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By W. R. McMillan, E. A. Gulbransen, K. F. Andrew

Annealed and electrolytically polished pure iron was oxidized between 650° and 850°C at oxygen pressures of 0.1 to 2 microns Hg. Electron optical studies showed that oxidation occurs discontinuously over the surface and orients crystallographically with the substructure of the metal grains. IN previous papers', " the authors described the formation of oxide films on high purity iron at norrnal pressures and at temperatures below 300°C. Electron optical studies showed that the oxide film consisted of many individual oxide crystallites having nearly random orientation on each metal grain. The size of the oxide crystallites depended upon the temperature and upon the extent of oxidation. In these studies the crystallite size varied from 250 to 1800Å. Recently, Bardolle and Benard3 studied the crystal habit of the oxide crystallites formed on Armco iron between 650" and 850°C in what might be defined as a "poor vacuum" atmosphere in which the pressure could be varied between 10-1 to 10-3 mm of Hg. Their results showed that, at 850°C and a vacuum of l0-2 to 10-3 mm of Hg, a few well oriented nuclei of oxide were formed on the metal grains. At pressures between l0-1 to 10-2 mm of Hg, many oriented nuclei of oxide were formed. At 750°C the metal surface was bright although an oxide was present. Unfortunately, the extent of oxidation, the oxygen pressure, and the influence of carbon in the metal were not determined, and it was, therefore, impossible to give a theoretical interpretation to the very beautiful light micrographs. Bardolle and Benard used the light microscope to determine the crystal habit of the oxide and X-ray diffraction to determine the orientation relationships. It was believed that the use of controlled amounts of oxidation at high temperature is an important method for the study of the initial stages of oxidation of metals at high temperatures. This paper presents the first results of an electron optical study of this problem for iron. Since the electron microscope and electron-diffraction methods using stripped oxide films and surface replicas yielded finer details of the crystal habit and structure of oxide film, these methods were used in this study. Two types of iron having different carbon contents were used: Puron and Armco* iron. A com- parison of the results for these materials made possible a study of the influence of the surface oxide-carbon reaction on the initial stages of oxidation. Before discussing the experimental results, the thermodynamic equilibria of 1—the oxidation reaction, 2—the surface oxide-carbon reaction, and 3—the solubility of oxygen in iron, will be considered. In addition, it is important to consider the kinetic-theory predictions on the rate of collision of oxygen with the iron surface. Thermodynamic and Kinetic-Theory Calculations Only one type of reaction is usually considered in the oxidation of iron at normal pressures at high temperatures: Fe(a) + 1/2O2(g) = FeO(s) 3Fe(a) + 2O2(g) = Fe3O4(s) 2Fe(a) +3/2O2(g) = a-Fe2O3(s). [11 However, two other reactions may occur: FeO(s) + C (solid solution in Fe) + Fe(a) + CO(g) [2] and Fe(a) + O2(g) e Fe(a) (solid solution of 0,). [ 3 ] In addition, iron will react with the higher oxide at certain temperatures to form FeO. For a complete interpretation of the oxidation of iron at low pres-

Jan 1, 1955

By L. L. McDaniel

Copper smelters of various kinds have operated in the Morenci district since 1872, but all have been abandoned with the exception of the present Morenci Smelter of Phelps Dodge Corporation, which was completed in 1942. During the five-year period starting in 1937, the Morenci ore body was prepared for open pit mining, pilot mill test work was carried out, and a complete reduction works, of which the Smelter is a part, was designed and erected. Actual construction work on the Morenci Smelter was started in the fall of 1940, and warming up of the units began on April 1, 1942. Charging of the reverberatory furnaces commenced on April 18, 1942, and the first anode copper was produced on April 26, 1942. The smelter was originally designed to handle the production of the Morenci Concentrator on a 25,000 ton per day program, but by the time the smelter was in operation, plans were already underway to increase the smelter capacity to handle the production of the concentrator which was being enlarged to 45,000 tons a day capacity as a war-time necessity. This extension to the smelter was completed and the new units were put in operation toward the beginning of 1944. The original smelter consisted of a smelter crushing plant, bedding plant, two direct-smelting reverberatory furnaces with two waste-heat boilers on each furnace, three converters, an anode department, a stack, and all of the usual accessory smelting equipment. The extension consisted of increasing the bedding plant from three to five beds, the reverberatory department from two to four furnaces, and from four to eight waste-heat boilers, and the converter department from three to six converters. A third converter aisle crane was added and additions were made to the flue systems and conveyor systems throughout the smelter; but no change was made in the smelter crushing plant or the anode department, and the same stack was used for all additional Smelter units. A blister casting machine was installed at that time in the south end of the converter aisle to handle excess and emergency production above the capacity of the anode department and in 1947 a converter aisle skull breaker and a lime burning plant were added as the final units for a complete plant. The choice of direct smelting over calcine smelting for the Morenci Smelter was made after careful study by members of the Western organization of Phelps Dodge Corporation and after test runs on direct smelting of Morenci concentrate had been made at the Douglas Smelter of Phelps Dodge Corporation. The Morenci furnace charge is made up of comparatively high grade concentrate with no ores of smelting grade available and with only flux, a small amount of copper precipitate and the usual amount of smelter secondaries to be smelted with the concentrate. The simplicity of direct smelting for this charge and the large amount of waste-heat steam available from direct smelting operations were factors influencing the decision to adopt direct smelting for Morenci. The design of the Morenci Smelter and the type of units selected followed best experience at the Douglas Smelter of Phelps Dodge Corporation. A description of the original smelter before operations started was given in an article in the May 1942 issue of Mining and Metallurgy. The purpose of the present article is to describe the enlarged Morenci Smelter, with a discussion of metallurgy and operating practice and to show tabulations of operating and metallurgical results obtained. Because of beginning operations during the early years of World War 11, many problems caused by labor shortage were encountered, but no major difficulties developed in starting the new plant. However, because of labor shortage, full scale Smelter production was not reached until the fall of 1946. Fig 1 shows a general plan of the Morenci Reduction Works. The arrangement of the smelter equipment is shown in Fig 2, a sectional view of the smelter is shown in Fig 3, and the smelter flow sheet is shown in Fig 4. Metallurgy The metallurgy of direct smelting, being more or less fixed by the character of the charge, is not subject to the control available in calcine smelting. Slags may be modified by the addition of suitable fluxes, but the grade of the matte is determined almost entirely by the iron:copper ratio of the concentrate. The direct smelting operation involves distributing the wet concentrate along the sidewalls and in the bath of a reverberatory furnace by means of some suitable feeding device and raising the temperature of the charge so that first the moisture is driven off, then the first-atom sulphur is eliminated, and finally the sulphide portion of the charge melts and runs into the bath, carrying with it the non-sulphide portion which has been partially fluxed to form a suitable slag. The fusion of the non-sulphide portion is completed by contact with the irony converter slag which is regularly being poured into the reverberatory furnace. The smelting rate of the charge is influenced by the mineralogi-cal composition of the sulphide portion of the concentrate and by the composition and amount of the non-sulphide portion including the fluxes added. The copper in Morenci concentrate is chiefly in the form of chalcocite, intimately associated with pyrite, and non-sulphide content is very low so that

Jan 1, 1950

By Lucius W. Mayer

The iron-mines of the Ilsede Hutte Co. are at a town called Peine, about 20 miles east of the city of Hanover, on the railroad to Brunswick (Braunschweig). Hanover, the capital of the province, is a military city, of approximately 250,000 inhabitants, and Brunswick, 33 miles to the westward, has half this number. The mines here described are located in a hamlet called Bulten. The Ilsede Hutte Co. operates two mines, 1.5 miles apart, in this district, Gruber Bulten Adenstadt and Gruber Lengede Bodenstadt. It also operates an iron-mine north of Hanover, known as Eiserhaven, and one in the Harz mountains, the Georg Friedrich, at Grauhof. At Bulten a coarse conglomerate, a, Figs. 1 and 2, contains nodules of limonite, cemented together by calcium phosphate. The ore contains Fe, 25 to 45; Mn, 3 to 4; P, 0.6 to 1.4; '5, 0.02 to 0.09; and CaCO,, 40 per cent. Directly above the conglomerate is limestone, 6, followed by a mixture of clay and sand, c. Below the conglomerate is a hard clay floor, d. The ore-body, from 10 to 12 km. long, and from 3 to 4 km. wide, has a maximum thickness of 20 m. It dips approximately 10" S.E., and strikes K 45° E. Diamond-drill prospecting shows that the thickness diminishes to 1 m. as the end of the deposit is approached to the northward. At this point the deposit is 250 m. below the surface. In Fig. 2, the arrow, A, indicates the general direction of the work along the face, a, which is carried forward in a straight line for its entire length. At B, a train is approaching, which has come from the bench-track, shown at C, by a circuitous route, and is dumping the overburden behind the face, in the space left by the excavated rock. Formerly the work at this mine mas essentially open-cut, the deposit having a very strong outcrop. Figs. 1 and 2 show also

Jan 1, 1909

Albert Ladd Colby, New York, N. Y. (communication to the Secretary†):—I observed (Trans., xxxvii., 585) that to obtain tenders from several American mills, the foreign engineer should modify his maximum phosphorus to 0.10 per cent., not as Mr. E. Windsor Richards quotes me, that no American rail-maker can produce rails under 0.10 per cent. of phosphorus. Mr. Richards claims that no English engineer would agree to accept 0.10 per cent. of phosphorus on any terms whatever. Mr. Webster writes that only after an engineer has .been convinced that rails can be made in America equal in every respect to those he is getting abroad, should he be asked to modify ally conditions in his specifications. I know it to be a fact that during recent years in many cases, as, for instance, When delivery could be secured more promptly in the United States than in Europe, the consulting engineers of several British and colonial railroads have frequently agreed to modify their phosphorus requirement to a maximum of 0.10 per cent., and the rails delivered' under these modified specifications have, under like conditions, given just as satisfactory service and proved to be no more brittle than similar sections of 0.07 per cent. phosphorus rails, rolled in England under the same specification except without modification as to phosphorus. Furthermore, it would appear from the analyses of British rails, quoted by E. A. Dancaster,2 in his discussion of Mr.

Jan 1, 1908

By E. A. Steigerwald

E. A. Steigerwald (Thompson Ramo Wooldridge, Inc.1— he authors' results clearly indicate that cracking can be produced by the hydrogen pressure developed during a charging operation. This type of cracking or blistering has also been observed in polycrystalline materials24"28 when the charging conditions are sufficiently severe and is often referred to as irreversible embrittlement since it cannot be removed by a baking treatment. There are additional data, however, which must be considered before a pressure theory can be generally employed to account for all failures which occur as a result of hydrogen. In many cases, hydrogen embrittlement in a tensile test or in delayed failures under static loads is a reversible phenomena which cannot be simply explained on the basis of preexisting cracks generated by the charging operation. It is this aspect of the problem which has prompted many investigators to seek mechanisms other than hydrogen pressure to explain their results.24'n728 Fig. 15 indicates an example where, under specific experimental circumstances, hydrogen embrittlement can occur at liquid nitrogen temperatures. In this case, which has been previously decribed,'' specimens were charged with varying quantities of hydrogen, immediately quenched, and tested in liquid nitrogen (-320°F). A companion set of identical specimens were charged, aged at 300°F to remove the hydrogen, and also tested at -320°F. When the current density was greater than lo-' amp per sq in., embrittlekent occurred in both sets of specimens, indicating that cracking had occurred during charging and the embrittlement, as in the case of Fe-Si single crystals, was irreversible. At current densities between approximately 103 and lo-' amp per sq in, the embrittlement was present only for those specimens which contained hydrogen during the testing sequence. The embrittlement was therefore reversible with respect to the aging and charging operations. Since extensive hydrogen movement would not be expected at -320°F, it is difficult to reconcile these data with a mechanism which requires pressure and pressure dependent growth of preexisting cracks. There are other features of hydrogen embrittlement such as the reversibility of the incubation time for delayed failure with respect to applied stressg0 and the influence of prestraining31 which are also difficult to explain using a pressure model. Any general mechanism of hydrogen embrittlement will have to consider the reversible aspects of the embrittlement data as well as the irreversible portion which has been clearly presented for the Fe-Si crystals and which is consistent with a pressure model. A. S. Tetelman and W. D. Robertson (authors' reply)—he authors agree with Dr. Steigerwald that a general mechanism of hydrogen embrittlement must be applicable in all cases where embrittlement occurs. Dr. Steigerwald's experiments were performed on an iron alloy which has an extremely complex microstructure, and therefore does not lend itself to the direct and detailed observations that can be made in Fe-Si. The change in the characteristics of cracks as a consequence of annealing at 300°F is not really known in detail but it is probable that stress-relaxation (blunting) occurs, dislocations produced near the crack tips will be pinned by carbon atoms, and hydrogen will be lost to the atmosphere. Any, or all of these effects of annealing will alter the ease with which a crack subsequently propagates under applied stress. A quantitative treatment of the problem must take these effects into account. Since diffusional processes are presumably eliminated at -320°F, the general mechanism proposed by Dr. Steigerwald's colleagues cannot be operative at this temperature. A detailed discussion of the general' inapplicability of this mechanism has been presented elsewhere. However, the data presented by Dr. Steigerwald in his discussion can be explained in terms of a pressure model. Crack propagation under internal pressure P and applied stress occurs when where is the total energy expended in creating new surface area and by plastic work at the crack tip. The total crack length increases with increasing current density, since we have shown that it systematically increases with hydrogen concentration and Dr. Steigerwald has shown that hydrogen concentration increases with current density. For large L (high current density) Eq. [I] can be satisfied even if P = 0 and the embrittlement process does not require the presence of hydrogen. Specimens charged at a lower current density will con-

Jan 1, 1963

By S. A. Braley

DRAINAGE water from coal mines is probably the most serious water pollution problem today, varying in importance according to location of the mines and geological structure. Drainage may be either acid or alkaline in character. Acid discharge, the most severely detrimental to a stream, is caused by natural oxidation of the sulfuritic material (FeS2) in the strata associated with the coal seam. Since the acid is the result of a natural reaction the acid water differs because it does not cease with abandonment of the mining operations. There is no known economical method of neutralizing acid mine water or any practical method to prevent oxidation of exposed pyrite. Since production of acid from a mine does not stop when mining stops, the total quantity produced depends entirely upon the excavated areas. The increasing volume of acid water in manv mines has greatly increased operating costs. Pumping is expensive and acid mine waters are destructive of all equipment, especially metals in pumps and piping, and necessitate the use of corrosion-resistant materials. Discharge of the acid mine drainage into streams neutralizes their normal alkalinity, causes them to become acid, and produces an environment unfavorable for aquatic life and unsuited for industrial or domestic use without costly treatment. Mine drainages vary in percentage composition over wide limits, although the usual dissolved substances are ferrous and ferric iron, aluminum, calcium and magnesium sulfates, and lesser amounts of sodium, potassium and manganese sulfates and chlorides. Some alkaline discharges may contain heavy concentrations of iron as iron bicarbonate. These waters may produce iron hydroxide deposits in the receiving stream but do not cause it to become acid. In the extensive literature on acid mine water there appears to be a great deal of confusion about the importance of various components and the methods for their determination. In many instances faulty conclusions have been drawn from use of unsuitable methods of analysis. It is desirable that the factors and terms used in evaluation of analyses of mine waters should be so clearly defined that any interested person could properly appraise any analytical report. Some analysts report complete chemical analyses of mine waters and neglect to record drainage volumes. Others report only a minimum of analytical data after taking no precautions to preserve the original composition of the water during the time elapsing between collection and analysis. Some use methods of analysis intended for so-called pure waters of the potable and boiler water classes. These methods are not applicable to highly buffered waters such as mine water. Probably the most common criteria for evaluation are pH, free acidity, or acidity or alkalinity to methyl orange or methyl red, total acidity or acidity to hot phenol-phthalein, and the sulfate content. If these determinations are made on carelessly collected samples after a few days to weeks standing in warm rooms, they do not in any way represent the character of the water flowing from the mines. It is hoped that a brief discussion of the fundamental value of some of these factors may lead to a bettqr understanding of the need for more careful evaluation of mine water discharges. The term pH is one used by chemists to express relative acidity or alkalinity in terms of concentration of effective hydrogen ion in a solution. It is defined as the negative logarithm of the hydrogen ion concentration or activity in equivalents per liter. pH = logarithm A neutral solution, which is one containing the same number of hydrogen and hydroxyl ions, has a pH of 7. As the hydrogen ions increase and the solution becomes more acid, the pH decreases toward zero; and as the hydroxyl ions increase and the solution becomes more alkaline, the pH approaches 14. When dissolved in water to a dilute solution acids like sulfuric and hydrochloric, commonly known as strong acids, ionize completely, and the pH or hydrogen ion concentration varies with molar concentration of the dissolved acid. However, in high concentrations of such acids, the pH or hydrogen ion concentration is less than the acid concentration because the acid does not completely ionize. In only very dilute solutions does the pH represent the total amount of acid that can be neutralized by an alkali. All ionization reactions are equilibrium reactions. If other chemicals are added to the solution of an acid and the added chemical produces an ion that is the same as one of the ions of the acid, the degree of ionization of the acid is altered and the pH changes to some value that represents the active hydrogen ion of the new solution. Thus if iron sulfate is added to a solution of sulfuric acid the pH increases, since the common sulfate ion suppresses the degree of ionization of the sulfuric acid and decreases the effective hydrogen ion. However, the total acidity of the solution is increased. There are two salts composed of iron and sulfate— ferrous and ferric sulfate. In these salts there is no hydrogen ion that can ionize to give an acid solution, but when they are dissolved in water, the pH is less than 7 and the solution becomes acid. This is caused by a reaction known as hydrolysis and is represented by the equations FeSO4 + 2H2O ? Fe(OH)2 + 2H + SO,: or Fe,(SO,)3 + 6H2O ? 2Fe(OH)3 + 6H+ + 3504 A solution with a total acidity of 5000 ppm according to the first equation will have a pH of 4.40 but one with an acidity of 75 ppm, according to the sec-

Jan 1, 1958

By J. C. Fisher, J. H. Hollomon

The fundamental problem concerning the fracture of both crystalline and noncrystalline solids is the divergence between the actua1 and the theorcticallY computed fracture stresses; the stress required for fracture, computed from the forces between atoms, is many times that actually observed with commcrcinlly available materials. Computatiolls have been made,,2 indicating that the theoretical fracture stress should be from 100 to 1000 times that actually observed. There are other incidental problems that have arisen, perhaps the most importallt of which is the problem of size effect often observed in the measurement of the fracture stress of non-metallic solids, such as glass. Another effect conccrns the relation between deformation and the stress required for fracture, Experiments recently made with pearlitic steels indicate that the tensile fracture stress increases with increasing tensile deformation and decreases with increasing prior com-pressive deformation, This marked ani-sotropy of the effect of deformation on the fracture stress is in contrast with the essential isotropy of the flow stress. Early experiments on rock salt crystals by Joffe, et al.3 have illustrated the effect of tensile strain in increasing the tensile stress required for fracture. A consistent theory must be constructed that will explain not only the divergence, of the measured fracture stress from the theoretical value, the size effect, and the ergence of deformation; but will also explain and predict the effects of combined stress, of temperature, of strain rate, and of metallurgical structure. With respect to this last variable, it has now been relatively well established that the carbide particle is the clement of structure controlling the fracture of steels. In steels carbide particles vary in shape from plates to spheroids. It has been found that not only docs the magnitude Of the Fracture stress depend upon the size and shape of these particles. but also its dcpendencc upon strain is affected by changes in 'hap' an' size Or the particles. The precipitate resulting from the age hardening Of duralumin also modifies the fracture stress of this alloy. Nonmetallic inclusions greatly lower the fracture stress of all metals. The magnitude of the lowering depends 0' the size and shape of the included particles. In glass, the major source of the low fracture stress has been fairly conclusively demonstrate' by Griffith4 '0 arise from real flaws or cracks present in the material. He showed that the stress concentration at the end of a defect was of suficient magnitude to raise the stress at this location to a value comparable with the theoretical strength Of the material. If the cracks were reduced in size, Griffith showed that the observed fracture slrength the by virtue Of the decrease in stress concentration. He also pointed out that cracks disposed perpendicularly to the applied tensile stress would be more effective in lowering the fracture

Jan 1, 1947

By J. H. Hollomon, J. C. Fisher

The fundamental problem concerning the fracture of both crystalline and noncrystalline solids is the divergence between the actua1 and the theorcticallY computed fracture stresses; the stress required for fracture, computed from the forces between atoms, is many times that actually observed with commcrcinlly available materials. Computatiolls have been made,,2 indicating that the theoretical fracture stress should be from 100 to 1000 times that actually observed. There are other incidental problems that have arisen, perhaps the most importallt of which is the problem of size effect often observed in the measurement of the fracture stress of non-metallic solids, such as glass. Another effect conccrns the relation between deformation and the stress required for fracture, Experiments recently made with pearlitic steels indicate that the tensile fracture stress increases with increasing tensile deformation and decreases with increasing prior com-pressive deformation, This marked ani-sotropy of the effect of deformation on the fracture stress is in contrast with the essential isotropy of the flow stress. Early experiments on rock salt crystals by Joffe, et al.3 have illustrated the effect of tensile strain in increasing the tensile stress required for fracture. A consistent theory must be constructed that will explain not only the divergence, of the measured fracture stress from the theoretical value, the size effect, and the ergence of deformation; but will also explain and predict the effects of combined stress, of temperature, of strain rate, and of metallurgical structure. With respect to this last variable, it has now been relatively well established that the carbide particle is the clement of structure controlling the fracture of steels. In steels carbide particles vary in shape from plates to spheroids. It has been found that not only docs the magnitude Of the Fracture stress depend upon the size and shape of these particles. but also its dcpendencc upon strain is affected by changes in 'hap' an' size Or the particles. The precipitate resulting from the age hardening Of duralumin also modifies the fracture stress of this alloy. Nonmetallic inclusions greatly lower the fracture stress of all metals. The magnitude of the lowering depends 0' the size and shape of the included particles. In glass, the major source of the low fracture stress has been fairly conclusively demonstrate' by Griffith4 '0 arise from real flaws or cracks present in the material. He showed that the stress concentration at the end of a defect was of suficient magnitude to raise the stress at this location to a value comparable with the theoretical strength Of the material. If the cracks were reduced in size, Griffith showed that the observed fracture slrength the by virtue Of the decrease in stress concentration. He also pointed out that cracks disposed perpendicularly to the applied tensile stress would be more effective in lowering the fracture

Jan 1, 1947

By D. K. Crampton, H. l. Burghoff, J. T. Stacy

The study of copper alloys of the age-hardening type has received considerable attention, and, among the alloys which the authors have, considered, those containing small amounts of nickel and phosphorus as essential constituents seem especially interesting. Such alloys have attractively great capacity for being hardened and also have relatively high electrical and thermal conductivity in the hardened state. In addition, it has been found that the increase in hardness and strength imparted by aging can be greatly augmented by cold-working, so that excellent combinations of conductivity and strength are obtainnble. In view of the possible importance of the alloys, it was considered desirable to investigate the solubility relationships in the copper-rich portion of the copper-nickel-phosphorus system. This paper present's some of the results obtained in this investigation to date and also gives propertics of typical alloys that appear to be of commercial interest,. Review of literature Copper-nickel System,.—The binary coppcr-nickcl system has long been known to consist of a series of simple solicl solutions, copper and nickel being miscible at all tempcrat'ures and concentrations. This was establisl~cd by Guertler arid Tammannl in 1907 and confirmed by Tafel2 in 1908. Copper-phosphorus System.—The copper phosporus system has been studied by numerous investigators, so that the copper-rich portion is now definitely known. As most recently determined by Lindlief," his system has a cutectic at 8.38 per ccnt P, cuteetic temperature being 714° C. Components of the cutectic are Cu3P and alpha solid solution. Solid solubility of phosphorus in copper, according to Mertz arid Mathewson decreases from a maximum of about 1.75 per cent at 714' C. to about 0.6 per cent at 300' C.

Jan 1, 1940

By D. K. Crampton, H. l. Burghoff, J. T. Stacy

The study of copper alloys of the age-hardening type has received considerable attention, and, among the alloys which the authors have, considered, those containing small amounts of nickel and phosphorus as essential constituents seem especially interesting. Such alloys have attractively great capacity for being hardened and also have relatively high electrical and thermal conductivity in the hardened state. In addition, it has been found that the increase in hardness and strength imparted by aging can be greatly augmented by cold-working, so that excellent combinations of conductivity and strength are obtainnble. In view of the possible importance of the alloys, it was considered desirable to investigate the solubility relationships in the copper-rich portion of the copper-nickel-phosphorus system. This paper present's some of the results obtained in this investigation to date and also gives propertics of typical alloys that appear to be of commercial interest,. Review of literature Copper-nickel System,.—The binary coppcr-nickcl system has long been known to consist of a series of simple solicl solutions, copper and nickel being miscible at all tempcrat'ures and concentrations. This was establisl~cd by Guertler arid Tammannl in 1907 and confirmed by Tafel2 in 1908. Copper-phosphorus System.—The copper phosporus system has been studied by numerous investigators, so that the copper-rich portion is now definitely known. As most recently determined by Lindlief," his system has a cutectic at 8.38 per ccnt P, cuteetic temperature being 714° C. Components of the cutectic are Cu3P and alpha solid solution. Solid solubility of phosphorus in copper, according to Mertz arid Mathewson decreases from a maximum of about 1.75 per cent at 714' C. to about 0.6 per cent at 300' C.

Jan 1, 1940

By S. E. Bronisz, Dana L. Douglass

a Uranium was deformed by cold rolling, and the effects of this plustic deformation on the microstruc-ture of the metal were observed by the technique of transmission elecbon microscopy. The recrystalli-zation of selected cold-wmked samples was also studied by this method. The samples were prepared for examination by electrolytic thinning in a standard metallographic electrolyte which has not been previously reported as being used in producing thin foils of uranium. The microstructural changes observed in the a uranium were generally similar to those seen by optical microscopy. The changes in the microstructure of a uranium following cold work and recrystallization treatments have been the subjects of several studies employing optical and X-ray techniques.12-19 These studies indicated that twinning was the redominant mode of deformation at room temperature20 and that the regions of high energy associated with the deformation twins were preferred sites for the initiation of recrystallization.15,18, Recently several workers have prepared thin foils of uranium suitable for examination by transmission electron microscopy.'-lo The foils thus prepared have been used to study fission fragment damage; a particular dislocation reaction,' and gas precipitation." At this laboratory the microstructural changes occurring during the cold working and recrystallizing of a uranium samples have been studied by using transmission electron-microscopy techniques. The foils used in this work were electrolytically thinned in a polishing bath not reported previously in the literature as being used for this purpose. EXPERIMENTAL PROCEDURE The uranium used in this investigation was depleted a uranium sheet 4 mils thick. The results of a spectrochemical analysis of this material are shown in Table I. The as-received uranium was cut into strips, 1 in. wide by 5 in. long, and annealed in vacuo at 600°C for 2-1/2 hr. The resulting microstructure consisted of relatively uniform, equiaxed grains having diameters of 10 to 50 p. Cold Working. The cold-worked samples were prepared by rolling several of the annealed uranium strips to various thicknesses. The strips were reduced 3.5 ± 0.5, 6.0 ± 0.6, 10.0 ± 0.5, 19.5 ± 1.0, and 28.5 ± 2.0 pct in thickness. It was not possible to achieve these reductions with a single pass through the rolling mill, so the strips were turned end for end during the rolling procedure. The cold-rolled strips were stored in dry ice until samples from them could be thinned and examined (within 24 hr after rolling). Annealing. The samples used in studying the re-crystallization behavior of a uranium were obtained by annealing sections of the strips which had been reduced 10.0 and 28.5 pct. These samples were sealed in evacuated Pyrex capsules and were annealed in a tube furnace at temperatures from 200" to 600°C and for times from 1/2 to 2 hr, see Table l. Thinning: The samples from the rolling and heat treatments were prepared for examination in the electron microscope by electropolishing in a bath composed of 25 g chromic acid, 133 ml glacial acetic acid, and 25 ml water. This electrolyte has been used and recommended for preparing specimens for optical metallography It was necessary to mask the edges of the sample with a stop-off paint in order to prevent preferential attack in these areas. The paint used was made by dissolving polystyrene in benzene. The electrolytic cell consisted of a cylindrical stainless-steel cathode placed in a beaker containing the electrolyte, with the sample as the anode positioned at the cell axis. The temperature of the electrolyte was held below 15°C by cooling with liquid

Jan 1, 1963

By H. Foster Bain

Jan 1, 1910

By Yoichi Ishida, Ching-Yao Cheng, John E. Dorn

Tile creep behavior of a iron was investigated over the range of temperatures from 375° to 1150°K. Apparent activation energies for creep, obtained by the effect of sudden changes in temperature on the creep rate, revealed the presence of- four distinguishable regions. The creep behavior of a iron in Regions II (480° to 774°K) and 111 (775° to 1045°K) was found to correlate well with a model where the creep rate is controlled by the nonconsevualive motion. of jogged screw dislocations. An anomalous increase in the apparent activation energy fur creep in Region III was found to be in harmony with the known decrease in the free activation energy for self-diffusion over the Curie transformation range. Furthermore, the creep rates in Regions II and III were found to increase with stress due not only to the effect of stress on the activation energy but also to an increase in density of mobile dislocations. The evidence suggests that pipe diffusion along moving dislocations could be a significant factor over the lower temperatures of Region II. ALTHOUGH the creep properties of iron and steel have been of interest to metallurgists for some time and an extensive literature is now available, most of the published information has not produced much toward understanding the fundamental dislocation processes controlling the creep behavior of these materials. Whereas the activation energy for high-temperature creep of metals usually agrees well with that for self-diffusion, Sherby, Orr, and Dorn1 deduced from the data of Tapsell -and c1enshaw2 that the activation energy for creep of Armco iron is about 78,000 cal per mole and more recently Lytton and sherby3 reviewed the data of Jenkins and Mellor4 and found an activation energy for creep of a iron of 80,000 cal per mole. Both values are substantially greater than the activation energy for self-diffusion in a iron. Because of the limited data suitable for purposes of identifying the controlling dislocation mechanisms of creep and the unusually high activation energies for creep quoted above, it was considered desirable to reinvestigate in detail the creep of a iron by more reliable techniques which would provide sufficient data for determination of the creep mechanisms. EXPERIMENTAL TECHNIQUE Creep specimens were prepared from 3/8 by 4 in. iron bar stock of the following composition by weight percent: 0.001 C, 0.0120 0, 0.001 N, 0.004 S, and 0.003 P. The as-received bars were cold-rolled to a thickness of 0.100 in., annealed under argon for 30 min at 1113°K, cold-rolled to a final thickness of 0.063 in., and machined into tensile specimens having gage section 0.250 in. wide and 1.70 in. long. Finally they were recrystallized under argon at 1113°K. Specimens to be crept above 1060°K were recrystallized at 1173°K. Both recrystallization treatments gave the same reproducible equiaxed ASTM No. 4 grain size. Creep testing was conducted in machines fitted with Andrade-Chalmers arms that maintained a constant stress to within ±0.2 pct of the reported values. Deformation over the specimen gage section was sensed with a linear differential transformer and recorded auto-graphically as a function of time. The strains deduced from these measurements were sensitive to ±5 x 10-5. During creep the specimens were contained in an argon-filled chamber which was immersed in a temperature-controlled molten tin bath. Creep temperatures, as measured by thermocouples attached to the specimen, were maintained to within ±10.25°K of the reported values. For activation-energy determinations rapid changes in temperature of about 12°K were obtained within 30 sec by direct resistance heating of the creep specimen, and maintained to ±1°K of the reported values. Observations of structural details of specimens before and after creep tests were made by electrolytic polishing and etching in acqueous ammonium persulfate. EXPERIMENTAL RESULTS A typical example of the determination of apparent activation energies, Q, by the effect of small changes in temperature is illustrated in Fig. 1. Q is defined by

Jan 1, 1967

By E. P. Pfleider, W. G. Pariseau

This paper reports the theoretical and experimental results of an analysis of ore pass drawdown as a problem in soil plasticity. The method of analysis developed appears to be a promising technique of investigating the mechanics of fragmented materials. A reconstructed plasticity theory brings experiment and theory into reasonable agreement, and hence may provide the foundation needed for rational ore pass design. The gravity-induced movement of broken rock through ore passes is an economical method of transporting fragmented materials through large vertical distances in underground mines, provided the ore pass is well designed. Unfortunately, the design procedures now followed do not very often result in ore passes that function properly. On the one hand, the huge accumulation of empirical data pertaining to the movement of materials in gravel bunkers, storage bins, deep grain silos and other structures that have features in common with ore passes remains uncorrelated. On the other hand, there is a dearth of experimental data substantiating theoretical models of material behavior. Consequently, reliable generalizations encompassing the broad spectrum of problems involved have not been forthcoming. AS an initial step towards improving the situation, a detailed case study of two-dimensional ore pass drawdown was made. The mechanics of the process were analyzed theoretically as a problem in soil plasticity and tested experimentally through observations of a laboratory ore pass model. THEORY Taylor1 defines a soil as a "mass commonly considered to consist of a network or skeleton of solid particles, enclosing voids of varying size." Broken rock in an ore pass is such a material. In plasticity theory this material is replaced by an idealized substance that deforms elastically up to some state of stress at which slip or yield occurs,2 For com-pressive states of stress, the Mohr-Coulomb criterion is a satisfactory yield condition. After the yield point is reached, the ideal soil deforms in accordance with the concept of plastic potential.4 Under plane strain conditions the governing equations separate into a system of stress equations and a system of velocity equations.' Only stress variables appear in the stress system. The velocity system, however, contains a stress variable. The two systems are, therefore, coupled. Both systems are hyperbolic, and each has two real, distinct families of characteristic curves that coincide according to the classical theory of ideal soil plasticity. The

Jan 1, 1969

By W. A. Oates, J. A. Lambert, P. T. GaIIagher

Monte Carlo methods have been used to compute the arrangements of interstitial atoms dissolved in tetrahedral sites in bcc lattices. It is assumed that the presence of an interstitial atom "blocks " a certain number of neighboring sites and prevents their occupancy. Sites "blocked" by more than one filled site are allowed for. The computed values of. the mean occupation number (defined as the ratio of the total number of sites blocked to the number of solute atoms are used to calculate the configurational entropies of the solutions. These entropies are compared with those resulting from previous theoretical studies of this problem and also with available experin~ental data for the p Zr-H, Nb-H, V-H, and Ta-H systems. Evidence is also given that the "blocking" explanation of low limiting compositions in these systems, rather than this being due to initial limitations on the number of sites available, is probably correct. THE ideal partial configurational entropy of mixing of an interstitial solute in a metal is given by: where p is the number of interstitial sites per metal atom and Xi is the atomic fraction of the interstitial. For the bcc lattice. which we shall be concerned with in this paper, the interstitial positions are shown in Fig. 1. It can be seen that for the tetrahedral sites, p=6. whereas for the octahedral sites, p = 3. Different emphasis has been placed on the relative importance of energy and entropy effects in determining deviations from ideality in interstitial solid solutions. In some cases the same system, e.g., Fe-C, has been described by the contradictory regular and athermal solution models indicating that the enthalpy and entropy functions, derived from equilibrium data, are frequently not accu.rate enough to differentiate between these treatments. However, for certain metal-hydrogen solutions the equilibrium data is available over sufficiently wide ranges of temperature and composition to permit a reasonably accurate determination of the compositional variation of the heats and entropies. Hoch&apos; has attempted to interpret the results of interstitial solid solutions in terms of a regular solution model. In the case of the Ta-H system where 13 = 6, this model entails fitting the experimental relative partial entropies of solution, asH, to the equation: where ASgs is the relative partial excess entropy of solution of hydrogen. Hoch found that the results of Mallett and Koeh1 could be fitted to this equation with an approximately constant value of AF up to XH = 0.25. However, it is apparent from the solubility isotherms in this system which become asymptotic to the composition TaH that, since (Xh /6 - ~Xh ) becomes infinite only at TaH6, it is necessary that AS<&apos; tends to infinity at TaH. In other words, the low saturation composition of TaH, instead of the anticipated TaH,, eliminates the possibility of applying regular solution theory to such systems. Rather large negative excess configurational entropies must exist at higher hydrogen concentrations in order to explain the lower saturation values. To account for these low limiting compositions and excess entropies two distinctly different approaches have been followed. Rees and many others1-l2 have assumed that not all interstitial sites are crystallographically equivalent with respect to the interstitial addition; that is, in Eq. [I] p is less than the value anticipated from geometrical considerations. To describe, say, a bcc metal-hydrogen system with a limiting composition of MH by this approach one would consider that p = 1 in the first instance instead of p = 6.&apos;j3 In some cases, nonintegral values of B have been taken in order to improve the fit with the experimental data over limited ranges of composition. The other approach which has been used to explain the low saturation compositions is to assume that, although all sites are available for occupancy, strong repulsive interactions exist between the neighboring interstitial atoms, and hence occupancy of any site excludes or blocks a certain number of neighboring sites from being occupied. Earliest treatments of this concept considered the exclusion of an integral number, of nearest-neighbor sites from being occupied at all concentrations. In this case, the partial configurational entropy is given by: These early treatments failed to allow for the overlap of the blocked sites which will arise at all but the very lowest concentrations. More recently attempts have been made to calculate the effect of this decrease in the number of blocked sites on the configurational entropy. Using the quasichemical treatment of interstitial solid solutions as given by Lacher and assuming that an infinite repulsive interaction energy existed between the solute atoms. atom obtained an approximate configurational entropy applicable to the blocking with overlap case:

Jan 1, 1970

By Carl Scholz

Discussion of the paper of Carl Scholz, published in Bi-monthly Bulletin, No. 22, July, 1908, pp. 551 to 559. HOWARD N. EAVENSON, Gary, W. Va. (communication to the Secretary*) :-For some time before the publication of Mr. Scholz&apos;s paper, I had been collecting data bearing upon its subject, and I now take pleasure in presenting my results to the Institute in the form of a discussion. It has long been a matter of common opinion among mining-men that mice-explosions are, more frequent during the colder, or winter months, than during the warmer ones, and it is a matter of common knowledge among them that the air-ways and road-ways in most mines are much drier and are more in¬clined to be dusty during the winter than during the summer. In many mines, places which are wet and sloppy in the summer are dry and sometimes dusty during the winter. These changes, of course, can only be due to atmospheric conditions, and are caused by differences in temperature and humidity. Until recently, however, very little attention has been paid to the part that atmospheric conditions may play in mine-explosions, or, rather, to the effect they may have in rendering mine-conditions peculiarly dangerous, and in spreading and rendering more disastrous the effects of what would otherwise probably have been .small explosions. To show the difference in mine-conditions during sunnier .and winter months, I have tabulated in Table I. the results of 24 observations of hygrometric conditions in several different mines at different times of the year. Mines Nos. 1, 2, and 6 are located in the Pocahontas.coal -region, in McDowell couuty, W.Va., the first one being a shaft-mine shaft mine and the others drift. Mines 1A and 2A are drift-mines located in Logan county, W. Va. All of these are mines of fair size, but none of them has been in operation more than six years,

Jun 1, 1909

By H. I. Aaronson, C. Wells

Configurations of ferrite crystals have been found in a plain carbon steel which appear to have resulted from the nucleation of new ferrite crystals at the interphase boundaries of previously formed crystals despite the high carbon concentrations which necessarily develop at these boundaries. This phenomenon has been termed sympathetic nucleation. An attempt has been made to reconcile the occurrence of sympathetic nu-cleation with current nucleation theory. THIS investigation is one of a series on the formation of proeutectoid ferrite from austenite. From the viewpoint of chemical composition, this reaction consists of the nucleation and diffusional growth of crystals of carbon-poor ferrite within a matrix of carbon-rich austenite. The austenite adjacent to the austenite-ferrite boundaries will be greatly enriched in carbon, approximately to the value of the y/(a + y) equilibrium curve or its metastable extrapolation at the temperature of transformation. Those areas of austenite appreciably farther removed from the growing ferrite, on the other hand, will be relatively unaltered in composition, especially at the earlier stages of transformation. Since rates of nucleation are considered to decrease exponentially with decreasing supersaturation,&apos; the frequency with which ferrite nuclei appear at austenite-ferrite boundaries should be negligible in relation to that at which they form in other regions of the austenite. During this investigation, however, many groupings of ferrite crystals have been found which appear to have resulted from the nucleation of ferrite at austenite-ferrite boundaries. This phenomenon has been given the name of sympathetic 71.1tcleation. A number of micrographs of morphological configurations caused by sympathetic nucleation will be presented, after which an explanation for this reaction will be proposed in terms of current nucleation theory. Some of the structures to be considered are composed of bainite, an aggregate of ferrite and carbide, rather than of ferrite. Since ferrite and bainite differ only in that bainite forms under conditions which result in the nucleation of carbides behind the advancing austenite-ferrite boundaries,&apos; it will usually be unnecessary, for the purpose of this paper, to distinguish between the two reaction products. All studies were performed on an electric furnace steel (obtained from the Vanadium Alloy Steel Co.) containing 0.29 pct C, 0.76 pct Mn, 0.25 pct Si, 0.005 pct P, and 0.007 pct S. The alloy was cast as a 150 Ib, 7x7 in. cross section ingot and forged into bars 2x2 in. in cross section. These bars were homogenized for 48 hr at 1250°C in an Endo-Gas atmosphere. The depth to which decarburization penetrated during this heat treatment was determined by chemical and microscopic analyses and the affected metal was removed by machining. Specimens for isothermal transformation studies were cut from the remaining material; most of these specimens were 1/2x1/4X1/16 in., though some with a thickness of 1/32 in. were prepared for use at the shorter reaction times and lower reaction temperatures. Specimens were austenitized for 30 min at 1300°C, isothermally reacted for various times at temperatures ranging from 775" to 475 "C, and then quenched in iced water. The austenite grain sizes within individual specimens ranged from ASTM Nos. 1 through —4. A commercial heat-treating salt which was continuously deoxidized by an immersed graphite crucible served to minimize the loss of carbon during austenitizing; thick covers of powdered graphite and immersed graphite rods effectively prevented decarburization in the lead pots employed for the isothermal reaction treatments. The heat-treated specimens were sectioned and mounted in Bakelite. Following the completion of standard grinding and mechanical polishing procedures, the specimens were electrolytically polished with a Buehler-Waisman apparatus and etched in 2 pct nital. Experimental Results Rules of Evidence for Sympathetic Nucleation—On the basis of observations made on a single plane of polish, one precipitate crystal may be considered to have been sympathetically nucleated at the inter-phase boundary of another precipitate crystal when the following conditions are fulfilled: 1) The sympathetically nucleated crystal is not in contact with a grain boundary or a subboundary in the matrix phase. 2) The shape, size, and location of the crystal at whose boundary sympathetic nucleation occurred (hereafter termed the base crystal) and the crystal formed by sympathetic nucleation substantially pre-clude the possibility that the plane of polish em-ployed may have concealed the fact that both crys-tals actually nucleated at a grain boundary or a sub-boundary in the matrix phase.

Jan 1, 1957

By M. von Heimendahl, G. Thomas

The microstructure of TD-Ni has been examined by transmission electron microscopy in the extruded, annealed. and deformed states. The tensile properties hove been correlated with the observed microstructures and the results ore com-pared with those obtained from pure nickel. The important conclusions are that the thorin particles in TD-Ni act as strong burriers to dislocntion motion during both deformation (slip) and annealing (climb). During deformation. the dislocations tangle around the particles and a cell structure is devleloped after 10 pct or more strain. The cell size appears to be determined by the spacing of the largest particles and is about five times smaller than that in pure nickel for the same strain. The higher work-hardening rate in TD-Ni compared to nickel is probably due to the more rapid rate of dislocation multiplication in the alloy as a result of dislocation-particle interactions. The Th0,particles inhibit recrystallization and twin growh so that some strengthening may arise from the high density of small annealing twins. THE strengthening of materials due to the presence of a dispersed second phase has been the subject of considerable experimental and theoretical investigation in recent years. One of the newest dispersion-strengthened alloys to be developed is TD-Ni,1 a system of approximately 2 vol pct thoria (ThO2) dispersed in a matrix of commercially pure nickel. This material is fabricated by powder-metallurgical techniques and offers high-temperature stability and useful mechanical properties virtually to the melting point of the base metal. While the mechanical properties of this system have been investigated,2,3 there have been no reports in the literature concerning the microstruc-ture of TD-Ni and its correlation to mechanical properties. This paper describes a transmission electron microscopy investigation of the micro-structure of TD-Ni together with its mechanical properties. The results are compared with the structure and properties of pure nickel.

Jan 1, 1964

Jan 1, 1902

By Cyril Stanley Smith

Jan 1, 1949