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By J. H. Keeler

The tensile characteristics of Zr-Fe binary alloys containing up to 5 atomic pet Fe are reported for the temperature range —195o to 500°C. A linear relation between stress at constant strain and volume fraction ZrFe2 was found. The coincidence of data from unalloyed zirconium with zero volume fraction ZrFe2 indicated little or no solid solution in IL-zirconium, in agreement with Hayes, Roberson, and O'Brien.' The absolute increase in strength due to particle strengthening, although decreasing with increasing temperature, was a greater percentage at high temperature. ZIRCONIUM is of interest for use in nuclear reactors because of its low neutron absorption, good corrosion resistance, and high melting temperature. The alloying of zirconium with iron has been considered as a means of increasing the mechanical strength of zirconium without seriously increasing the neutron absorption " over that of unalloyed zirconium. The Zr-Fe system has a eutectic at 934°C and 23.7 atomic pet Fe and a eutectoid at 800°C and 4.0 atomic pet Fe. The zirconium-rich end of this system determined by Hayes, Roberson, and O'Brien' is shown in Fig. 1. The intermetallic phase coexisting with a and ß-zirconium has been reported as Zr2Fe3,1 with a,, - 7.04A, and as ZrFe2,2 face-centered-cubic, the phase being of the MgCu, type (C-15). It was more recently agreed to be ZrFe33 and face-centered-cubic. This intermetallic phase is essentially insoluble in a-zirconium, the hexagonal-close-packed modification; and the lack of solubility makes the system particularly interesting metallurgically. The system is strengthened almost exclusively by particles of in-termetallic phase, and there is very little solid solution strengthening to complicate the analysis. The Bureau of Mines, in its survey of zirconium-base alloys,' reported the tensile properties of Zr-Fe alloys made from chloride process zirconium, induction melted in graphite crucibles, and swaged at 850°C in iron sheaths. Additional data on these ZrFe alloys were given by Hayes, Roberson, and O'Brien.' Chubb and Muehlenkamp% have recently reported the strength of Zr-Fe alloys containing up to about 1.25 atomic pet Fe. These alloys were made from crystal bar zirconium, hot worked at 820°C, annealed at 700°C, and tested both at room temperature and at 316°C. Experimental Procedure The materials used in this investigation were high purity zirconium made by the iodide process and electrolytic iron. The composition of the zirconium as obtained by spectrographic analysis and the nominal composition of the iron are given in Table I. Alloy ingots weighing 100 g were made by are-melting under argon in water-cooled copper crucibles in a multihearth furnace."

Jan 1, 1957

Executive ERLE V. DAVELER. Chair u W. B. HEROY PAUL D. MERICA JOHN M. LOVEJOY WILLIAM WRAITH Finance H. G. MOULTON, Chairman H. T. HAMILTON HENRY KRUMB Admissions JOHN L. CHRISTIE, Chairman GEORGE D. BARRON, Vice-Chairman FRED H. KAY PHILIP KRAFT H. Y. WALKER

Jan 1, 1938

By F. M. Smith, R. H. Moore, J. R. Morrey

Electrodiffusion in y cerium reported by Henrie has been confirmed and a Preliminary estimate made of the relative rates of electrodiffusion of iron, cobalt, and nickel. These diffuse to the anode at rates decreasing in that order. In addition, copper and manganese exhibit slow, but detectable, diffusion to the anode and molybdenum exhibits detectable diffusion to the cathode. The electrodiffusion of carbon, .zirconium, antimony, magnesium , and silicon in y cerium could not be detected. Iron and cobalt diffuse in y cerium at rates proportional to the current density and with no apparent dependence on temperature. Decreasing polarization of iron and cobalt with increasing temperature, which cancels the expected rate increase, would account for this behavior. The electrodiffusion rate of iron in y uranium and in E plutonium has been measured. Diffusion of iron is anode-directed. Tin was found to diffuse to the cathode, in y uranium, at an appreciable rate. In all of these solvent metals, negative ions diffuse to the anode and positive ions to the cathode. The potential field effect appears to account satisfactorily for these results. FROM early experimental work summarized by Jost1 and Seith,2 the driving force for electrodiffusion was attributed to the potential field acting on ions in a metal. More recently, Heuman,3 Wever,4 and Huntington5 have shown that momentum interchange between conduction electrons and mobile entities in the metal contributes to electrodiffusion. Electron momentum interchange is anodically directed and the direction of diffusion resulting from the field force is dependent upon the charge on the diffusing entity. These two effects may either reinforce or oppose each other. Glinchuk6 has pointed out that momentum transfer in defect conductors should be cathode-directed and this appears to be the case as demonstrated by wever's4 work on iron. Barnett's7 work, on the other hand, indicates that, even in defect conductors, electrons show a negative E/m ratio when accelerated with respect to the lattice and should lead to anode-directed momentum transfer. In discussing this problem, Wever and seith8 suggest that defect electrons interact preferentially with activated ions so as to allow a net movement toward the cathode while still maintaining an electron momentum transfer in the anode direction. Williams and Huffine9 and Henriel0 have demonstrated that electrodiffusion may be useful for purification of yttrium and cerium. In yttrium, Williams and Huffine note that movement of several metallic impurities toward the anode is in keeping with observations in most other metallic systems and indicates that yttrium remains a normal electronic conductor at least to 1230°C. Close inspection of their data shows, however, that oxygen, nitrogen, and the transition elements diffused toward the anode, while nontransition elements diffused toward the cathode. This suggests that potential field effects may have been appreciable. The present work was concerned with the applicability of electrodiffusion as a technique for purification of plutonium, but, because of the obvious hazard inherent in work with this metal, experiments to develop the technique were carried out using cerium and uranium. The results of electrodiffusion measurements on these metals and on plutonium are reported here. EXPERIMENTAL The metal specimens prepared for this work were 6 in. long, 1/4 to 1/2 in. wide, and 1/16 to 3/32 in. thick. The uranium specimens were machined from a bar which analyzed 310 ppm Fe and the electrodiffusion of iron was followed by spectrographic and by chemical analysis. Cerium and plutonium specimens were cut from sheet rolled from ingots obtained from molten salt-metal equilibrations during which radioactive tracers were introduced. The electrodiffusion of the tracers was subsequently determined by counting methods. The specimens were electrolyzed between nickel electrodes containing resistance heaters used to equalize the specimen and electrode temperatures, thereby reducing thermal gradients. The temperature of the electrodes adjacent to the ends of the specimen was measured with chromel-alumel thermocouples which were connected to the heater controls. The surface temperature of the specimen at a point midway between the electrodes was measured with a sapphire rod pyrometer, the output of which controlled the dc power supply. This assembly was enclosed within an evacuable chamber containing a quartz viewing window. The temperature of the specimen over its entire length could be scanned with a portable pyrometer through

Jan 1, 1965

By E. P. Pfleider, D. H. Yardley

Layers of magnetic taconite of above average magnetic iron content extend down dip on the Mesabi Range to depths beyond the reach of open pit mining. A selected layer with thickness of 75 to 100 ft underlies many square miles. Such a selected layer can provide over 50 million tons of recoverable concentratc per square mile, at lower concentration ratios than in the present open pit taconite operations. The system contemplated would consist of large scale underground quarrying by a lane and pillar method. Working heights would be 60 to 100 ft; room widths, 50 to 75 ft; and productivity targets, about 40 tons per man-shift. The most critical problems would he roof control and blasthole drilling. The successful operation of large open pits and concentrating plants for treatment of magnetic taconites indicates that the basic techniques and economic problems of pellet production have been solved. The open pit reserves are large, but they are not necessarily available in sufficient quantity or quality to provide an adequate raw materials base for all potential producers. Furthermore, as the more easily available open pit crudes are used up, the pits will become deeper, stripping costs per ton of concentrate will increase, and recoveries will decrease as leaner crudes are utilized. The time will come when supplementary and replacement reserves of magnetic taconite will be required. One way these can be obtained is by underground mining of the down-dip extension of the Mesabi magnetic taconites, especially those layers averaging well over 25% recoverable iron. A key point in such a proposal is the possibility of realizing substantial savings by beneficiating an ore of 30% magnetic iron at 2.5 to 1 ratio of concentration. This contrasts with current practice in Mesabi commercial taconite plants, where the ore averages 22 to 25% magnetic Fe, with concentration ratios of about 3.0 when producing 61% Fe pellets. Two factors which favor the eventual development of underground taconite mining are: 1) the desirable physical structure and high grade of taconite pellets in general and 2) the improved engineering techniques in underground mining. Experience in large scale room and pillar mines demonstrates that, given strong rock strata immediately above a high grade mining

Jan 1, 1963

By Michael B. Bever, John R. Anderson

Carbon may affect the alloys of copper in several ways. Provided an alloying element does not oxidize preferentially, even minute quantities of carbon dissolved in liquid alloys of high copper content will form insoluble carbon oxide gases under oxidizing conditions. Gas porosity in castings of high-copper alloys can originate in this way. In certain alloys of low copper content carbon may have considerable solubility and may be an effective deoxidizer. In these alloys carbon will tend to suppress porosity. Carbon that is dissolved in the molten alloy is likely to be retained in the solidified metal. The effects of carbon on the physical properties of the metal are determined by the form in which it is present. Depending on the alloying elements and also on the cooling rate, carbon may precipitate as graphite, may form a carbide or may remain in solid solution on cooling. As solid copper does not dissolve a measurable amount of carbon, a carbon-bearing solid solution can occur only if the copper is alloyed with a large excess of an element that forms such a solution. The effect of graphite or of carbides on the properties of an alloy will depend on the size and distribution of the precipitated particles. As Hensel pointed out in discussion,' the formation of an alloy carbide may interfere with the age-hardening properties of a copper alloy. One would also expect that the presence of carbides or of graphite will under certain conditions promote corrosion or high-temperature failure in nonferrous alloys. Since carbon has an effect on the soundness of castings and affects the structure and behavior of solid copper alloys, its solubility in the liquid alloys is of practical importance. The isothermal change of carbon solubility with alloy composition is of interest from a theoretical standpoint. The binary alloys of copper with manganese and with nickel are used industrially and serve as a base for more complex alloys. The solubility of carbon in each of these metals is known, but its solubility in their alloys has not been determined. Earlier Data The solubility of carbon in molten pure copper is about o.oooi pct at II00°C and 0.0004 pct at 1475°C.l Various authors2""6 have published data on the solubility of carbon in molten manganese. There is agreement on a value of about 6.7 pct in the temperature range r2170 to 1245°c This solubility value corresponds to the formula Mn3C. It increases very little with increasing temperature. Corson7 states that carbon is soluble in copper-manganese alloys and that the

Jan 1, 1947

By John R. Anderson, Michael B. Bever

Carbon may affect the alloys of copper in several ways. Provided an alloying element does not oxidize preferentially, even minute quantities of carbon dissolved in liquid alloys of high copper content will form insoluble carbon oxide gases under oxidizing conditions. Gas porosity in castings of high-copper alloys can originate in this way. In certain alloys of low copper content carbon may have considerable solubility and may be an effective deoxidizer. In these alloys carbon will tend to suppress porosity. Carbon that is dissolved in the molten alloy is likely to be retained in the solidified metal. The effects of carbon on the physical properties of the metal are determined by the form in which it is present. Depending on the alloying elements and also on the cooling rate, carbon may precipitate as graphite, may form a carbide or may remain in solid solution on cooling. As solid copper does not dissolve a measurable amount of carbon, a carbon-bearing solid solution can occur only if the copper is alloyed with a large excess of an element that forms such a solution. The effect of graphite or of carbides on the properties of an alloy will depend on the size and distribution of the precipitated particles. As Hensel pointed out in discussion,' the formation of an alloy carbide may interfere with the age-hardening properties of a copper alloy. One would also expect that the presence of carbides or of graphite will under certain conditions promote corrosion or high-temperature failure in nonferrous alloys. Since carbon has an effect on the soundness of castings and affects the structure and behavior of solid copper alloys, its solubility in the liquid alloys is of practical importance. The isothermal change of carbon solubility with alloy composition is of interest from a theoretical standpoint. The binary alloys of copper with manganese and with nickel are used industrially and serve as a base for more complex alloys. The solubility of carbon in each of these metals is known, but its solubility in their alloys has not been determined. Earlier Data The solubility of carbon in molten pure copper is about o.oooi pct at II00°C and 0.0004 pct at 1475°C.l Various authors2""6 have published data on the solubility of carbon in molten manganese. There is agreement on a value of about 6.7 pct in the temperature range r2170 to 1245°c This solubility value corresponds to the formula Mn3C. It increases very little with increasing temperature. Corson7 states that carbon is soluble in copper-manganese alloys and that the

Jan 1, 1947

By R. P. Abendroth

This study is concerned with the kinetics of selective oxidation of chromium in a commercial Fe-Cr-Ni alloy. Selective oxidation of chromium in this alloy, by use of a low oxygen-potential atmosphere, leads to the formation of a compact, protective layer of Cr2O3. This layer serves to protect this alloy from gross scaling when it is subsequently exposed to severe oxidizing conditions at high temperature. The interaction of low oxygen-potential atmospheres close to equilibrium with Fe-Cr and Ni-Cr alloys has been studied by others."' These studies werk concerned with the surface-structure variations under slightly oxidizing conditions. NO detailed study was made of the oxide scale formation kinetics, however. The alloy samples were cut from 0.012-in.-thick sheet, with an apparent surface area of 7.1 sq cm. These sheet samples were abraded through 4/0 metallographic paper, and washed in alcohol and acetone. The analysis of the sheet alloy is (in weight percent): 42 pct Ni, 5.5 pct Cr, 0.09 pct C, 0.18 pct Al, 0.36 pct Si, 0.26 pct Mn, balance Fe. The weight gain vs time data were obtained with a 2-g capacity fused-silica spring—cathetometer system. The spring deflection was optically magnified ten times before being read by the cathetometer. A sensitivity of about 0.01 mg was attainable. The spring was enclosed in a water jacket maintained at 60°C to minimize the effect of temperature changes. The sample was suspended from the spring with a fused-silica hangdown and was positioned in the thermal center of a mullite furnace tube. Sample temperature was read with the aid of a thermocouple placed outside the mullite tube and an inside vs outside temperature calibration. Temperature change during the course of a run was ±0.25°C, with a temperature gradient of less than l.O°C over the length of the sample. Total temperature uncertainty was no more than ±3.0°C. Alignment difficulties between the hangdown and radiation shields in the furnace tube required that the sample be positioned in the furnace when cold, and heated with the furnace until the temperature stabilized at the desired point. This required 5 to 6 hr, and was carried out in Matheson ultrahigh-purity hydrogen. Oxidation was started, after evacuation, by introducing a hydrogen-water vapor mixture, obtained by saturating hydrogen with water vapor at 31.00o ± 0.02oC. Oxidation was continued for 90 min. Gas flow was 300 ml per min during heat up and oxidation. Since only several milligrams of oxide are formed on each sample, chemical analysis of the oxide is difficult. A representative analysis is: 80 pct Cr2O3, 5 pct Fe2O3, 3 pct Al2O3, 4 pct MnO, 7 pct SiO2, 1 pct or less NiO. X-ray diffraction analysis of the oxide as formed on the alloy gives rhombohedra1 Cr2O3, and barely distinguishable amounts of a cubic spinel phase, and possibly AlZOs and SO2. The identification of these latter two compounds is by no means certain. The spinel phase could be based on iron or manganese as these elements are present in significant amounts in the oxide. The results of the kinetic studies using 31°C dew-point hydrogen-water vapor mixtures were found to conform to a parabolic rate law. In many cases the parabolic plot consisted of two intersecting straight lines, defining an early and a late rate for a particular run, and in the other cases the parabolic plot consisted of one straight line for the entire run. The slopes of the various straight lines were determined by the method of least squares. Reproducibility of the data was good enough for multiple runs at the same temperature such that the value given for the rate constant is the average for two or more closely similar values, rather than widely varying values of the rate, where more than one determination is indicated in Table I. The exhibition of only one or of two rate constants during a run can happen at the same temperature. Thus, Table I shows that at 11'74°C a single rate constant was obtained from one sample, while other samples oxidized at the same temperature gave an early and a late rate constant. It should be noted that the single rate constant corresponds very closely with the early rate constant. This is also true at 1153°C. The time at which the late rate started to appear was variable, usually occurring 20 to 40 min after oxidation had started.

Jan 1, 1964

By E. F. Koch, J. L. Walter

oriented crystals of iron and iron with 3, 5, and 6.25 pct Si were rolled to reductions of 10 and 70 to 97 pct at room temperature. Similarly oriented crystals were deformed in tension. Dislocation substructures of the deformed crystals were observed by transmission electron microscopy to determine the effect of silicon on the formation of substructures. Pole figures were obtained to relate orientation changes to substructure. When rolled 10 pct, the iron crystals and the 3 pct Si-Fe crystals formed cells, 1 and 0.2 u in diameter, respecliuely. Cells were absent in the higher-silicon crystals. Extended dislocations and possible stacking faults were observed in the 6.25 pct Si-Fe crystal rolled 10 pct and annealed at 650°C. The stacking-fault energy was estimated to be 20 ergs per sq cm. Rolling to 70 pct resulted in the formation of sub-bands (0.9 µ wide) ill the iron crystals and transition bands (containing 0.2-µ-wide subbands) in the 3 pct Si crystals. No subbands formed in the 5 pct Si-Fe crystal until it was ankzealed. SliP occurred on (112) planes ill tension. The slip traces on the 3 pct Si crystal were wary while those on the 5 pct Si crystal wvere straight. The strain-hardening coefficient for the 5 pct Si crystal was nearly zero. Cells did not form, at least at elongations up to 10 pet. The results suggest that cross slip of iron is restricted by additions of silicon beyond about 3 pct possibly by formation of immobile extended dislocations. IN a previous paper' the authors described the substructures developed in (100)[001]-oriented crystals of 3 pct Si-Fe which were rolled to reductions of 10 to 90 pct at room temperature. At low reductions (10 to 20 pct) cells, approximately 0.2 to 0.3 ja in diameter, were formed. The cell walls consisted mainly of edge dislocations. With increasing reduction (up to 50 pct) the cells were seen to elongate in the rolling direction. In certain regions of the crystal there were significant reorientations which were characterized as rotations about an axis normal to the (100) or rolling plane. These regions were called "transition bands". The regions in which there were no reorientations were called ('deformation bands". At reductions of 60 to 70 pct the elongated cells in the transition bands became sub-bands separated by low-angle tilt boundaries with angles of disorientation of about 2 deg. The elongated cell structure in the deformation band was replaced by a general distribution of dislocations. It was noted that the width of the subbands in the transition bands remained 0.2 to 0.3 µ; i .e., the width of the subbands was the same as the initial cell diameter for reductions up to at least 70 pct. From this, and from considerations of the mechanism of formation of the transition bands,' it was concluded that the subbands evolved directly from the initial cells. In order to check this conclusion, it was decided to examine the relationship between initial cell diameter and width of subbands produced by large rolling reductions. Cell size is known to be dependent upon the temperature of deformation.2,3 However, preliminary experiments with 3 pct Si-Fe crystals indicated that the change in cell size with increasing temperature of deform,ation was not sufficient for the present purpose. On the other hand, cell diameters generally reported for iron deformed at room temperature2'3 range from 1 to 2 p, a factor of 3 to 10 larger than the cells in 3 pct Si-Fe rolled to 10 pct reduction,' indicating the possibility of a marked dependence of substructure (at least in terms of cell size) on the amount of silicon in iron. Thus, the investigation was enlarged to include the study of the effects of varying silicon content on substructure in lightly rolled as well as in heavily rolled crystals of iron and iron with 3, 5, and 6.25 pct Si. The crystals used in this study all had the same orientation, (100)[001], with respect to rolling plane and rolling direction. These were rolled to reductions of from 10 to 97 pct and the substructures determined by electron transmission microscopy in both the rolled state and after annealing. In addition, stress-strain curves were obtained from (100)[001]-oriented crystals of iron and 3 and 5 pct Si-Fe to determine the effect of silicon on tensile properties. The dislocation substructure of the tensile specimens was also determined for Samples pulled to 2 and 10 pct elongation at room temperature for comparison with the substructures produced by rolling. 1) EXPERIMENTAL PROCEDURE Crystals with 3, 5, and 6.25 pct Si were prepared by annealing 0.012-in.-thick sheets of high-purity Si-Fe in purified argon at 1200°C to effect growth

Jan 1, 1965

By L. H. Levenson, Charles S. Barrett

Numerous determinations1-' of the texture of cold-rolled polycrystalline iron, steel, and ferritic alloys have been made with good agreement among the various observers as to the principal features of the texture common to all, but there has been no adequate explanation of the texture in terms of, the behavior of individual grains. This study presents an explanation of the texture based on the observed rotation of single crystals when deformed in a manner similar to a grain in the aggregate, a method we have found useful in leading to a better understanding of compression and tension textures;8,9,10 in particular, the aim has been to determine experimentally the end orientations of rolled single crystals of iron. These are discussed in connection with the point of view of Weverl and of Boas and Schmid2 that the rolling texture is a simple compression texture (compression normal to the rolling plane) superimposed on a simple tension texture (tension in the rolling direction), and the point of view of Kurdjumow and Sachs3 that three ideal end orientations exist. Experimental Method The single crystals used were in the form of disks cut from a stock of crystalst pre- pared in this laboratory by a strain-anneal method from mild steel decarburized and purified in hydrogen, the details of which have been described elsewhere.11 To ensure maximum elongation in the rolling direction and to simulate approximately the rolling of a grain in an aggregate, lateral flow was constrained by placing each crystal in a close-fitting hole in a plate of copper or iron of equal thickness and rolling the plate and crystal together. About one-third of the crystals were rolled in a "sandwich" pack by adding top and bottom cover plates. The two-high mill used had 8-in. diameter rolls and was operated at 15 r.p.m. The initial diameter of the crystals was between 1/4 and 1/2 in., while the starting thickness varied from 0.031 to 0.376 in. With a single exception, which was rolled 63 per cent, the crystals were rolled to a final reduction in thickness of 82 to 97 per cent in 20 to 40 passes, alternately changing the sense of the rolling direction. The initial orientations of the crystals were determined either by X-ray back reflection12 or by optical reflectionl3 from etch pits; the mean final orientations were determined by X-ray Laue photograms using molybdenum, silver, or tungsten radiations, by optical reflection, and in many cases by both methods. Results Twenty-six crystals were studied. It was found that there were three typical be-

Jan 1, 1941

By Charles S. Barrett, L. H. Levenson

Numerous determinations1-' of the texture of cold-rolled polycrystalline iron, steel, and ferritic alloys have been made with good agreement among the various observers as to the principal features of the texture common to all, but there has been no adequate explanation of the texture in terms of, the behavior of individual grains. This study presents an explanation of the texture based on the observed rotation of single crystals when deformed in a manner similar to a grain in the aggregate, a method we have found useful in leading to a better understanding of compression and tension textures;8,9,10 in particular, the aim has been to determine experimentally the end orientations of rolled single crystals of iron. These are discussed in connection with the point of view of Weverl and of Boas and Schmid2 that the rolling texture is a simple compression texture (compression normal to the rolling plane) superimposed on a simple tension texture (tension in the rolling direction), and the point of view of Kurdjumow and Sachs3 that three ideal end orientations exist. Experimental Method The single crystals used were in the form of disks cut from a stock of crystalst pre- pared in this laboratory by a strain-anneal method from mild steel decarburized and purified in hydrogen, the details of which have been described elsewhere.11 To ensure maximum elongation in the rolling direction and to simulate approximately the rolling of a grain in an aggregate, lateral flow was constrained by placing each crystal in a close-fitting hole in a plate of copper or iron of equal thickness and rolling the plate and crystal together. About one-third of the crystals were rolled in a "sandwich" pack by adding top and bottom cover plates. The two-high mill used had 8-in. diameter rolls and was operated at 15 r.p.m. The initial diameter of the crystals was between 1/4 and 1/2 in., while the starting thickness varied from 0.031 to 0.376 in. With a single exception, which was rolled 63 per cent, the crystals were rolled to a final reduction in thickness of 82 to 97 per cent in 20 to 40 passes, alternately changing the sense of the rolling direction. The initial orientations of the crystals were determined either by X-ray back reflection12 or by optical reflectionl3 from etch pits; the mean final orientations were determined by X-ray Laue photograms using molybdenum, silver, or tungsten radiations, by optical reflection, and in many cases by both methods. Results Twenty-six crystals were studied. It was found that there were three typical be-

Jan 1, 1941

By E. J. Eisenach, W. E. Jones

SAFETY and industrial hygiene have always been recognized as highly important in company policy, and the co-operative support of the company officials and entire plant personnel has contributed largely to the present success of the Company's program in this field. Growth has necessarily been slow, and dependent, at times, on trial and error but the program in its present form combines the regulations, working methods, and equipment that have proved their value under actual operating conditions. Every effort is made to keep the program on a practical basis. Continuous experimental work is carried on in conjunction with the health and safety program, with resultant periodic changes for improvement. As a proof of accomplishment, in 1945 the frequency and severity rates for accidents were the lowest in the history of the operation. A full-time safety engineer was employed in 1933 and an assistant safety engineer in 1936. During the following year a stenographer was employed in the office and a safety inspector was added for the mine. During the gradual expansion of operations that was climaxed by

Jan 1, 1946

By Charles Albert Ashburner

The coal-fields of the United States have been variously classified as to their geographical positions. In 1887 I proposed slight changes to the classification generally used, for more convenient description of our coal-fields in my report on the statistical history of coal in the States during 1886 for the United States Geological Survey. This new classification seems to meet all practical requirements and has been generally adopted. The coal-areas are grouped in two divisions—the anthracite division and the bituminous division. The anthracite division, in a commercial sense, may be said to include the anthracite districts of Pennsylvania alone, although small amounts of anthracite are mined in Colorado and have been

Jan 1, 1890

By M. Metzger, J. C. Bilello

Microyielding in 99.999 pct Cu occuwed in two distinct parabolic microstages and was substantially indeoendent of grain size at the relatiz~ely large grain sizes stzcdied. The strain recouered on unloading was a significant fraction of the forward strain and was initially higher in a copper-coated single crystal than in poly crystals. Results were interpreted in terms of cooperative yielding and short-range dislocation motion activated otter a range of stresses, and a formalism was given for the first microstage. It was suggested that models involving long-range dislocation motion are more appropriate for impure or alloyed fcc metals. THERE are still many unanswered questions concerning the degree and origin of the grain size dependence of plastic properties. In the microstrain region, a theory of the stress-strain curve proposed by Brown and Lukens,' based on an exhaustion hardening model in which the grain boundaries limit the amount of slip per source, accounted for the variation with grain size of microyielding in iron, zinc, and copper.' This theory assumes N dislocation sources per unit volume whose activation stress varies only with grain orientation. Dislocations pile-up against grain boundaries until the back stress deactivates the source, which leads to a relationship between the axial stress and the strain in the microstrain region given by: where G is the shear modulus, D the grain diameter, a the flow stress, and a, is the stress required to activate a source in the most favorably oriented grain.3 If this or other grain-boundary pile-up models are correct, then the reverse strain on unloading would be much larger for a polycrystalline specimen than for a single crystal. Also, the microplasticity would become insensitive to grain size if this could be made larger than the mean dislocation glide path for a single crystal in the microregion. These questions are examined in the present work on polycrys-talline copper and a single crystal coated to provide a synthetic polycrystal. EXPERIMENTAL PROCEDURE Tensile specimens 3 mm sq were prepared from 99.999 pct Cu after a sequence of rolling and vacuum annealing treatments similar to those recommended by Cook and Richards4-6 to minimize preferred orientation. Grain size variation from 0.05 to 0.38 mm was obtained by a final anneal at temperatures from 310" to 700°C. Dislocation etching7 revealed pits on those few grains within 3 deg of (111). For all grain sizes dislocation densities could be estimated as -107 cm per cu cm with no prominent subboundaries. The single crystals, of the same cross section, were grown by the Bridgman technique with axes 8 deg from [Oll] and one face 2 deg from (111). An anneal at 1050°C produced dislocation densities of 2 x 106 cm per cu cm and subboundaries -1 mm apart in these single crystals. A Pb-Sn-Ag creep resistant solder was used to mount the specimens, with a 19 mm effective gage length, into aligned sleeve grips fitted to receive the strain gages. All specimens were chemically polished and rinsed8 to remove surface films just prior to testing. The synthetic polycrystal was made by electroplating a single crystal with 1 µ of polycrystalline copper from a cyanide bath. Mechanical testing was carried out on an Instron machine using two matched LVDT tranducers to measure specimen displacement, the temperature and the measuring circuit being sufficiently stable to yield a strain sensitivity of 5 x 107. At the crosshead speeds employed, plastic strain rates were, above strains of 10¯4, about 10¯5 per sec for polycrystalline specimens and 10-4 per sec for the single crystals. Plastic strain rates were an order of magnitude lower at strains near l0- '. A few checks at strain rates tenfold higher were made for reassurance that the initial yielding of polycrystalline copper was not strongly strain-rate dependent. Test procedures followed the general framework outlined by Roberts and Brown.9,10 An alignment preload of 8 g per sq mm for polycrystals, and 2 to 4 g per sq mm for single crystals, was used for all tests. These gave no detectable permanent strain within the sensitivity of the present experiments; although at these stress levels, small permanent strains are detectable in copper with methods of higher sensitivity.11 12 stress and strain data are reported in terms of axial components. RESULTS General. The initial yielding is shown in the stress vs strain data of Fig. 1. For polycrystals, cycle lc, the loading line bent over gradually without a well-defined proportional limit, and almost all of the plastic prestrain appeared as permanent strain at the end of the cycle. The unloading curve was accurately linear over most of its length with a distinct break indicating the onset of a significant nonelastic reverse strain at the stress o u, indicated by the arrows. The yielding in subsequent cycles, Id and le, had the same general character. The single crystal behavior, shown to a different scale at the right of Fig. 1, was different in that initially the nonlinear reverse strain was unexpectedly much greater than for polycrystals. It should be noted that these soft crystals had a small elastic

Jan 1, 1970

By P. C. J. Gallagher

A number of recmt determinations for the ratio of extrinsic to intrinsic stacking fault energy in fcc solid solutions are examined. Some of these arise from incomplete analyses which can yield only approxi?nate values for the ratio. Reliable results, on the other hand, obtained using extrinsic-intrinsic fault pairs, show that the extrinsic and intrinsic fault energies are essentially equal in several materials. There is some reason to believe that this finding is of general applicability to fcc elements and alloys. A wide range of values has been obtained for the relative magnitudes of the extrinsic and intrinsic stacking fault energies (yext and yint, respectively) in recently published studies in a variety of materials. In contrast, Hirth and Lothe' using a central force model have shown that out to tenth nearest-neighbor interactions the perturbation in energy caused by both types of fault is the same. Although the model used is not completely valid in metals, there is nevertheless some indication that marked variations of yext/nnt should not be observed from one material to another. In early work in Cu-A1, Cu-Ge, Ni-Co, and stainless steel all the deformation faults observed in the electron microscope were found to be intrinsic in nature, which led to an attitude that the extrinsic fault energy must be considerably greater than the intrinsic. Extrinsic faulting arising from deformation has, however, more recently been directly observed in Au-4.8 at. pct n;~ Ag-6 at. pct Sn and Ag-8 at. pct sn; Ag-7.5 at. pct In and Ag-11.8 at. pct 1n;"' pure silwer and Ag-0.5 at. pct ~n;' and Cu-22 at. pct Zn, Cu-30 at. pct Zn, and Cu-7.5 at. pct ~1.l' Multilayer loops containing extrinsic faulting have also been observed in quenched aluminum." While peak asymmetries in X-ray faulting probability studies were generally attributed to the presence of twins,Lelel2 has recently reinterpreted earlier X-ray data in Ag-Sb alloysU in terms of the presence of extrinsic faulting. The determinations of yeXt/yint made from the above studies are shown in Table I, with a brief description of the techniques employed. A number of the methods utilized are deficient in one or more respects, and the reliability of the values listed will be discussed. ~ele'~ recognizes that his approximate determinations of yext/yint assumes equal numbers of extrin-sically and intrinsically faulted dislocations. It is well-known, however, that such an assumption is not at all justified since extrinsic faulting has but rarely been observed in samples studied in the electron microscope. The only conclusion that should be drawn from the X-ray results at present is that the total intrinsic scattering cross section (i.e., the product of the width of the intrinsically faulted dislocations with their density) is approximately ten times greater than for extrinsic faulting in these particular samples. An important point is that the relative magnitudes of the energies cannot be inferred from results of this type, unless the intrinsic and extrinsic faults form with equal ease. One must recognize that, although a formation barrier may restrict the amount of extrinsic faulting which occurs, this in no way implies that the extrinsic and intrinsic energies should be different. It is unlikely that a worthwhile estimate of the relative densities of extrinsically and intrinsically faulted dislocations can be made at the high deformations present in X-ray samples. ~oretto,'~ from a statistical argument applied to the nonobservation of extrinsically faulted tetrahedra out of a large sample, concluded that yeXt/yint could not be less than -4.5. However, the present author feels that a high-energy formation barrier as just supposed also explains this finding satisfactorily and that no conclusion can possibly be drawn concerning the actual extrinsic stacking fault energy. The same argument also serves to explain the fact that extrinsic faulting has been relatively little observed in the electron microscope. Extrinsic-intrinsic node pairs and isolated extrinsic nodes were first reported by Loretto~ and subsequently by Ives and Ruff,' Gallaher,' and Gallagher and Wash-burn.' Ives and Ruff' found a wide spread in the ratio of extrinsically to intrinsically faulted area in the node pairs they observed, and drew the very tentative conclusion that yeXt/yint 2 2. They recognized that a straightforward comparison of the size of the faulted areas could provide no more than a qualitative result without a theoretical analysis of the dislocation geometry associated with extrinsic faulting. A theoretical

Jan 1, 1969

By B. S. Tani, R. V. Schablaske, M. G. Chasanov

MEASUREMENTS of the solubility of scandium in liquid cadmium from 349" to 606°C by Chasanov, Hunt, Johnson, and eder' led to the isolation and characterization of the intermetallic compound ScCQ. The solid phase found in equilibrium with a saturated solution of scandium in liquid cadmium above 422°C is ScCQ. The equilibrium solid phase below this temperature has not as yet been characterized. Hexagonal needles of ScCG were isolated from a 5 wt pct Sc alloy which had been ice-quenched from 500°C. Free cadmium was leached away from the intermetallic with saturated ammonium nitrate solution. The concentration of cadmium in successive leaches was followed polarographically and the leaching process was terminated when the rate of cadmium dissolution decreased markedly. Chemical analysis of the intermetallic thus isolated is as follows: 11.5 wt pct Sc and 88.3 wt pct Cd. The composition of ScCQ is 11.8 wt pct Sc and 88.2 wt pct Cd. X-ray diffraction powder photographs of ScCds taken in a 114.6-mm Debye-Scherrer camera with CuKa, radiation can be indexed on the basis of a hexagonal nit cell. Lattice coonstants are a. = 6.330 ± 0.001A to 6.324 i 0.001A and co = 4.853 i 0.001A. The a0 has a slight range with the lower value seemingly associated with the cadmium-rich terminus of the phase. With eight atoms in the unit cell the calculated intermetallic density is 7.54 g per cu cm; the density as determined by a liquid-displacement method is 7.7 g per cu cm. Powder-diffraction data for ScCQ are recorded in Table I. Stoichiometry, symmetry, unit-cell dimensions, and the number of atoms per unit cell indicate the MgsCd (D019) type structure for ScCQ; space group is D,&-P6,/mmc. Atomic coordinates are:

Jan 1, 1964

By H. W. Peirce

Identified and utilized Arizona salt deposits are of two ages: 1) Permian in the Colorado Plateau, and 2) Tertiary in the Basin and Range country. Uses include: a) storage of energy fluids in man-made solution cavities in both Permian (Supai Formation) and Tertiary (Luke salt body) salt and b) production of marketable products by solution and evaporation of tertiary salt. The two liquid petroleum storage Projects have a combined storage capacity in excess of 380 million L (100 million gal). Current production of salt products approximates 32 kt/a (32,000 stpy). Increasing demand for both storage and salt products is anticipated.

Jan 1, 1983

By C. F. Jenkins, G. V. Smith

Serrated plastic flow in stable austenitic alloys based on Fe/Ni has been shown to be related to the presence of carbon and/or chromium in the systems. Strength peaks and plateaus in the serrated-flow temperature region for a commercial alloy correlate with an increased dislocation content, arising, presumably, from enhanced multiplication as a result of a strong interaction between dislocations and solute atoms. The data generally support a mechanism controlled by migration of vacancies, with the energy for vacancy motion being modified by the presence of chromium. Chromium atom -dislocation interaction is responsible for effects above 500°C, whereas the defect interacting with dislocations between 200" and 500°C is suggested to be a carbon-vacancy Pair. ThE phenomenon of jerky flow, serrated flow, or the Portevin-le Chatelier (P-C) effect in austenitic stainless steels is usually attributed to substitutional at1,2 mospheres1,2 or to precipitates&apos;-4 which form at dislocations during plastic deformation. On the other hand, evidence exists which supports a direct inter-stitial-dislocation interaction mechanism for serrated flow in fcc Ni-C,5,6 Ni-H7-9 and in nickel-austenites containing carbon." The present work consists in a study of serrated plastic flow in stable austenitic al-loys. The effects of carbon and of chromium were investigated separately, and a commercial stainless steel with different levels of interstitial impurity concentration was studied in an attempt to delineate the combined effects of the alloying elements. EXPERIMENTAL TECHNIQUES a) Materials and Fabrication. A commercial AISI 330 stainless steel and several specially prepared aus-tenitic alloys have been studied. The experimental alloys were prepared by arc melting the constituents under purified argon. Analyses of the materials are given in Table I. The commercial alloy was obtained as 5/8 in. bar stock and rolled to 0.092 in. sq, with several intermediate anneals. At this stage some of the material was annealed in Pd-purified hydrogen at 1100°C to establish different levels of interstitial content. All other heat treatments were in vacuum (10-5 torr). The "pure" alloy ingots were swaged to 0.120-in. rod and annealed in Pd-purified hydrogen at 1100°C. The analyses for these conditions are also contained in Table I. Following the above treatment, the final wire sizes Table I. Chemical Analyses of Test Materials Hrin Hydrogen at Cr, Ni, Alloy 1lOO°C wt pct wt pct C, ppm* N, ppm* Type 330 As-received 14.78 33.25 430 300 Type 330 64 14.78 33.25 40 50 Type 330 200 14.78 33.25 27 21 Fe/35 Ni 72 - 35.10 <10 62 Fe/35 Ni 200 35.10 <I0 44 Fe/35 Nil15 Cr 72 14.95 34.94 <I0 61 Fe/35 Ni/15Cr 200 14.95 34.94 <10 45 Fe/35 Ni/C $ 35.OM 380 *Sensitivity: N t 5 ppm Ct10ppm. f Nominal Ni content. % A master NiC alloy was used in preparation of this material; courtesy of D.E. Sonon. were obtained by either swaging or cold drawing. The test results did not vary with these techniques. b) Specimen Preparation. Two sizes of specimen and two gripping systems were used. i) 0.070-in. wire with a chemically milled gage section: 0.75 in. long, 0.060 in. in diam. These were fastened into grips containing tapped grooves. ii) 0.050 in. wire, gage length 1.5 in. Ball bearings were welded to the ends of the wires and the gage length was taken to include all material between the welds. Socket-type grips were used with these specimens. With specimens of type ii), joining was performed in a specially constructed brass jig, under argon, and automatic timing was utilized in the procedure. No adverse effects of welding were noted. Specimens were encapsulated and solution treated for 1 hr at temperatures selected to produce the same average grain size, -50 µ. Annealing twin boundaries as well as normal crystal boundaries were counted. The temperatures used are listed in Table 11. Table 11. Specimen Size. Temperature of Heat Treatment and Resulting Grain Diameters for Test Materials Recrystallization Resulting Material Condition Temperature Grain Sue AISI 330 Not H purified 0.070 120O°C 45 to 55µ in, wire AlSl 330 H , pure, 0.070 in. 1150°C 45to55µ wire Fc/35Nil15Cr Pure, 0.070 in. wire 1000°C 45tossp Fe/Ni Pure. 0.070 in. wire 775°C 45 to 55µ Fe/Ni/C Pure, 0.050 in. wire 850°C 10 to 20p AlSl 330 Not purified, 0.050 1150CC 45to55p in. wire AlSl 330 ti, pure, 0.050 in. 1150°C 45to55p wire

Jan 1, 1970

By Carl F. Cline, Richard R. Vandervoort, Willis L. Barmore

THE objective of this investigation was to determine the high-temperature plastic deformation behavior of stoichiometric uranium mononitride as a function of stress and temperature. Interest in the properties of this material stems from its potential use in high-temperature nuclear reactor systems. The creep of other refractory compounds containing uranium (e.g., U02, UC) has been studied by various investigators.1"4 Fassler et al.4 have studied the creep of UN in vacuum from 1100° to 1350°C at stresses of 6000 and 8000 psi. In the present work, the creep of stoichiometric UN was investigated from 1500° to 1800°C at stresses from 2000 to 5000 psi in a partial pressure of 200 mm of nitrogen. The specimens were prepared by hot isostatic pressing of UN powder into cylinders of $ in. diam by about 1 in. high. After pressing, the specimens were heat-treated in nitrogen at 1900°C for 50 hr. The densities of individual specimens were determined by the water displacement method. All specimens were theoretically dense, based on a value of 14.32 g per cu cm.5 Principal metallic impurities in ppm by weight were: Ca, 50; Cu, 5; Fe, 30; Mg, 5; Ni, 10; and Si, 20. Oxygen content was 400 ± 50 pprn and carbon content was 100 i25 ppm. The nitrogen content was 5.56 ±0.05 wt pct. The average grain size for five specimens, as determined by the intercept method, was 0.14 i 0.01 mm. One specimen had a grain size of 2.0 mm. This large grain size is an anomaly, since all specimens had the same chemical and thermal histories. Specimens of 1/4 in. diam by 1/2 in. high were creep-tested in compression in a clam shell furnace heated by W-25 pct Re sheet elements. Temperature was measured to ilODC by an optical pyrometer which had been calibrated by a standard source. The distance between fiducial marks on the specimen was measured before placement into the furnace. The furnace chamber was evacuated to 10-5 Torr and back-filled to 200 mm N2. After heating rapidly to temperature, the load was applied and controlled to ±2 pct by an Instron testing machine. Upon initial loading, the specimen was deformed until a constant crosshead rate was obtained, then quenched to room temperature, remeasured, and replaced in the furnace. Upon subsequent reloading at temperature, the crosshead rate was constant for the selected condition indicating steady-state creep.

Jan 1, 1969

By J. S. Kirkaldy, D. H. Weichert, G. R. Purdy

Two-phase diffusion couples have been used to simulate the growth of proeutectoid ferrite in ternary Fe-C-Mn austenites. It has been shown, theoretically and expermentally, that the results fall into two classes: a high-super saturation class in which the major role of manganese additions is to influence the boundary conditions for carbon diffusion; and a low-supersaturation class in which the partition of manganese is required. In the latter case, a drastic inhibition of the reaction rate is to be expected. As an aid to the kinetic analysis, a portion of the iron-rich comer of the Fe-C-Mn constitution diagvam has been determined. The conclusions drawn from this work have a direct bearing on the kinetics of the grain boundary ferrite precipitation reaction and thus yield insight into the manner in which alloying elements can influence the rate of austenite-decomposition reactions. THE role of alloying elements in the austenite-decomposition reactions has provoked considerable interest, since it is apparent that an understanding of this phenomenon will yield insight into the harden-ability problem. In the present investigation, attention is focused upon the proeutectoid-ferrite transformation in the system Fe-C-Mn, and upon the manner in which manganese additions affect the growth rate of ferrite. When hypoeutectoid austenite is supersaturated, the ferrite first formed usually exhibits two distinct types of morphology. At low super saturations, grain boundary layers grow into the austenite grains with an approximately planar interface, and usually possess at least one incoherent phase boundary. At high supersaturations, Widmanstiitten plates appear, which bear an orientation relationship&apos; to the parent austenite. In this case, there is a chance of partial lattice matching along the sides of the plates and an attendant semicoherent interface structure. Purdy and Kirkaldy2 have used a two-phase binary Fe-C diffusion couple to demonstrate that carbon volume diffusion controls the incoherent reaction, while Rouze and rube,&apos; using thermionic-emission microscopy, have shown that the thickening of Widmanstatten ferrite plates is appreciably slower than expected for carbon-diffusion control. This suggests that the plates are bounded by partially coherent, low-mobility interfaces. The redistribution of alloying elements during transformation has been the object of studies by Aaronson4 and owmman,5 who have shown that no alloy partition occurs during ferrite precipitation in the systems Fe-C-Cr and Fe-C-Mo, respectively. More recently, Aaronson et al.6 have shown that some manganese partition occurs at low super-saturations in the system Fe-C-Mn, but that no partition occurs at higher super saturations. Pickle-simer et al.7 observed that no manganese partition occurred during the early stages of the pearlite transformation in a manganese steel, and concluded that volume diffusion of the alloying element is not the rate-deter mining factor. The diffusion coefficients pertinent to this investigation have been measured by Wells, Batz, and Mehl8 (carbon in austenite), R. P. smith9 (carbon in ferrite), Wells and Mehl 10 (manganese in austenite), and Kirkaldy and Purdy11 (diffusion of carbon on a manganese gradient in austenite). Kurdjumov 12 has shown that the diffusivity of substitutional elements in ternary austenites up-quenched from martensite may be greatly enhanced, due, apparently, to the presence of a persistent defect structure. The recent work of Krauss 19 showing high densities of tangled dislocations in reversed Fe-Ni martensite is in agreement with this conception. THEORETICAL Diffusion in ternary or higher-order systems may be described with the aid of Onsager&apos;s extenbion of Fick&apos;s first law,14 in which the flux of each of the n components is assumed to be a linear function of all concentration gradients:

Jan 1, 1964

By F. G. Stone

A strain anneal process has been developed for the production of iron tensile test specimens, the gauge length consisting substantially of a single crystal. Since the method has been quite successful and the results of general interest, the process will be described in detail. The essential feature of the method is the continuous, slow increase of furnace temperature during the grain growth annealing treatment. Briefly, the procedure is as follows: I. Heat machined bars to 950°C in vacuum, hold I hr, furnace cool. 2. Strain to 3.5-3.8 pct elongation (axial loading). 3. Anneal, continuously raising furnace temperature from 450 to goo°C at a rate of so0 per day. 4. Hold at 900°C for 100 hr, furnace cool. Tensile test bars with a 1/4- X I-in. gauge section have been machined from 35 in. Armco iron plate and from 3/8 in. rounds of Puron, a high purity laboratory iron. The axes of the test bars were parallel to the rolling direction. During the machining operation the bars were polished in the lathe with No. 600 emery paper, and this polished surface proved satisfactory for subsequent macrographic examination. A micrographic examination of the materials showed that both were high in FeO inclusions, those of the Puron being smaller but much more numerous. An initial vacuum anneal of I hr at 950°C followed by furnace cooling resulted in a ferritic grain size of ASTM No. 3 for Armco and No. I for Puron. Special heat treatments which reversed these initial grain sizes produced no marked improvement in single crystal production after subsequent treatments. The strain for subsequent grain growth was determined by measuring the decrease in diameter of the tensile bar during elongation. The change in diameter could be measured with a micrometer to +0.0001 in., corresponding to an accuracy of 0.08 pct for the elongation. The accuracy of the diameter measurement is also dependent on grain size because of surface roughening during elongation, and for this reason, a No. 3 grain size is preferable. Optimum grain growth was obtained for strains between 3.5 and 3.8 pct elongation. Once this critical range had been cstablished, all tests were held within it, and thus only meager data were obtained on grain growth following strains outside this range. In general, grain size decreased with increasing strain to about 5.5 pct elongation. Grain growth was occasionally ohserved with less than 3.5 pct elongation although this may have been the result of error in measurement. The program control device for the grain growth anneal consisted of a I rpm motor and worm gear drive, operating the dial shaft of a pyrometer controller through a pulley. Dial speeds of 33 and 50°C per day were tried, but the results at the slower speed were not sufficiently better to warrant the increased furnace time. The furnace tube was evacuated at intervals during the run and kept sealed the remainder of the time. When the controller reached 900°C, it was stopped and the temperature held for 100 hr. This eliminated most of the numerous minute crystallites of about 0.5 mm dimension usually visible on the etched surface of the single crystal. Since recrystallization occurs at the A3 point, the top temperature of 900°C provided a 10"

Jan 1, 1949