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By Richard Downs, Stephen P. Burke

The oxidation of pyritic sulphur associated with coal is important for the following reasons: 1. It is the predominant cause for the formation of acid mine drainage issuing from bituminous coal seams. This drainage pollutes the streams in coal regions, making the water unfit for industrial purposes and causing the disappearance of fish and wild life. As a consequence the movement of industry and especially recreational industry, so important to the population of these areas as an alternative means of livelihood, is impeded. 2. It is instrumental in effecting a series of reactions, which bring about the degradation and ultimately result in the spontaneous combustion of bituminous coal in storage. 3. It contributes to the breaking and shattering of the coal structure and is one of the causes of roof falls and floor lifts in mines. 4. It is the primary cause of the many nuisances associated with gob piles and the refuse of cleaning plants. 5. Its proper control and application might possibly be employed in the preparation of coal to reduce the inorganic sulphur content. The research that has been conducted on the oxidation of the various forms of iron sulphides is extensive and the literature voluminous. Nevertheless, few efforts have been made to determine experimentally and with some precision the mechanism of the reaction under the conditions of its occurrence in bituminous coal mines. It has generally been accepted that the oxidation of pyritic sulphur proceeds according to the reaction 2FeS2 + 2H2O + 7O2 ? 2FeSO4 + 2H2SO4 [1] The ferrous sulphate in the drainage streams is further oxidized by air to produce ferric hydroxide and more acid. Yet the literature fails to disclose any pertinent investigation on the mechanism of this reaction. The present contribution is concerned primarily with this aspect of the problem and while the work to be reported is not yet complete, it has yielded results from which interesting and significant conclusions may be drawn.

Jan 1, 1938

By C. R. Austin

In a recent paper1 the authors presented information on a refinement of the Rohn type of creep test with data on pure iron that exemplified the behavior of the apparatus. The present paper extends that work to nickel and cobalt and to the examination of the comparative high-temperature properties of two widely used commercial alloys. Careful attention has been given to the effect of plastic deformation in decreasing creep rate, using the elementary metals iron, nickel and cobalt for purposes of analysis. In any endeavor to develop new materials for high-temperature service one soon encounters a real problem as to the sort of test to be employed in evaluating the commercial possibilities of the alloys. At one time it was considered satisfactory to determine the tensile strengths at elevated temperatures and to use these values as a criterion for the commercial application of the alloys. More recently the proportional limit has been used as a means of classification. Data obtained from a form of bend test have also shown promise as providing a "merit index" of high-temperature serviceability.= Koerber and Pomp3 state that since the influence of testing time is small, the high-temperature yield point of steel furnishes sufficiently reliable and concordant values up to about 350" C. (and a maximum of 450" C. for alloy steels) to serve as a suitable basis for comparison evaluations of materials and for judging permissible stresses. Koerber and Pomp consider, however, that above these temperatures creep limit must be substituted for the high-temperature yield point as the all-important characteristic of the material. Whatever may be their definition of

Jan 1, 1934

By Maurice L. Pinel, Thomas Wright, Thomas T. Read

The erroneous, but until recently widely prevalent, belief that iron castings were first made in Europe in the fourteenth century has been adequately refuted in a number of earlier papers;1, ll, l² but except for an unpublished metallographic study by the late William Campbell, and a phosphorus analysis by T. A. Wright of the metal of the Han dynasty cast-iron stove described by Laufer,2 nothing was known of either the chemical composition or the metallographic structure of the metal of any ancient iron casting, although data on castings of recent manufacture are abundantly available. The metal of the stove, which had been buried in a grave for at least 15 centuries, was so corroded that it seemed inadvisable to publish the results on it until morc and better specimens from other ancient castings could be obtained. During a journey through China, extending from Peking in the north to Canton in the south and Cheng-tu, Ssu-chuan, in the west, in the late summer and autumn of 1936, one of us (T. T. Read) was fortunate enough to obtain, and bring home for study, nine castings, all more than 1000 years old, of which the date of manufacture is precisely known because of inscriptions cast in them, another that lacks a dated inscription, but of which the date, as explained below, can be otherwise established, and a specimen from the largest iron casting ever made," which is also dated. The period covered by this suite of specimens extends from 502 to 1093 A.D. In addition, a sample was obtained from a casting of date unknown, but which was certainly cast before 1000 A.D. and possibly as early as the third century A.D. A detailed description of these specimens is as follows: I. 502 A.D. A pair [right and left) of recumbent lions (Fig. 1). Base 7¼ by 113/8 in., height over-all 5½in, weight 26 Ib. each. The tranblation of the inscription on the base is: "Made on the twenty-fourth day of the seventh month of the third pear of Ching Ming of Great Wei" (Sept. 11, 502 A.D.).

Jan 1, 1938

By Maurice L. Pinel, Thomas Wright, Thomas T. Read

The erroneous, but until recently widely prevalent, belief that iron castings were first made in Europe in the fourteenth century has been adequately refuted in a number of earlier papers;1, ll, l² but except for an unpublished metallographic study by the late William Campbell, and a phosphorus analysis by T. A. Wright of the metal of the Han dynasty cast-iron stove described by Laufer,2 nothing was known of either the chemical composition or the metallographic structure of the metal of any ancient iron casting, although data on castings of recent manufacture are abundantly available. The metal of the stove, which had been buried in a grave for at least 15 centuries, was so corroded that it seemed inadvisable to publish the results on it until morc and better specimens from other ancient castings could be obtained. During a journey through China, extending from Peking in the north to Canton in the south and Cheng-tu, Ssu-chuan, in the west, in the late summer and autumn of 1936, one of us (T. T. Read) was fortunate enough to obtain, and bring home for study, nine castings, all more than 1000 years old, of which the date of manufacture is precisely known because of inscriptions cast in them, another that lacks a dated inscription, but of which the date, as explained below, can be otherwise established, and a specimen from the largest iron casting ever made," which is also dated. The period covered by this suite of specimens extends from 502 to 1093 A.D. In addition, a sample was obtained from a casting of date unknown, but which was certainly cast before 1000 A.D. and possibly as early as the third century A.D. A detailed description of these specimens is as follows: I. 502 A.D. A pair [right and left) of recumbent lions (Fig. 1). Base 7¼ by 113/8 in., height over-all 5½in, weight 26 Ib. each. The tranblation of the inscription on the base is: "Made on the twenty-fourth day of the seventh month of the third pear of Ching Ming of Great Wei" (Sept. 11, 502 A.D.).

Jan 1, 1938

By James Norman, Benjamin S. Lindsey

Barite (BaSO4) is the most important industrial barium mineral from the standpoint of quantity consumed. In 1938 the amount was 365,000 tons. Its uses are numerous, some of the more important being in the production of pigments, as an inert filler in a wide variety of products, as a weighting material in oil-well drilling muds, in the manufacture of some binds of glass, and in the production of barium chemicals. The barite studied in this investigation occurs as the massive variety in a shale replacement formation near Magnet Cove, Ark. It is intimately mixed with quartz and small amounts of iron oxide and residual shale. Complete liberation of barite and quartz is not obtained when the rock is ground to I00 per cent through 325 mesh. The crude rock with which all test work was done assayed 85.1 per cent BaS04, II.II. per cent SiO2, and 2.85 per cent R2O3. Its specific gravity was 4.03. It was found in the course of the investigation that the barite contained a small amount of uniformly distributed carbonaceous material, so intimately dispersed that it could not be seen with the microscope, but gave a definite gray cast to the barite concentrates. The color of the barite in polished sections of the crude rock ranged from gray to almost black, while finely ground powder was a reddish gray. The reddish hue was due to the iron oxide present. In 1939, under the supervision of Oliver C. Ralston,* the Bureau of Mines, in cooperation with the Milwhite Company, of Houston, Texas, undertook to study the flotation of barite from Magnet Cove, Ark. Flotation of several southern barite ores had already been investigated by the Bureau of Mines.' The Magnet Cove barite was unique, however, in that it had to be ground to such an extremely small particle size for liberation. The flotation of non-metallic minerals in the presence of a large amount of slime is usually very difficult, and when done is an innovation calling for conditions different from those under which granular material is separated. Laboratory Flotation Work Preliminary investigation showed that the flotation reagents recommended by O'Meara and Coel for separating barite and siliceous material were suitable, but much larger quantities of reagents were required to separate such finely divided material. Moreover, it was found that careful control of the frothing was necessary. When oleic acid and sodium silicate were used a voluminous froth was observed at the beginning of a test, and toward the end there was not enough froth to effect complete recovery of barite. The addition of pine oil as a frother gave proper frothing for the duration of the test, and the substitution of coconut fatty acid (crude lauric acid) for oleic acid produced a more heavily burdened froth. Two different paper-mill fatty-acid products were tested

Jan 1, 1943

By Benjamin S. Lindsey, James Norman

Barite (BaSO4) is the most important industrial barium mineral from the standpoint of quantity consumed. In 1938 the amount was 365,000 tons. Its uses are numerous, some of the more important being in the production of pigments, as an inert filler in a wide variety of products, as a weighting material in oil-well drilling muds, in the manufacture of some binds of glass, and in the production of barium chemicals. The barite studied in this investigation occurs as the massive variety in a shale replacement formation near Magnet Cove, Ark. It is intimately mixed with quartz and small amounts of iron oxide and residual shale. Complete liberation of barite and quartz is not obtained when the rock is ground to I00 per cent through 325 mesh. The crude rock with which all test work was done assayed 85.1 per cent BaS04, II.II. per cent SiO2, and 2.85 per cent R2O3. Its specific gravity was 4.03. It was found in the course of the investigation that the barite contained a small amount of uniformly distributed carbonaceous material, so intimately dispersed that it could not be seen with the microscope, but gave a definite gray cast to the barite concentrates. The color of the barite in polished sections of the crude rock ranged from gray to almost black, while finely ground powder was a reddish gray. The reddish hue was due to the iron oxide present. In 1939, under the supervision of Oliver C. Ralston,* the Bureau of Mines, in cooperation with the Milwhite Company, of Houston, Texas, undertook to study the flotation of barite from Magnet Cove, Ark. Flotation of several southern barite ores had already been investigated by the Bureau of Mines.' The Magnet Cove barite was unique, however, in that it had to be ground to such an extremely small particle size for liberation. The flotation of non-metallic minerals in the presence of a large amount of slime is usually very difficult, and when done is an innovation calling for conditions different from those under which granular material is separated. Laboratory Flotation Work Preliminary investigation showed that the flotation reagents recommended by O'Meara and Coel for separating barite and siliceous material were suitable, but much larger quantities of reagents were required to separate such finely divided material. Moreover, it was found that careful control of the frothing was necessary. When oleic acid and sodium silicate were used a voluminous froth was observed at the beginning of a test, and toward the end there was not enough froth to effect complete recovery of barite. The addition of pine oil as a frother gave proper frothing for the duration of the test, and the substitution of coconut fatty acid (crude lauric acid) for oleic acid produced a more heavily burdened froth. Two different paper-mill fatty-acid products were tested

Jan 1, 1943

By M. A. Grossman

The harden ability of most steels can be predicted within 10 to I5 per cent provided the complete chemical composition is known, including "incidental" elements; and provided the as-quenched grain size is known; and provided, finally, that the composition and heating temperatures for hardening are such as to result in austenite free from carbide particles. In the method proposed herein, the steel is considered as having a base hardenability due to its carbon content alone (the hardenability of a "pure steel" of the given carbon content, without any other elements), and this base hardenability is multiplied by a multiplying factor for each chemical element present. After multiplying all these together, the final product is the hardenability. Grain size may be taken into account either in the base hardenability or after the multiplication. Hardenability is stated in terms of "ideal critical diameter", namely, the diameter of bar, in inches, that will just harden all the way through (absence of un-hardened core) in an "ideal" quench, and the calculation may also be related to the Jominy test The data bring out certain features rather clearly. For example: i. It is quite useless to attempt to predict hardenability unless all elements, including "incidentals,,) are known; thus an "incidental,, chromium content of 0.20 per cent increases the hardenability by about 50 per cent. 2. The relative effectiveness of different alloys is sometimes unexpected; thus molybdenum when calculated in this way appears to be of the same order of effectiveness as manganese, rather than much more powerful, as would appear to be common experience; observe that an increase from no manaanese to 0.20 per cent Mn provides a multiplying factor of 1.67, and an increase from no molybdenum to 0.20 per cent Mo provides a factor of 1.63, an increase of over 60 per cent in each case. However, if to a steel containing 0.50 per cent Mn there is added "20 points of manganese," the factor is raised from 2.65 (for 0.50 per cent Mn) to 3.35 (for 0.70 per cent Mn), or an increase of only 26 per cent. Thus the fist small addition of an element has a much more powerful percentage effect than an equal further addition when some is already present, and in most cases the effect of molybdenum is considered in relation to a steel in which molybdenum is absent. 3. If two elements are equally effective, a greater hardenability will be obtained by using, for example, 0.5 per cent of each than by using I.o per cent of either of them alone. 4. A knowledge of the as-quenched grain size is essential for precise work, since a difference of only one grain size number (say No. 7 instead of No. 6) makes a difference of almost 10 per cent in hardenability (in these units); this, however, does not apply to certain It should be emphasized that in chromium steels (over 0.30 per cent Cr) and chrome-molybdenum and chrome-vanadium steels, un-dissolved carbides are likely to be present in the steel as quenched, and that in such cases the charts can indicate only a maximum Passible hardenability, whereas the extent of hardening actually obtained may be much less. Thus tests on a number of chrome-molybdenum steels have indicated a degree of hardening amounting to only 50 to 65 per cent of the maximum possible, and in chromium steels from full hardening (100 per cent) down to as low as 70 per cent. On the other hand, when the amount of such elements is small (Cr under 0.30 per cent, Mo up to 0.25 per cent in the

Jan 1, 1942

By M. A. Grossman

The harden ability of most steels can be predicted within 10 to I5 per cent provided the complete chemical composition is known, including "incidental" elements; and provided the as-quenched grain size is known; and provided, finally, that the composition and heating temperatures for hardening are such as to result in austenite free from carbide particles. In the method proposed herein, the steel is considered as having a base hardenability due to its carbon content alone (the hardenability of a "pure steel" of the given carbon content, without any other elements), and this base hardenability is multiplied by a multiplying factor for each chemical element present. After multiplying all these together, the final product is the hardenability. Grain size may be taken into account either in the base hardenability or after the multiplication. Hardenability is stated in terms of "ideal critical diameter", namely, the diameter of bar, in inches, that will just harden all the way through (absence of un-hardened core) in an "ideal" quench, and the calculation may also be related to the Jominy test The data bring out certain features rather clearly. For example: i. It is quite useless to attempt to predict hardenability unless all elements, including "incidentals,,) are known; thus an "incidental,, chromium content of 0.20 per cent increases the hardenability by about 50 per cent. 2. The relative effectiveness of different alloys is sometimes unexpected; thus molybdenum when calculated in this way appears to be of the same order of effectiveness as manganese, rather than much more powerful, as would appear to be common experience; observe that an increase from no manaanese to 0.20 per cent Mn provides a multiplying factor of 1.67, and an increase from no molybdenum to 0.20 per cent Mo provides a factor of 1.63, an increase of over 60 per cent in each case. However, if to a steel containing 0.50 per cent Mn there is added "20 points of manganese," the factor is raised from 2.65 (for 0.50 per cent Mn) to 3.35 (for 0.70 per cent Mn), or an increase of only 26 per cent. Thus the fist small addition of an element has a much more powerful percentage effect than an equal further addition when some is already present, and in most cases the effect of molybdenum is considered in relation to a steel in which molybdenum is absent. 3. If two elements are equally effective, a greater hardenability will be obtained by using, for example, 0.5 per cent of each than by using I.o per cent of either of them alone. 4. A knowledge of the as-quenched grain size is essential for precise work, since a difference of only one grain size number (say No. 7 instead of No. 6) makes a difference of almost 10 per cent in hardenability (in these units); this, however, does not apply to certain It should be emphasized that in chromium steels (over 0.30 per cent Cr) and chrome-molybdenum and chrome-vanadium steels, un-dissolved carbides are likely to be present in the steel as quenched, and that in such cases the charts can indicate only a maximum Passible hardenability, whereas the extent of hardening actually obtained may be much less. Thus tests on a number of chrome-molybdenum steels have indicated a degree of hardening amounting to only 50 to 65 per cent of the maximum possible, and in chromium steels from full hardening (100 per cent) down to as low as 70 per cent. On the other hand, when the amount of such elements is small (Cr under 0.30 per cent, Mo up to 0.25 per cent in the

Jan 1, 1942

By J. T. Eash, N. B. Pilling

As a group, the alloys of iron, nickel and carbon are, in application, one of the most versatile of the ferrous alloy family, and while many investigations have been made of their properties and structure only a few attempts have been made to show the microstructural relation over a wide range of composition. It is neccssary at once to be clear about the kind of structural relation with which we are concerned. The equilibrium diagram provides quantitative data regarding structural make-up and its variation with temperature, but equilibrium structures often are far different from the technologically significant ones. This is particularly true of steels and cast irons, and some of the most important cornponents of their structure may have no place in the diagram of equilibrium. The fugitive phases that result from transFormation are dealt with in a highly detailed and descriptive manner in. the S-curves originated by Bain. The present effort lies in a still different field, which is to portray the relation between sweeping changes in composition and in resultant structure, under controlled but nonequilib-rium conditions of thermal treatment. The Guilletl diagram presented in 1903 was the initial attempt at such a correlation and frequent references to this diagram can be found in the literature even though later work has shown it to require considerable modification. Kase2 published in 1925 a diagram that was based upon observations of furnace-cooled melts: At low carbon contents this diagram agreed fairly well with experience in showing pearlite to exist in alloys containing up to 6 per cent nickel, and completely austenitic steels at 24 to 28 per cent nickel. At high carbon contents, however, irons were indicated as being martensitic at around 2 per cent nickel and austenitic at 12 per cent nickel; these interpretations are open to serious question. Based upon experience with steels and cast iron, Wickenden3 suggested a diagram that agreed fairly well with Kase's in the steel range but which presented a wide departure from it in the higher-carbon, high-nickel regions. In its broad picture, the Wickenden diagram is an approach to "practical" structures. Reference may be made at this point to the efforts of Marsh5 to construct an iron-nickel-carbon equilibrium diagram by the coordination of scattered data, which are described at length in the monograph cited. None of these preceding attempts has appeared to meet the need for an exposition of the structural sequence that is encountered in traversing the nickel-steel nickel-cast-iron range under what might be called ordinary departures from equilibrium. ExperimentaT. Conditions Since the intent has been to establish structures developed under arbitrary conditions, experimental details have perhaps more than usual importance. Three of these conditions should particularly be noticed: (I) the material was cast and not subjected

Jan 1, 1942

By J. T. Eash, N. B. Pilling

As a group, the alloys of iron, nickel and carbon are, in application, one of the most versatile of the ferrous alloy family, and while many investigations have been made of their properties and structure only a few attempts have been made to show the microstructural relation over a wide range of composition. It is neccssary at once to be clear about the kind of structural relation with which we are concerned. The equilibrium diagram provides quantitative data regarding structural make-up and its variation with temperature, but equilibrium structures often are far different from the technologically significant ones. This is particularly true of steels and cast irons, and some of the most important cornponents of their structure may have no place in the diagram of equilibrium. The fugitive phases that result from transFormation are dealt with in a highly detailed and descriptive manner in. the S-curves originated by Bain. The present effort lies in a still different field, which is to portray the relation between sweeping changes in composition and in resultant structure, under controlled but nonequilib-rium conditions of thermal treatment. The Guilletl diagram presented in 1903 was the initial attempt at such a correlation and frequent references to this diagram can be found in the literature even though later work has shown it to require considerable modification. Kase2 published in 1925 a diagram that was based upon observations of furnace-cooled melts: At low carbon contents this diagram agreed fairly well with experience in showing pearlite to exist in alloys containing up to 6 per cent nickel, and completely austenitic steels at 24 to 28 per cent nickel. At high carbon contents, however, irons were indicated as being martensitic at around 2 per cent nickel and austenitic at 12 per cent nickel; these interpretations are open to serious question. Based upon experience with steels and cast iron, Wickenden3 suggested a diagram that agreed fairly well with Kase's in the steel range but which presented a wide departure from it in the higher-carbon, high-nickel regions. In its broad picture, the Wickenden diagram is an approach to "practical" structures. Reference may be made at this point to the efforts of Marsh5 to construct an iron-nickel-carbon equilibrium diagram by the coordination of scattered data, which are described at length in the monograph cited. None of these preceding attempts has appeared to meet the need for an exposition of the structural sequence that is encountered in traversing the nickel-steel nickel-cast-iron range under what might be called ordinary departures from equilibrium. ExperimentaT. Conditions Since the intent has been to establish structures developed under arbitrary conditions, experimental details have perhaps more than usual importance. Three of these conditions should particularly be noticed: (I) the material was cast and not subjected

Jan 1, 1942

By E. H. Dix

The work of Merical and other investigators indicates that the phenomenon of age-hardening in alloys of the duralumin type is primarily dependent upon the variation in the solubility of copper with temperature. In addition to copper, however, these alloys contain small amounts of magnesium, silicon, manganese and iron, which may affect the age-hardening either directly or indirectly. The effect of these elements on the solubility of copper and on the manner in which this solubility varies with the temperature is of considerable interest, therefore. The effect of magnesium is of especial interest because apparently it exerts a marked effect on the natural or room-temperature aging of alloys of the type described.2 A series of investigations3 has been in progress in the research laboratories of the Aluminum Company of America to determine the functions * Metallurgist, Aluminum Research Laboratories. f Metallurgical Division, Aluminum Research Laboratories. Formerly with Metallurgical Division, Aluminum Research Laboratories. 1 P. D. Merica, It. G. Waltenberg and H. Scott: Heat Treatment of Duralumin. U. S. Bur. Stds. Sn. Paper 347 (1910). 2 M. Gayler: Constitution and Age-Hardening of Alloys of Aluminum with Copper, Magnesium, and Silicon in the Solid State. Jnl. Inst. Met. (1922) 28, 213. W. Fraenkel: Vergutbare Aluminiumlegiengen. Ztsch. Melallkunde. (1920) 12, 427. E. H. Dix, Jr.: Note on the Microstructure of Aluminum-Iron Alloys of High Purity. Proc. Amer. Soc. Test. Mat. (1925) 26, Pt. 2, 120. E. H. Dix, Jr. and H. H. Richardson: Equilibrium Relations in Aluminum-copper Alloys of High Purity. Trans. A. I. M. E. (1926) 73, 560. E. H. Dix, Jr. and W. D. Keith: Equilibrium Relations in Aluminum-manganese Alloys of High Purity. Proc. Inst. Met. Div., A. I. M. E. (1927) 315. E. H. Dix, Jr. and A. C. Heath, Jr.: Equilibrium Relations in Aluminum-silicon and Aluminum-iron-silicon Alloys of High Purity. Proc. Inst. Met. Div., A. I. M. E. (1928) 164. E. H. Dix, Jr. and F. Keller: Equilibrium Itelations in Aluminum-magnesium Alloys of High Purity. Proc. Inst. Met. Div., A. I. M. E. (1920) 351. E. H. Dix, Jr., F. Keller and R. W. Graham: Equilibrium Relations of Aluminum-magnesium Silicide Alloys of High Purity. Trans. A. I. M. E., Inst. Met. Div. (1931) 404. W. L. Fink and K. R. Van Horn: Constituents of Aluminum-iron-silicon Alloys. Trans. A. I. M. E., Inst. Met. Div. (1931) 383.

Jan 1, 1932

By Cyril Wells, Robert F. Mehl

The purpose of this investigation was to prepare high-purity iron-carbon alloys, to determine as precisely as possible the A3(GOS), the Acm(SE), and the A1(PSK) transformation temperatures in the meta-stable iron-iron carbide system (up to 1.4 per cent C), and to study the influence of carefully controlled and constant rates of heating and cooling (1/8 to 2o C. per minute) upon the transformation temperature and upon the resulting microstructure. Apart from the general metallurgical importance attending the completion of such a task, it will be noted that highly precise transformation temperatures are of interest and importance in the thermodynamic study of this system1. Several determinations of the iron-iron carbide diagram have been made2. These suffer generally from the low purity of the alloys used, and from the application of methods of investigation of low sensitivity. Attempts to compare and weight the many data available in an effort to construct as accurate a diagram as possible have, in the main, been unsuccessful. In general, the wide differences in the results of different workers, the lack of complete analytical data, the omission of important details relating to the heat-treatment of the alloys, and the meager description of the methods of investigation applied, render such a process of averaging nearly meaningless. It may be seen from the summaries by Epstein2 and Körber and Oelsenl that variations as great as 30' C. exist in the reported data on the A3 temperatures in iron-carbon alloys. Fortunately, the Aa temperature in pure iron is now known to be 910" C. ± 1° C.3 The best recent work on iron-carbon alloys is that of Esser4 on hypoeutectoid steels and that of Sato5 on both hypoeutectoid and hyper-eutectoid steels. Esser made a dilatometric and magnetic study of iron and iron-carbon alloys containing 0.06 to 0.86 per cent C, for which a high purity is claimed. Presumably the electrolytic iron was reasonably pure, but the alloys contained considerable impurities, on the average totaling 0.35 per

Jan 1, 1937

By H. A. Bright, H. C. Vacher, J. G. Thompson

The methods employed for the determination of oxides and oxygen in ferrous materials may be roughly classed in two groups, "wet" methods and "hot" methods, the first group including the iodine, electrolytic, mercuric chloride, hydrochloric acid, nitric acid, and chlorine methods; the second group including the vacuum-fusion and hydrogen-reduction methods. The wet methods depend upon preferential solubility in a selected medium to separate the metallic portion of the sample from the oxygen-containing constituents. Subsequent analysis of the insoluble residue permits the isolation and separate determination of individual oxides and compounds. The hot methods depend upon the reduction of the oxide constituents of the sample by means of carbon or hydrogen at elevated temperatures. With the exception of the recently developed fractional vacuum-fusion method, the hot methods do not identify individual oxides and compounds but yield only a single value representing the sum of the oxygen contents of several or all of the oxide constituents present. With such diversity in the principles and aims of the different groups, it is not surprising that concordance of results by different methods has usually been difficult to obtain. The present cooperative attempt to define more rigorously than has been possible heretofore the accuracy and limits of usefulness of the various methods, originated in correspondence between Dr. John Johnston, Director of Research of the United States Steel Corporation, and other interested metallurgists. The plan was, briefly, to submit identical samples to a number of laboratories for analysis by different methods and to collate the results of these analyses. The project was endorsed by the Iron and Steel Division of the American Institute of Mining and Metallurgical Engineers at the annual meeting in February, 1933, and has been conducted under the joint sponsorship of the Iron and Steel Division and the National Bureau of Standards. The latter organization undertook

Jan 1, 1937

By Cyril Stanley Smith

For many years sulphur and its congeners selenium and tellurium have been regarded as very harmful elements in copper and copper-rich alloys. Like many similar prejudices, this has been found to be partly wrong. All three of these elements actually have no great effect on the working properties of copper and its alloys, and are desirable additions in that they considerably enhance the machinability of alloys in which they are present. Because of their possible commercial importance, a study of the machinability and other properties of the pure binary alloys was made, as described in this paper, and the effect of selenium on a large number of copper alloys was determined. The current opinion regarding the deleterious effects of elements in this group undoubtedly arose because of occasional failures of tough-pitch copper containing unusually high tellurium, and because of the well-known fact that sulphur causes spewing and unsoundness in tough-pitch copper. Siebe,1 also Deretchey and Margolina,2 studied the effect of sulphur on copper and showed that in the absence of oxygen it was present in the form of copper sulphide, which was less harmful to the properties than an equivalent amount of copper oxide. No data have been published on selenium and tellurium, although the statement is often made, following Eggleston,3 that tellurium makes copper hot-short. Copper specifications call for only traces of these elements. Skowronski and Mosher4 give data on the effect of selenium and tellurium on the conductivity of tough-pitch copper. In private communication Mr. Skowronski says that the samples were hot-forged from small castings and drawn to 0.081 in. diameter, but it should not be inferred from this that these elements are harmless to the working properties of wirebars and commercial shapes. Constitution and Microstructure Constitution.—Sulphur, selenium and tellurium exist in their alloys with copper in the form of copper sulphide, selenide or telluride. These compounds are practically insoluble in the solid state and possess limited

Jan 1, 1938

By Cyril Stanley Smith

For many years sulphur and its congeners selenium and tellurium have been regarded as very harmful elements in copper and copper-rich alloys. Like many similar prejudices, this has been found to be partly wrong. All three of these elements actually have no great effect on the working properties of copper and its alloys, and are desirable additions in that they considerably enhance the machinability of alloys in which they are present. Because of their possible commercial importance, a study of the machinability and other properties of the pure binary alloys was made, as described in this paper, and the effect of selenium on a large number of copper alloys was determined. The current opinion regarding the deleterious effects of elements in this group undoubtedly arose because of occasional failures of tough-pitch copper containing unusually high tellurium, and because of the well-known fact that sulphur causes spewing and unsoundness in tough-pitch copper. Siebe,1 also Deretchey and Margolina,2 studied the effect of sulphur on copper and showed that in the absence of oxygen it was present in the form of copper sulphide, which was less harmful to the properties than an equivalent amount of copper oxide. No data have been published on selenium and tellurium, although the statement is often made, following Eggleston,3 that tellurium makes copper hot-short. Copper specifications call for only traces of these elements. Skowronski and Mosher4 give data on the effect of selenium and tellurium on the conductivity of tough-pitch copper. In private communication Mr. Skowronski says that the samples were hot-forged from small castings and drawn to 0.081 in. diameter, but it should not be inferred from this that these elements are harmless to the working properties of wirebars and commercial shapes. Constitution and Microstructure Constitution.—Sulphur, selenium and tellurium exist in their alloys with copper in the form of copper sulphide, selenide or telluride. These compounds are practically insoluble in the solid state and possess limited

Jan 1, 1938

By W. E. Remmers

The defect in wire known as "cuppiness" has appeared and disappeared from time to time but the exact cause of its appearance or disappearance has not heretofore been known definitely. This defect is not limited to one particular metal or alloy but seems to be found at various times in all of the materials that are drawn into wire. Fig. 1 represents cuppy wire made from an aluminum alloy and Fig. 2 illustrates copper wire that became cuppy in drawing without intermediate annealing. Differences of opinion are current among the manufacturers of wire and in the literature (see bibliography at end of paper), some believing that the source of the trouble lies in segregation in the wire rod, oxides, sulfides, slag, etc.; others that the trouble is created by an unevenness of stress distribution across the section of the wire, usually thought of as being a function of die shape. All of the published work is of a qualitative rather than a quantitative nature. With this in mind, it was deemed advisable to make a study of the shape of the wire-drawing dies, as well as the oxygen content of the copper to be drawn. Experimental After several methods were tried, it was found that by studying the contour of the butt-end of the rod after drawing a measure of the "working" across the section of the wire could be made. The butt-end of the annealed rod was not sheared but was sawed off. The end was then smoothed with a fine file so that the plane of filing was perpendicular to the drawing axis. It is to be noted that this method is not an absolute measure of the distribution of cold working but is a very good indicative means of studying comparative values. The method of examining a tension break in wire was found to be the most sensitive in detecting cuppiness. Other methods, such as microscopic examination of longitudinal sections, X-ray radiographic studies, etching away of outer layers with nitric acid, and fracture by bending, can all be used to identify cuppy wire but the tension break will give the fracture characteristic of cuppiness before any of the other methods can

Jan 1, 1930

By C. T. Eddy, R. W. Drier

The conductivity of copper wire is of prime importance to the electrical industry and consequently to the copper refiner and wire manufacturer. Annealed copper wire has a higher conductivity than hard-drawn wire, but, on the other hand, its tensile strength is lower. In an attempt to explain the reasons for these changes in properry. or at least to study the conditions existing in these two types of copper wire, the experiments described here were carried on in the Department of Metallurgy of the Michigan College of Mining and Technology This is only a partial and preliminary report on some of the work done to date on a research program of which the object is an intensive study of copper. It is offered with the hope that, though it is not an exposition of the most rigorous of conclusions, the general trend of inferences which may be drawn will be of value and interest. Effect of Direction of Drawing In 1928 some work was done on hard-drawn copper wires to determine whether wire drawn in a continuous machine (that is, all in one direction) would have a different structure from wire that had a reversal in direction at some stage of the drawing process. The diffraction spectra obtained indicated that as the position of the wire rayed approached the core, a preferential crystal orientation existed, and that the closer to the core the more preferred was the orientation. The data obtained partly corroborated the work done by Schmidt and Wassermanl and by Clark.2 Samples Used in Following Investigation The samples selected for use in both the diffraction work and the resistivity measurements were taken from Nos. 6, 8, 10 and 12 gage

Jan 1, 1930

By A. A. Smith, J. S. Smart

THe elements silver, cadmium, tin, antimony and tellurium either are found as impurities in commercial coppers or are intentionally added to produce coppers for special uses. When present in small quantities, each of these metals exerts a significant effect on the properties of copper, but despite considerable experience and investigation much remains to be learned about their specific behavior. The presence of extraneous elements, particularly oxygen, complicates the study of individual additions of impurities in the range o to 0.05 per cent, and the use of high-purity copper has been found extremely helpful in circumventing these difficulties. It has also been found that individual behavior can be satisfactorilv determined from measurements of two commercially important properties, conductivity and softening temperature, according to methods that have been described previously.1,2 Data of this type, obtained in the course of a general investigation of the effects of impurities on the properties of both oxygen-bearing 2nd oxygen-free copper are presented herewith. All samples except those containing cadmium were prepared as 3/8-in. continuously cast oxygen-free rod from pure copper and weighed amounts of a similarly synthesized master alloy. Composition was checked by chemical methods, which in every case verified the calculated analyses. Test wires were cold-drawn one B, and S. number per pass on a string-up machine using four 30-min. 600°C. anneals at 0.3125, 0.257, 0.204 and 0.162 in. and a final cold reduction of 75 per cent to 0.081 in. Some oxygen-bearing samples were produced directly from the 3/8-in. oxygen-free rods by diffusion from a surface scale at 850°C. and drawn to size as listed above, but most of the alloys were remelted in pure graphite and cast through air into a I-in. round mold. The slugs were then hot-rolled to 5/16 in., drawn to 0.162 in., annealed as listed above, and drawn to 0.081 inch. Conductivity wires were annealed for I hr. at 100°C. intervals between 300' and 800°F., using a hydrogen atmosphere for oxygen-free samples and purified nitrogen for the oxygen-bearing type. All samples were quenched from the annealing temperature in 10 per cent H²S04 and conductivity was measured on a Hoopes bridge that had been checked against a Kelvin bridge. The softening temperatures represent the half-hard stage of the annealing curve as determined by a standard procedure.' Effect of Silver Numerous excellent studies of the argentiferous coppers are found in the literature, and these have been adequately

Jan 1, 1943

By A. A. Smith, J. S. Smart

THe elements silver, cadmium, tin, antimony and tellurium either are found as impurities in commercial coppers or are intentionally added to produce coppers for special uses. When present in small quantities, each of these metals exerts a significant effect on the properties of copper, but despite considerable experience and investigation much remains to be learned about their specific behavior. The presence of extraneous elements, particularly oxygen, complicates the study of individual additions of impurities in the range o to 0.05 per cent, and the use of high-purity copper has been found extremely helpful in circumventing these difficulties. It has also been found that individual behavior can be satisfactorilv determined from measurements of two commercially important properties, conductivity and softening temperature, according to methods that have been described previously.1,2 Data of this type, obtained in the course of a general investigation of the effects of impurities on the properties of both oxygen-bearing 2nd oxygen-free copper are presented herewith. All samples except those containing cadmium were prepared as 3/8-in. continuously cast oxygen-free rod from pure copper and weighed amounts of a similarly synthesized master alloy. Composition was checked by chemical methods, which in every case verified the calculated analyses. Test wires were cold-drawn one B, and S. number per pass on a string-up machine using four 30-min. 600°C. anneals at 0.3125, 0.257, 0.204 and 0.162 in. and a final cold reduction of 75 per cent to 0.081 in. Some oxygen-bearing samples were produced directly from the 3/8-in. oxygen-free rods by diffusion from a surface scale at 850°C. and drawn to size as listed above, but most of the alloys were remelted in pure graphite and cast through air into a I-in. round mold. The slugs were then hot-rolled to 5/16 in., drawn to 0.162 in., annealed as listed above, and drawn to 0.081 inch. Conductivity wires were annealed for I hr. at 100°C. intervals between 300' and 800°F., using a hydrogen atmosphere for oxygen-free samples and purified nitrogen for the oxygen-bearing type. All samples were quenched from the annealing temperature in 10 per cent H²S04 and conductivity was measured on a Hoopes bridge that had been checked against a Kelvin bridge. The softening temperatures represent the half-hard stage of the annealing curve as determined by a standard procedure.' Effect of Silver Numerous excellent studies of the argentiferous coppers are found in the literature, and these have been adequately

Jan 1, 1943

By Alan Morris

In a previous paper1 the results of cutting tests on free-cutting brass rod were reported. Investigation was made of the effects of variation in lead content, microstructure and cold drawing. The author's reply to the discussion of that paper includes a study of the directional cutting properties of drawn and annealed rod. The present paper records the results of tests made on series of samples in which the tin, iron and copper contents have been varied. The apparatus used and method of testing are described in detail in the previous paper. The machine is of the pendulum-operated milling type used and described by Airey and Oxford.2 Angular readings of the height to which the pendulum rises after falling from a fixed position, both when a cut is made and when the pendulum swings freely, give the basis for calculation of the energy consumed in making a cut. Careful weighing of the sample before and after cutting gives a measure of the amount of metal removed. The results are expressed in footpoiinds per cubic inch of metal removed, and have been called "unit cutting energy." In the course of the discussion of the author's earlier paper, W. B. Price reported large-scale tests involving some 50,000 lb. of material. These tests indicated that the addition of as much as 0.6 per cent of iron and 0.25 per cent of tin had apparently no adverse effect on the highspeed cutting characteristics of the rod. The rod also contained a small amount of nickel. The test results reported here tend to confirm his observations. Effect of Variation in Tin Content The castings for this series were made 2 by 1 by 9 in. and were processed as follows: 1. Castings were annealed at 500" C. for 7 hr. 2. Cold-rolled to 0.700 in.

Jan 1, 1933