with aging.2 When they have grown thick enough to afford three-dimensional diffraction, powder X-ray photograms show that the structure is not that of the equilibrium precipitate y but that of a transition lattice ?&apos;. Since this is also platelike in shape and also lies upon the {111} matrix planes with the {110} direction in the matrix parallel to the {11.0} direction in ?&apos;, it seems likely that the original platelet particles are merely ?&apos; in an early stage of formation, and thus finely dispersed. The atomic spacing and pattern on the {00.0} plane in ?&apos; are identical with those on the {111} matrix plane to which it lies parallel, and since comparable directions in the two planes are parallel, the lattices are thus coherent at the interface; an analogous coherence has been found in aluminum-copper alloys.3 The structures ?&apos; and y are both close-packed hexagonal and are oriented alike; they differ only in interatomic distances. Consequently, ? &apos; is regarded as y strained from its ordinary dimensions by the lattice coherency between it and the matrix.2 The lattice movements that transform the matrix to the equilibrium precipitate appear to be very simple.2 The mechanism of precipitation in this system is simpler and is more precisely known than that in any other system,2,4 hence the system should be a profitable one for the difficult task of correlating property changes with structural alterations. The present report provides additional studies on powder X-ray diffraction from alloys of 10 per cent, 20 per cent and 30 per cent Ag, and presents the correlation of crystallographic changes with changes in microstructure, Brinell hardness and electrical resistivity of the three alloys. PREPARATION OF SAMPLES AND EXPERIMENTAL PROCEDURE The preparation of the 20.2 per cent Ag alloy has been described.2 Alloys containing 9.9 and 29.7 per cent Ag were prepared from 99.97 per cent Al and 99.99+ per cent Ag using a similar procedure. Rolled

Jan 1, 1943

By N. Tiner

THE mechanical properties of magnesium-alloy castings are greatly improved by grain refinement, and at present considerable attention is being paid to methods of obtaining fine-grained castings. One method of achieving this end is the use of proper melting and superheating techniques. These have been employed commercially to a great extent, but no comprehensive study of the subject appears to have been published at present. Numerous investigations found in the literature include some reference to superheating techniques, 1-4 and Achenbach, Nipper and Piwowarsky,5 based principally on thermal analysis, ascribe the grain-refining action of superheating to the influence of solid foreign particles or dissolved gases present in the melt upon the course of crystallization. The primary purpose of this paper is to present the principal facts concerning the effect of superheating on grain size of magnesium alloys. Attempts are also made to explain the experimental results in terms of a general hypothesis. The investigations are limited chiefly to common commercial casting alloys. In order to carry on this work, it was necessary to determine the factors influencing grain size and to develop a proper technique for the preparation of samples. The preliminary tests made by the author indicated that the grain size of magnesium alloys resulting from the solidification of a melt is determined by alloy composition, presence of impurities, rate of cooling during solidification, thermal history of the melt and to some extent the structure of the charge used. The rate of cooling is in turn dependent upon the mass of the melt, pouring temperature, and dimensions, properties and temperature of the mold into which the melt is poured. The final grain size of the alloys is still further modified by heat-treatment subsequent to casting. It is not within the scope of the present paper to discuss all of these factors, and it would suffice to note here that when equal amounts of magnesium alloys are prepared from the same alloying materials, melted in graphite crucibles under the same thermal conditions, then cast into graphite molds at a constant temperature, the .resultant solids have the same grain size. By maintaining all other factors constant, it is thus possible to vary thermal conditions of a melt and to examine the grain size of resultant castings. PREPARATION OF SAMPLES AND GRAIN-SIZE TESTING The alloys investigated in this paper were taken from ingots made by Permanente Metals Corporation or prepared by the author with pure carbothermic magnesium and necessary alloying elements. Melting was carried out under a flux in a graphite crucible heated uniformly by an

Jan 1, 1945