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By G. Sachs, J. W. Spretnak

The: iron-rich iron-nickel alloys have attracted considerable academic interest in recent years. The carbon-free alloys are of minor practical importance, but they are the base of many alloys with various outstanding properties. The iron-nickel alloys, therefore, have been investigated extensively regarding both their structures and their properties. The researches on these alloys up to 1938 have been collected and critically reviewed by J. S. Marsh,l and will be discussed in some detail in the sections of this paper dealing with specific subjects. These numerous investigations have not succeeded in establishing the equilibrium conditions in this system. Alloys containing more than a certain amount of nickel (8 to 10 per cent Ni) undergo the allotropic transformation extremely sluggishly, both on heating and cooling, showing a large hysteresis," which is not dependent upon the rate of cooling and persists even with very slow rates of cooling.3 Honda4 and Merica4 have therefore resigned themselves to proposing a diagram (Fig. I) for practical use, illustrating the structural relations under commercial conditions instead of attempting to establish the true equilibrium diagram. Marsh is less pessimistic and suggests an equilibrium diagram (Fig. 2) which conforms approximately to the facts known about this system. Recent X-ray investigations by Owen-Sully5 and Bradley-Gold-schmidt6 on powdered alloys indicate that the previous work on the iron-nickel system yielded very incomplete results. These investigators agree (Figs. 3 and ,+) that alloys in the powdered form containing more than 8 per cent and up to about 35 per cent Ni decompose into a stable heterogeneous mix-

Jan 1, 1941

ARIZONA Tucson University of Arizona, Mining Engineering Society. B CALIFORNIA Berkeley University of California, Mining Asso. B University of California, Library. T Los Angeles Chamber of Mines and Oil. B Southern California Local Section. T Public Library. T Oakland Oakland Free Library. T San Francisco California State Mining Bureau. T Mining and Scientific Press. B Stanford University Stanford University Geological and Mining Society. B

Jan 1, 1917

By B. Tani, K. Anderson, I. Johnson, R. Schablaske

INVESTIGATION of the various rare earth-cadmium binary systems discloses the existence of a compound corresponding to the composition MCd6 in all systems save the La-Cd system. Lattice constants for all of the MCde compounds, except LaCd6 which apparently does not form, and PmCd6 whose synthesis was not attempted, are also recorded herein. Iandelli and Ferro 1 report the existence of the compound CeCd6. No additional information, structural details, and so forth are given. Elliott and Lemons2,3' have measured the vapor pressure of cadmium over CeCd6 and have calculated the activity of cadmium in solid CeCd6. These authors find that CeCd6 exists over a composition range from 5.967 to 6.098 (Cd:Ce ratio) at 584oC, and from 5.971 to 6.118 at 639°C. The following is an excerpt from the paper by Elliott and Lemons: 2 "Recently Mr. F. H. Ellinger of this laboratory has indexed an X-ray diffraction powder pattern of CeCd6.00 which we had prepared by gas phase reaction. The compound has a primitive cubic unit cell with a = 15.783 + 0.001A Based on the volume of the cubes surrounding an elemental cerium or an elemental cadmium atom, Mr. Ellinger finds room for 24.10 CeCd6 formula units in the CeCd6 unit cell; similar calculations based on CeCd2 and CeCd11 yield 24.18 formula units per unit cell. The presence of 24 CeCd6 units per unit cell seems probable with an X-ray density of 8.255 grams per cubic centimeter. The most one can say about in-terstitial~ is that there appears to be room in the crystal even at room temperature." Measurements of the solubility of the rare earths in liquid cadmium4 led to the discovery of GdCd6,

Jan 1, 1964

By J. E. Johnson

Discussion of the paper of Prof. Henry M. Howe, presented in abstract by Bradley Stoughton at the Cleveland meeting, October, 1912, and printed in Bulletin No. 71, November, 1912, pp. 1181 to 1227. J. E. JOHNSON, JR., Ashland, Wis. :-This material is largely beyond the understanding of most of us practical men, but there are certain portions of that diagram that are of enormous importance. We have been conducting a, very extensive investigation of the quality of charcoal-iron and of all iron, and we have found that this eutectic point here (indicating on chart) is a sort of balance point between the good irons and the bad ones, and I have some slides to show what practical results we have found depending on this point here on the d diagram; and it would be a mistake for men who were -concerned with operation and were getting practical results, to think that these things are of no importance. They are exceedingly hard to understand, and I confess that a great deal of them is beyond me, but there is no doubt that the quality of iron depends to an enormous extent on the location of the carbon content of the iron to the right and left of this point, and the position of that point is dependent upon the silicon, and I wish to make a plea to the practical and operating members of the Institute not to disregard this material on account of its being highly scientific, because I hope to show later that there are matters of the highest practical importance that depend directly upon certain portions of this diagram. HENRY D. HIBBARD, Plainfield, N. J. :-T understand that washed metal, which, is practically pure iron and carbon, does not solidify at one instant, is cast-iron does, but passes through a mushy stage. That has been an enigma as to how and why it did so, and possibly some light might be thrown on it in this connection. BRADLEY STOUGHTON, New York, N. Y.:-If Wittorff's propositions are accepted, washed metal containing more than 4.1 per cent. of carbon would begin to solidify as liquid plus Fe4C

Dec 1, 1912

By R. M. Waterstrat, B. N. Das, Paul A. Beck

The central region of the Ti-Mn system was studied by means of x-ray diffraction and metallography. The following intermediate phases were found: an MgZn2-type Laves phase having a wide range of homogeneity, the p-phase of unknozvn structure, and the + -phase with a large tetragonal unit cell, stable at 930°C and lower temperatuves. MaYKUTH, Ogden, and jaffee1 determined the soh-inh bility limits of manganese in and titanium. They also confirmed the structure of the intermediate phase TiMn2 which was previously identified as a Laves phase of the MgZn2 type.2 In the equiatomic region they found an additional intermediate phase, y, which presumably formed by a peritectic reaction at approximately 1200°C. This last observation was disputed by Rostoker, Elliott, and McPhers0n,3 who reported the formation of TiMn by a peritectoid reaction between 900" and 1000° C, but found no evidence of any intermediate phase other than the Laves phase at higher temperatures. Elliott and Rostoker4 reported furthermore that the X-ray diffraction pattern of TiMn could be identified as that of a o phase, although their data were not consistent with this inter~retation. Margolin and Ence6 presented X-ray diffraction data for the and TiMn, phases, and obtained metallographic indications for the existence of additional intermediate phases. They concluded from metallographic observations that two Laves phases are formed, separated by another phase, designated as &. A phase diagram for the Mn-Ti system has recently been published by Savitskii and Kopetskii,' which shows considerable disagreement with the work of Hellawell and Hume-Rothery,' in particular with regard to the terminal solid solutions based on the allotropes of manganese. The present investigation was undertaken primarily to clarify the phase relationships in the equiatomic region of the Ti-Mn system. The metals used in preparing the alloy specimens Were iodide titanium and electrolytic manganese, the latter having a nominal purity of approximately 99.9 pet. The electrolytic manganese was covered with a thick coating of a brown manganese oxide which was reduced by heating the manganese flakes for several hours at a temperature of 1100°C in an atmosphere of dry hydrogen. Three alloys, see Table I, were made using sponge titanium and manganese not treated in hydrogen. The alloys were prepared by arc-melting in an atmosphere of helium or argon. The composition of each alloy was calculated by assuming that the entire weight loss during melting was due to evaporation of manganese. Subsequent chemical analysis of certain alloys indicated that the compositions calculated in this manner were usually correct within 1.4 pct, as shown in Table I. All alloy specimens were wrapped in molybdenum foil before sealing them in silica tubes containing argon at a pressure of 1 atm at the annealing temperature. After quenching in cold water, the alloy specimens were bright and clean, with no evidence of any surface reaction. The alloys listed in Table I were examined metallographically, using an etchant consisting of 20 pet HNO3, 20 pet HF, and 60 pet Glycerine. powder for X-ray diffraction examination was prepared by crushing a portion of each annealed alloy

Jan 1, 1962

By William A. Edmiston, R. E. Grace

A simplified model for the theory of reaction rates near equilibrium has been applied to the reduction of wustite. A linear relationship between the net rate of reaction and the Gibbs free-energy change, ?F, is predicted. The reduction of wustite in H2 -H2O gas mixtures was studied with a microbalance technique at temperatures from 850° to 950 °C. The predicted model was found to be valid to -?F/RT = 0.1 or approximately -200 cal per mole away from equilibrium. ThE theory of reaction rates near equilibrium has been developed by a number of authors. Prigogine, Outer, and Herbo1 have studied the catalytic hydrogena tion of benzene in an attempt to deduce some intrinsic connection between reaction rates near equilibrium and thermodynamics. Manes, Hofer, and weller2 have derived more general expressions for reaction rates near equilibrium from classical thermodynamics. Hollingsworth3,4 has commented briefly on the work of Manes et al. Benson5 has summarized in a general way the results of the earlier contributions. It is the purpose of this paper to apply the theory of reaction rates near equilibrium specifically to the reduction of wustite in H2-H2O gas mixtures. The basic premise is that the reduction of wustite proceeds by a surface reaction, rather than by solid-state diffusion ,or gaseous diffusion. Richardson and Dancy6 and Gellner and Richardson7 have suggested that the reduction of wustite may be governed by iron diffusion in wustite. Mckewan8-11 has proposed that reduced iron layers on various oxides are sufficiently porous to offer a negligible impedance to the reducing gas. The linear motion of interfaces reported by McKewan and discussed by Themelis and Gauvin12 indicates the lack of diffusive control during reduction. The reduction studies of magnetite reported by Quets, Wadsworth, and Lewis13 give additional evidence that reduction rates are linear when the reaction products are porous and nonprotective. The interpretation of measurements reported in this paper is predicated upon a surface-controlled reduction reaction, at least in the earliest stages of reduction when the reduced iron layer is thin.

Jan 1, 1967

By H. J. Stehli

Probably the earliest sinter from lead ore was made in the product sinter boxes attached to some hand reverberatory roasters. The ore was drawn from the roaster bed when dead roasted, and then by laborious effort fritted together by rabbling at a high temperature in the sinter box. This was not a true sinter, but was a great improvement over the dusty dead-roasted fine ores. The Huntington-Heberlein pots were the first real advance in the art, and produced some real sinter. They required that the sulphides be preroasted to 5 or 6 per cent sulphur, and the long cycle of operating and deep bed of material used in the pots fostered the formation of densely fused material and fines. This necessitated crushing of the densely fused cake and returning to the next charge large amounts of fines screened out. The Huntington-Heberlein pots made comparatively high lead losses because the deep bed and high internal temperature together favored the volatilization of lead. Lime (CaO) was added to the charges, and this addition constituted the patented feature of the Huntington-Heberlein process. Its sole function we now know was to act as an isolator of the sulphide particles, and any other substance—for instance, iron oxide—of equal fineness performed the same function. The Savelsberg process used limestone instead of burned lime, and in this there was a definite advantage. The converting of CaCO3, to CaO is a highly endothermic reaction, so the lime acted not only as an isolator of sulphide particles but absorbed excess heat and to some extent prevented premature fusion of the sulphides. The Carmichael-Bradford process used gypsum instead of limestone, and had the disadvantage of adding more sulphur to a charge from which it was desired to eliminate sulphur. Here again the gypsum served only as an infusible isolator of sulphide particles. The first Dwight-Lloyd apparatus to sinter lead ores commercially was installed at Perth Amboy in 1907. The fact that lime in any form was necessary to sintering was quickly disproved by making excellent sinter from Bunker Hill and Sullivan table concentrates, silica sand and iron oxide only.

Jan 1, 1937

By B. H. Kear

Clustering of slip bands in different systems has been observed in both ordered and disordered Cu3Au crystals compressed in the <110> orientation. Certain features of the slip band patterns are explained in terms of reactions between dislocations with Burgers vectors at 120 deg; in a few rare cases, the slip band evidence suggests that the Products of such reactions form diffuse tilt boundaries between the differently slipped regions of the crystal, similar to the known behavior of ionic crystals, but not nearly so well defined. WHEN crystals with orientations favorable for multiple slip undergo plastic deformation, slip may occur in different systems in localized regions, so that clusters of slip bands are developed. This phenomenon has been observed in fee1-4 metals and also in ionic crystals having the sodium chloride structure.5-8 In the ionic crystals, the boundaries formed between the differently slipped regions of the crystal assume characteristic orientations and are associated with macroscopic tilts that are plainly visible on the sides of the crystal. Recently, this interesting feature was explained in terms of the formation of diffuse low-angle boundaries as a result of interactions between families of glide dislocations in the different systems meeting in the boundaries.9 This paper describes an attempt to obtain similar evidence for boundary formation in an fee crystal. The alloy Cu3Au was chosen for the present study simply because this material is currently being used in a general study of differences in deformation behavior of the ordered and disordered phases of this alloy, which will be described elsewhere. EXPERIMENTAL PROCEDURE The two specially oriented compression specimens used in the present study were prepared from a melt-grown single crystal by careful cutting, grinding and polishing. The finished specimens were about 6 mm by 2 mm in cross section by 6 mm tall, with their ends parallel to (101) and sides parallel to (111) and (121); the broad faces of the specimens were made parallel to (711). Both specimens were annealed in an evacuated quartz tube at 850oC for several hours, slowly cooled to 500°c, and then quenched into water in order to obtain the disordered state for the alloy. One of the specimens was partially ordered (with S- 0.8) by reannealing at 350oC for 100 hr. After these annealing treatments, both of the specimens were electropolished. 10 Finally, the specimens were compressed in the [loll orientation and their stress-strain curves were recorded. The deformation was carried out in increments of a few percent strain. At each stage in the deformation the specimens were unloaded, removed from the compression jig, and examined optically for slip bands. Before reloading, the specimens were repolished, so that the observed slip band patterns were characteristic of a particular stage in the deformation. EXPERIMENTAL RESULTS Fig. 1 show!; the stress-strain curves for the ordered and disordered specimens and also indicates the stages 1, 2, and 3 where the deformation was interrupted for examination of slip bands. The curves show marked differences in flow stress and in work hardening rate in the two specimens, as observed by previous workers.11,12 Also, it was found, in agreemement with the observations of Taoka and Sakata,&apos;3 that the plastically deformed disordered alloy showed the characteristic coarse slip bands of alloys, whereas the ordered alloy exhibited a fine slip band structure similar to that of pure metals. Slip Band Observations. In what follows, the description of the slip band patterns, with accom-

Jan 1, 1962

By Henry R. Joesting

DURING the past year and a half, the Territorial Department of Mines in Alaska has conducted a modest experimental program for the purpose of determining the extent to which magnetic and resistivity methods can be used in interior Alaska in connection with prospecting, mining and geological studies. Since little information is available concerning previous work,1,2 and since conditions differ considerably from those in most other regions, it was considered advisable to make a general study of the possibilities and limitations of the two methods, rather than a detailed study of any single problem. PROBLEMS One of the most serious handicaps to prospecting and geological study in interior Alaska, especially in the mature regions, is a cover of unconsolidated deposits ranging in thickness from a few feet to several hundred feet. These deposits, some of which are permanently frozen, consist of silt with varying proportions of vegetation and windblown material in the valleys and of residual deposits on the hills.3,4 The problems treated here are caused by the existence of this overburden: I. Location of buried placers. 2. Determination of depth and areal distribution of permanently frozen and of thawed unconsolidated deposits. 3. Location of water-bearing beds under unconsolidated deposits. INSTRUMENTS AND METHODS Magnetic and direct-current resistivity methods were used because they are relatively simple, rapid and inexpensive and because generally they are well suited to the study of the problems indicated. The instruments used were a vertical Schmidt-type magnetometer and a direct-current resistivity instrument similar to those used by the Geophysical Branch of the U. S. Geological Survey.5 For placer surveys with the magnetometer, a sensitivity of about 25 gammas per scale division was found suitable. For resistivity studies of frozen and thawed overburden and of underground water, the Lee partitioning method6 was found to be most generally suitable. In the Lee method a central potential electrode is placed midway between the two potential electrodes of the Wenner four-electrode configuration.7 Nonpolarizable electrodes were made from unglazed porcelain pots about 10 cm. high and 5 cm. in diameter. In order to retard evaporation of the electrolyte the sides of the pots were glazed, inside and out, with clear Duco lacquer. For resistivity work in cold weather, a nonfreezing electrolyte consisting of equal parts of ethylene glycol and a saturated water solution of copper sulphate proved satisfactory. Stainless steel rods of 3/4-in. diameter made excellent current electrodes because their bright finish enabled good ground contacts to be made.

Jan 1, 1941

By H. R. Thresh

An oscillational vis cometer has been constructed to measure the viscosity of liquid metals and alloys to 800°C. An enclosed cylindrical interface surrounds the molten sample avoiding the free surface condition found in many previous measurements. Standardization of the apparatus with mercury has verified the use of Roscoe&apos;s formula in the calculation of the viscosity. Operation of the apparatus at higher temperatures was also checked using molten lead. Extensive measurements on five different samples of zinc, of not less than 99.99 pct purity, indicate i) impurities at this level do not influence the viscosity and ii) the apparatus is capable of giving reproducible data. The variation of the viscosity ? with absolute temperature T is adequately expressed by Andrade&apos;s exponential relationship ?V1/3 = AeC/VT , where A and C are constants and V is the specific volume of the liquid. The values of A and C are given as 2.485 x 10-3 and 20.78, 2.444 x 10-3 and 88.79, and 2.169 x 10-3 and 239.8, respectively, for mercury, lead, and zinc. The error of measurement is assessed to be about 1 pct. Prefreezing phenomena in the vicinity of the freezing point of the zinc samples were found to be absent. AS part of an over-all program of research on various phases of melting and casting nonferrous alloys, a systematic study of some physical properties of liquid metals and their alloys was undertaken in the laboratories of the Physical Metallurgy Division.1,2,3 The most recent phase of this work, on zinc and some zinc-base alloys, was carried out in cooperation with the Canadian Zinc and Lead Research Committee and the International Lead-Zinc Research Organization. One of the properties investigated was viscosity and the present paper gives results on pure zinc; the second part, on the viscosity of some zinc alloys, will be reported separately. Experimental interest in the viscosity of liquid metals has virtually been confined to the past 40 years. The capillary technique was already established as the primary method for the viscosity of fluids in the vicinity of room temperature; all relevant experimental corrections were known and an absolute accuracy of 1 to 2 pct was possible. Ap- plication of the capillary method to liquid metals creates a number of exacting requirements to manipulate a smooth flow of highly reactive liquid through a fine-bore tube. Consequently, the degree of precision usually achieved in the high-temperature field rarely compares with measurements on aqueous fluids near room temperature. However, the full potential of the capillary method has yet to be explored using modern experimental techniques. As an alternative, many investigators in this field have preferred to select the oscillational method. Unfortunately, the practical advantages are somewhat offset by the inability of the hydrodynamic theory to realize a rational working formula for the calculation of the viscosity. In attempting to overcome this restriction many investigators have employed calibrational procedures, even to the extent of selecting an arbitrary formula for use with a given shaped interface. However, where calibration cannot be founded on well-established techniques, the contribution of such experiments to the general field of viscometry is questionable. A critical appraisal of the viscosity data existing for pure liquid metals reveals a somewhat discordant situation where considerable effort is still required to establish reproducible and reliable values for the low-melting point metals. The means of rectifying this situation have gradually evolved in recent years. Here, the theory of the oscillational method has undergone major advances for both the spherical and cylindrical interfaces. The basic concepts of verschaffelt4 governing the oscillation of a solid sphere in an infinite liquid have been adequately expressed by Andrade and his coworkers.5,6 Employing a hollow spherical container and a formula, which had been extensively verified by experiments on water, absolute measurements on the liquid alkali metals were obtained. The extension of this approach to the more common liquid metals has been demonstrated by culpin7 and Rothwel18 where much ingenuity was used to surmount the problem of loading the sample into the delicate sphere. Because of the elegant technique required to construct a hollow sphere, the cylindrical interface holds recognition as virtually the ideal shape. On the other hand, loss of symmetry in one plane increases the complexity of deriving a calculation of the viscosity. The contributions of Hopkins and Toye9 and Roscoe10 have markedly improved the potential use of the cylindrical interface in liquid-metal viscometry. The relatively simple experi-

Jan 1, 1965

By Clark L. Corey, Bogdan Lisowsky

Electrical resistivity, X-ray line positions, degree of order, and microstructures have been investigated for Ni-A1 alloys near the Ni3Al composition. The results indicate that Ni3Al undergoes disordering between 1250oC and the mp; also supersaturated y, produced in y + y&apos; alloys by gas quenching, is extensively ordered prior to y&apos; (Ni3Al) phase separation. The latter reaction, if not both, must follow the cooperative phenomena model. Shifts in line position as a function of quench-indulced super satulration are shown. Lattice pavarneters of equilibriunz and nonequilibrium phases are given. THE objective of this investigation was to determine the mechanism and kinetics of the reactions which occur in Ni3A1 and hypostoichiometric Ni3A1 alloys. The results are of particular significance relative to pre-precipitation phenomena. Early work on Ni-A1 binary compositions near the Ni3A1 composition (13.6 wt pct Al) has been adequately reviewed by Hanssen,1 whose phase diagram is presented in Fig. 1. williams2 verified the suggestion made by Taylor and Floyd3 and others4 that y&apos;, Ni3A1, may precipitate coherently on (100) planes of the y phase (see Fig. 1 for phase nomenclature); he further suggested a two-step precipitation mechanism consisting initially of probably short-range ordering followed by actual precipitation of y&apos;. The precipitation stage in low-aluminum hypo-eutectic compositions has been studied by a number of investigators;*"7 short-range order or "zone" formation have been suggested as explanations for various diffuse X-ray scattering effects. The ordering reaction in Ni3A1 alloys is characterized by a) a very rapid rate of ordering in nonstoi-chiometric compositions, b) absence of a disordered phase region for the stoichiometric compound, y&apos;, or Ni3A1, c) precipitation phenomena as a dominant aspect in hypoeutectic alloys, and d) an increase in elec-trical resistivity on ordering.&apos; The latter two factors were found by Newkirk to characterize ordering in Co-Pt, for which an extensive and detailed analysis was made.&apos; An electrical-resistivity increase on ordering has also been reported for cuAu3.10 PROCEDURE Ni-A1 alloys in the form of 1300-g chill-cast ingots were prepared by vacuum melting electrolytic nickel and high-purity (99.99 pct) aluminum. Very small heats prepared from high-purity carbonyl nickel, supplied through the courtesy of Dr. Goff of the Naval Research Laboratory, were used for comparison with the larger ingots and no differences were noted. The cast material was homogenized in purified argon for a minimum of 72 hr at 1200°C and water-quenched from 1350°C. Compositions studied are given in Table I. The 10 pct A1 alloy was both hot- and cold-rolled. X-ray superlattice line intensities and peak positions were obtained from -270 mesh filings, using CuK, radiation with a LiF crystal monochromat adjusted to receive both 01 and a2. One-degree slits and a 1/8 deg per min scan rate were used to record line traces. A standard tungsten powder, obtained through the courtesy of G.E. Research Laboratory, was used to calibrate line positions.

Jan 1, 1968

By W. C. Ellis, E. S. Greiner, M. E. Fine

C. H. Samans and W. R. Ham (Chicago, Ill., and Dix-field, Maine, respectively)-—For several years we have been studying transitions of this basic type in metals, alloys, glasses, etc. Usually, however, they are not so clearly marked as those which the authors have found, and hence are much more difficult to determine accurately. Since our studies indicate that most of them occur virtually unchanged (as far as temperature is concerned) regardless of the form in which the element appears, we believe that they are a characteristic of the atom. Specifically, we believe that there is an additional rotational degree of freedom possessed by the nucleus which has not been considered heretofore. This nuclear rotation is made up of several components, each related to the several quantum shells of electrons. In chromium there are four of these shells and hence four separate series of characteristic transition temperatures. The lowest temperature at which any transition occurs, based on the present state of our computations, is 125°K, 4° higher than the authors&apos; value of 121°K. A convergence of this series, we believe, shows up at the higher temperature of 2085 °K, surprisingly close to the transformation temperature of 2103°K recently announced by N. J. Grant of M.I.T. for a body-centered to face-centered transformation in chromium. Likewise, our computations indicate a temperature of 311°K for the second transition temperature, reported by the authors as 310 °K. A convergence of this series, we believe, shows up at a higher temperature as the melting point at 2163°K. Although our work on these series must, in a sense, still be regarded as empirical, since we do not understand fully as yet just what the series mean, it is based on a reasonably firm picture. The individual constants, from which the various series are computed for each element, comes directly from the X-ray K absorption limit. Furthermore, the same basic method has accounted for transformation and melting temperatures in about 50 of the chemical elements, which is all we have tried thus far. In many cases the only known transformation is the melting point, but in others the occurrence of transformations or other transitions, equally as well marked as those of the authors, has been pointed out by others. These observations have assisted us greatly. Consequently we were very pleased to see the authors&apos; excellent work in finding these two transitions in chromium. With these confirming data, our picture of this element is clarified considerably, so we expect that at least some of our work can be published in the near future. R. C. Ruder (E. I. du Pont de Nemours & Cu., Wilmington, Del.)—The authors&apos; interpretation of these transitions in terms of 3d to 4s electronic structure transitions is most interesting. It would be interesting to have additional experimental evidence of such transitions from the temperature dependence of the Hall coefficient in the neighborhood of the property changes discussed in this paper. Simple theory15 suggests the Hall coefficient as a measure of the free electron (or s electron) concentration per unit volume. It has been shown that for paramagnetic&apos;" and ferromagnetic1? metals the simple theory is in fact too simple. However, the existence of a discontinuity in the Hall coefficient would provide information which should aid both in our understanding of these transitions and the significance of the Hall coefficient in these metals. It was rather surprising that no significant paramagnetic effects were observed. In this connection the recent work of McGuire and Kriessman18 is cited. They measured the magnetic susceptibility of chromium from 20" to 1460 °C. They also observed no large change in the susceptibility although there might be a change in slope in the vicinity of the 40 °C transition. The existence of these 3d to 4s electronic transitions has been discussed in connection with the paramagnetic susceptibility behavior of nickel and nickel alloys.&apos;"-" Assuming a correspondence principle between classical and quantum mechanical paramagnetic theory and using classical theory to calculate the effective Bohr magneton number from the Curie constant for substances obeying the Curie-Weiss law," it is found that the effective magneton number is a function of temperature. The process of calculation involves the inverse of the differential of the 1/x4 vs. temperature curve so that good and numerous data are necessary to obtain significant results. The data of Fallot23 show a discontinuous increase of about 12 pct in the effective magneton number between 850" and 900 oC, followed by a continuous increase up to the melting point. The data of Sucksmith and Pearce24 show a possible 8 pct increase. The older data of Terry25 and Weiss and Foex26 show a continuous increase. It is possible that small amounts of impurity atoms change these electronic transitions significantly. Fallot&apos;s23 data on a nickel alloy with 4.5 atomic pct Fe indicate that the discontinuity occurs around 1300 °C. Systematic investigation of the transition metals for transitions of this nature should provide information which would be very valuable for our understanding of these metals. The absence of antiferromagnetic structures in chromium has been shown by Shull27 using neutron diffraction techniques. M. E. Fine, E. S. Greiner, and W. C. Ellis (authors&apos; reply)—The remarks by Drs. Samans and Ham are certainly very interesting, in particular those pertaining to the close agreement between the theoretically calculated values for transition temperatures in chromium and the experimental values reported by a number of investigators. This is a remarkable achievement and we shall look forward to a more detailed presentation of the method followed in their calculations. We do not believe that the transition in pure chromium near 40 °C remains temperature invariant with alloying, as was reported by Samans and Ham for a number of the substances that they studied. We have not done any work with alloys but base our belief on the results of earlier studies in which less pure chromium was included and considerably lower transition temperatures were observed. The transition tempera-

Jan 1, 1952

By E. T. Turkdogan, J. H. Swisher

bi the fivst part of the paper results ave given on the rate of decarburization of Fe-C melts ln CO2-CO atmospheres at 1580°C. The rate -controlling step is believed to he that irvlloluing dissociation of curbotz dioxide on the suvfuce of the melt. 4 genevral reaction mechanistm is poslnlated jor gels-t11eta1 veactions oc-curit~g on the surface of iron coutcotamncited with chemi-sovbed osygesL. Oxygen the present work on decavbuvization of liquid iron and previous studies on the kinetics of nitrogen absorption and desorplion are discussed in terms of the postulated mechanism, ManY of the early studies of rate of decarburization of liquid steel were of an exploratory nature and laboratory exppriments carried out pertained to open-hearth or oxygen steelmaking processes. References to previous work on this subject may be found in a literature survey made by Ward. Using more sophisticated experimental techniques, several investigators have recently studied the kinetics of decarburization of molten Fe-C alloys in oxygen-bearing gases. For example, Baker et al2.&apos; reported their findings on the rate of decarburization of liquid iron, levitated by an electromagnetic field, in carbon dioxide-carbon monoxide-helium atmospheres. In these levitation experiments the samples used were small in size, e.g., -0.6-cm-diam spheres weighing -0.7 g, and the rates were measured for decarburization from about 5 to 1 pct C at 1660°C. The rates obtained under their experimental conditions were considered to be controlled primarily by gaseous diffusion through the boundary layer at the surface of the levitated melt. Parlee and coworkers3 measured the rate of absorption of carbon monoxide in liquid iron. The rates were found to follow first-order reaction kinetics, yielding a reaction velocity or a mass transfer coefficient in the range 0.2 to 0.4 cm per min. The coefficient was found to decrease with increasing carbon content of the melt. These investigators attributed the observed rates to the transfer of carbon or oxygen through the diffusion boundary layer adjacent to the surface of the melt. In the work to be reported in this paper, an attempt has been made to study the kinetics of gas-metal surface reactions involved in the decarburization of liquid iron. EXPERIMENTAL The experiments consisted of melting 80-g samples from an Fe-1 pct C master alloy in an induction furnace and decarburizing in controlled CO2-CO mixtures at 1 atm pressure and 1580°C. The master alloy was prepared by adding graphite to electrolytic "Plastiron" melted in racuo. None of the impurities in the master alloy exceeded 0.005 pct. The reacting gases were dried by passage through columns of anhydrone; in addition, CO2 impurity in carbon monoxide was removed by passage through a column of ascarite. A schematic diagram of the apparatus is shown in Fig. 1. A 1.25-in.-diam recrys-tallized alumina crucible containing the sample was placed inside a 3-in.-diam quartz reaction tube, all of which was surrounded by an induction coil. A 450-kcps induction generator was used as the power source. Water-cooled brass flanges, which contained the gas inlet, gas exit, and sight port, were sealed to the top of the reaction tube with epoxy resin. The reacting gases were metered with capillary flowmeters and passed through a platinum wire-wound alumina preheating tube, 0.25 in. ID and 11 in. long. The gases were preheated to about 1300°C. A disappearing-filament optical pyrometer was used to measure the melt temperature. The pyrometer was initially calibrated against a Pt-6 pct Rh/Pt-30 pct Rh thermocouple. The temperature was controlled to within +10°C by manually adjusting the power input to the induction coil. In a typical experiment, an 80-g sample of the master alloy was melted in a CO2-CO atmosphere having pcO2/pco = 0.02 and flowing at 1 liter per min. A negligible amount of carbon was lost and no significant reduction of alumina from the crucible occurred during melting, e.g., 0.005 pct Al in the metal. After reaching the experimental temperature of 1580°C, the gas composition was changed to that desired for a particular series of decarburization experiments. The duration of the transient period for obtaining the desired gas composition at the surface of the melt was about 20 sec . The flow rate of the reacting gas was maintained at 1 liter per min. After a predetermined reaction time, the power to the furnace was turned off. During freezing, which took about 10 sec, the amount of gas evolution was not sufficient to result in a significant loss of carbon. The samples were analyzed for carbon by combustion and in a few cases they were analyzed for oxygen by the vacuum-fusion method. RESULTS A marked increase in the rate of decarburization of iron with increasing pcO2/pco ratio in the gas stream is demonstrated by the experimental results given in Figs. 2 and 3 for pco2/pco ratios from 0.033 to 4.0. In one series of experiments, denoted by filled triangles in Fig. 2, the reacting gas was diluted with argon (48 vol pct) resulting in a slower rate of decarburization. Samples from two series of experiments with pco2/pco = 0.033 and pco2/pco = 0.10 (with argon dilufion) were analyzed for oxygen. In these Samples the oxygen content increased with reaction time

Jan 1, 1968

By C. Laird, C. E. Feltner

An investigation into the effect of a material&apos;s slip character on its high strain fatigue properties has been carried out using copper and Cu-7.5 wt pct A1 as representative wavy and planar slip mode materials, respectively. In copper, the constant term and exponent in the Coffin-Manson equation, ?EpNf1/2 = const, are unaffected by the temperature of testing or the history of the metal. On the other hand, in Cu-7.5 wl pcl Al, while the exponent is invariant, the constant is increased with respect to copper and increased further with decrease in temperature. The life in Cu-7.5 wt pct A1 is double that of copper at room temperature and about four times at 78°K. Fractoflaphic studies indicate that these diffevences in life are associated with the early stages of cracking. In copper, severe surface rumpling provides crack nuclei at pain boundaries independent of&apos; testing temperature or the history of the metal. In Cu-7.5 wt pct Al, the planar slip mode of deformation prevents grain boundary folding; crack nucleation is therefore mainly transgranular and the increase in life with respect to copper is associated with a prolonged linking-up stage of such transgranulay cracks. At the lower temperature the increased difficulty of cross slip inhibits multiplication of trans-granular cracks and retards the linking-up process, giving a further enhaancement in life. It is expected that such behavior will be found general in materials of wavy and planar slip mode, respectively. STAGE II crack propagation in high strain fatigue takes place by a repetitive process of crack tip blunting in the tension part of a fatigue cycle followed by resharpening of the crack in the compression part.1-3 This mechanism has come to be called the "plastic relaxation process".3 At very high strains (lives to failure less than 103 cycles), most of the life of a specimen is spent in crack propagation by the plastic relaxation process.4,5 Since the differences in the cyclic strain hardening behavior of metals and alloys are comparatively small in this strain range,6,7 the amount of blunting at a crack tip depends primarily on the applied strain amplitude. The rate of crack propagation in this life range is therefore nearly constant with respect to material and temperature of testing. In the longer life portion of the high strain fatigue range (l03 to 103 cycles to failure), a considerable fraction of the lives is spent in crack initiation and Stage I growth. Grain boundaries have frequently4,5,8 been found to be the sites for this growth which is also associated with a surface folding process.4&apos;5 Such folding behavior may also be general in any material having a grain structure and capable of plastic deformation. It has therefore been suggested475 that the universality of the Coff in-Manson law,9&apos;10 constant,* where ?Ep is the plastic strain range and Nf the number of cycles to failure, is reflected in the approximate invariance of both the crack initiation and propagation behavior. It happens that, in most investigations of the phenomena associated with failure,4,5,8 materials with a wavy slip mode have been used as vehicles for the studies, or else "normally" planar slip mode materials have been tested under conditions giving rise to wavy glide deformation, e.g., stainless steels cycled at high temperature.&apos;&apos; The purpose of the present investigation was to determine whether or not different cracking phenomena would occur when the slip mode of a material is planar and if the associated life to failure would be different than that of a wavy slip

Jan 1, 1968

By E. J. Eisenach, Edward Matsen

AT the present time the Climax Molybdenum Co. is the largest molybdenum producer in the world and the operator of the largest underground mine in North America. It has grown steadily and rapidly since its beginning in 1917. Only 250,000 lb of MoS2 were produced during the first year from 1917 to 1918 when the company was formed. Operations were suspended shortly thereafter because of the lack of a market and knowledge of the uses of molybdenum. During World War I it was used as a substitute for some rare metals and for minor chemical purposes. After 5 years of intensive research and sales promotion, Climax metallurgists succeeded in finding proper applications for the newly discovered metal and the mine was reopened in 1924. Demand for molybdenum increased gradually and in 1930, 3.5 million lb of MoS2 were produced. In the meantime, research work for additional uses of molybdenum continued until it had established itself as one of the most important alloying elements in producing high quality steels. After the start of World War 11, from January 1942 to October 1953, 43 million tons of molybdenum ore were mined and 484 million lb of MoS2 were produced. Climax mine is located in Colorado, 100 miles southwest of Denver and 12 miles northeast of Leadville on the Continental Divide of the Rocky Mountains. The principal mine workings range from 11,170 to 12,000 ft in elevation. Topographically, it lies in the base of a large cirque that is surrounded by Mt. Bartlett to the north, Clinton Peak and McNamee Peak to the east and Ceresco Ridge to the south. This cirque opens to the west and to the Ten Mile Valley.

Jan 3, 1954

By Gerhard Derge

The extension of metallurgical control of steelmaking processes has always made it desirable to have some quick method for determining the oxygen content of molten steel. To meet the practical demands of the steel industry, this method must also be simple enough so that the sampling can be done by the regular furnace crew. This requirement was kept in mind continually in the work to be described. An oxygen value is required for proper control, whether it be of a rimming steel or of a fully killed steel. However, two factors have discouraged the development of such direct methods: i. The reaction C + FeO Fe + CO is rapid enough to make the correct sampling Of the bath a difficult problem. The most generally accepted means of circumventing this difficulty have been the aluminum-killed bomb test of McCutcheon and Rautiol and the aluminum-killed spoon test of Herty.2 The theory of these tests is that all of the oxygen in the iron is converted to Al2O3, which can then be determined by chemical methods. Even when simplified so that the analysis is made by a measurement of turbidity, this method is too slow to be used in routine control. Furthermore, the results obtained have never been entirely satisfactory, and some of the reasons for this will be discussed later in this paper. z. The ordinary chemical methods of analysis for oxygen in steel are not reliable. The only analysis that seems to possess sufficient dependability to be of value is vacuum fusion,3 and the apparatus and technique developed for this have been too complex and slow for routine work. Indirect Methods Indirect methods of estimating the oxygen have been resorted to in mill practice. Generally these depend upon the chemical equilibria involved. The oxygen in the bath is related to other components in the slag or metal that can be analyzed the readily. These methods have many difficulties in common. Steelmaking processes involve a complicated set of interrelated reactions, all of which tend to approach equilibrium at varying rates. The degree to which any particular equilibrium is approached is not well established. Moreover, a proper use of theoretical equilibrium constants requires a more extensive knowledge of the activities of the con- than we now have. This is well illustrated by the irregularities observed when trying to determine the oxygen in the metal by its ratio to the iron oxide in the slag. Equiliblium relations may be used mole readily if they are evaluated by plant experience, but the extent of approach to equilibrium remains an undetermined variable and lack of an entirely satisfactory mean, of determining oxygen for the calibration is felt keenly, For example, the statistical analysis of the relation between carbon and oxygen4.6 illustrates that even iia a single plant wide variations exist under llormal conditions of operation. Never. theless, this is one of the best methods now

Jan 1, 1943

By Gerhard Derge

The extension of metallurgical control of steelmaking processes has always made it desirable to have some quick method for determining the oxygen content of molten steel. To meet the practical demands of the steel industry, this method must also be simple enough so that the sampling can be done by the regular furnace crew. This requirement was kept in mind continually in the work to be described. An oxygen value is required for proper control, whether it be of a rimming steel or of a fully killed steel. However, two factors have discouraged the development of such direct methods: i. The reaction C + FeO Fe + CO is rapid enough to make the correct sampling Of the bath a difficult problem. The most generally accepted means of circumventing this difficulty have been the aluminum-killed bomb test of McCutcheon and Rautiol and the aluminum-killed spoon test of Herty.2 The theory of these tests is that all of the oxygen in the iron is converted to Al2O3, which can then be determined by chemical methods. Even when simplified so that the analysis is made by a measurement of turbidity, this method is too slow to be used in routine control. Furthermore, the results obtained have never been entirely satisfactory, and some of the reasons for this will be discussed later in this paper. z. The ordinary chemical methods of analysis for oxygen in steel are not reliable. The only analysis that seems to possess sufficient dependability to be of value is vacuum fusion,3 and the apparatus and technique developed for this have been too complex and slow for routine work. Indirect Methods Indirect methods of estimating the oxygen have been resorted to in mill practice. Generally these depend upon the chemical equilibria involved. The oxygen in the bath is related to other components in the slag or metal that can be analyzed the readily. These methods have many difficulties in common. Steelmaking processes involve a complicated set of interrelated reactions, all of which tend to approach equilibrium at varying rates. The degree to which any particular equilibrium is approached is not well established. Moreover, a proper use of theoretical equilibrium constants requires a more extensive knowledge of the activities of the con- than we now have. This is well illustrated by the irregularities observed when trying to determine the oxygen in the metal by its ratio to the iron oxide in the slag. Equiliblium relations may be used mole readily if they are evaluated by plant experience, but the extent of approach to equilibrium remains an undetermined variable and lack of an entirely satisfactory mean, of determining oxygen for the calibration is felt keenly, For example, the statistical analysis of the relation between carbon and oxygen4.6 illustrates that even iia a single plant wide variations exist under llormal conditions of operation. Never. theless, this is one of the best methods now

Jan 1, 1943

By ARTHUR S. DWIGH

Discussion of the paper of W. W. NORTON, presented at the Salt Lake meeting, August, 1914, and printed in Bulletin No. 92, August., 1914, pp. 1993 to 1999. ARTHUR S. DWIGHT, New York, N. Y.-Mr. Norton&apos;s chief argument is directed against the idea that the D. & L. sinter is any better material for the blast furnace than the H. & H. product. He supports this by citing two experimental furnace runs. Reducibility.-To discuss a furnace record like that quoted by Mr. Norton for the five days&apos; run in August, 1912, is manifestly difficult for an outsider, but a possible explanation for the poor reduction on Furnace No. 5, smelting D. & L. sinter, may lie in the fact that both sets of furnaces carried the same fuel charges. Other things being equal, if 11 ½ per cent. coke was right for the furnaces smelting H. & H. product, it Was too much for the furnace smelting D. & L. product, as I shall endeavor to show later, and incipient overfire, accompanied by higher leads in slag and matte, was induced. It may sound like a paradox to say that excessive fuel sometimes produces poor reduction, but it is a sad fact. In certain plants where practically the entire charge to the blast furnaces receives a preliminary treatment by being sintered on the D. & L. machines the peculiarities of this problem have had to be very carefully studied, for serious metallurgical difficulties presented themselves when the change was first made to D. & L. sinter in large quantities. Some of these plants had blast pots before they had D. & L. machines, and many opportunities were afforded for comparative study of this very point. There is reason to believe that, clue to the long period of blowing and the higher temperatures developed in the pots from greater mass action, the iron in the H. & H. product is present chiefly as Fe203, perhaps in the form of ferrites, while in the D. & L. product the iron is present as FeO. The fuel charge in the blast furnace must be so proportioned as to exactly meet the chemical and thermic requirements of reduction and melting. If ally of these functions have been performed before the material enters the furnace, a corresponding allowance should be made or the fuel balance will be disturbed and bad work will result. One of the functions of the coke is to reduce enough metallic Fe for the matte requirements, leaving the remainder of the iron as FeO to go into the slag. In smelting almost any other material than D. & L. sinter the iron must-be reduced from the higher oxides, Fe203 or Fe304, to the protoxide, FeO, before a true comparative basis is reached. Experience has shown that with about one-half D. & L. sinter on the charge the coke should-be cut about 10 per cent. This theoretical benefit is borne out by the practical blast-furnace results on a large scale in numerous plants. In fact, wherever this very important factor is ignored the evil symptoms of excessive fuel will be indicated,

Jan 11, 1914

The following is an incomplete list of members and guests who called at Institute headquarters during the period Sept. 10, 19188 to Oct. 10, 1918. Thomas J. Adams, Rahway, N. J. A. N. Mackay, London, England. Henry M. Ami, Washington, D. C. A. W. MacNichol, San Francisco, Cal. Chester Atkinson, Peru, South America. Ernest Marquardt, Casper, Wyo. Bennett R. Bates, Berkeley, Cal. Lieut. S. A. Mewhirter, Denver, Colo. Robert S. Botsford, Petrograd, Russia. William A. Nelson, Nashville, Tenn. Juan Felix Brandes, Santa Barbara, Cal. Robert W. Olinger, Bahia, Brazil, So. G. A. Collins, Seattle, Wash. Amer. C. V. Corless, Coniston, Ont., Canada. G. Preumont, La Paz, Bolivia, So. Amer. F. T. Eddingfield, Washington, D. C. William H. Rettie, Yonkers, N. Y. C. Mason Farnham, Barre Plains, Mass. . Julius Segall, Minneapolis, Minn. F. N. Flynn, Trail, B. C., Canada. Robert Y. Seip, Franklin, N. J. Duncan D. Forbes, Humboldt, Ariz. H. M. Schleicher, Boston, Mass. Alexandre Gouvy, Paris, France. Chester Steinem, Ft. Monroe, Va. Henry G. Granger, Cartagena, Colombia, A. L. Sweetser, Pittsburgh, Pa. So. Amer. . H: E. Treichler, Creighton Mine, Ont., E. Harms, El Paso, Tex. Canada. Alfred G. Heggem, Tulsa, Okla. Frank A. W. Tullock, Yumbo, Colombia, H. B. Henegar, Mascot Tenn. So. Amer. A. M. Kivari, Denver, Edward I. Williams, Ft. Monroe, Va. T. M. Kniffin, Brookline, Mass. Alfred W. G. Wilson, Ottawa, Canada. Charles Lehman, London, England. Donald H. McLaughlin, Camp Meade,Md. C. E. Addams, who recently resigned as general manager for the Arizona Hercules Copper Co., has leased the Ray silver-lead property three miles from Ray, Ariz. Bennett R. Bates has resigned his position as general superintendent of the Cubo Mining & Milling Co., in order that he may take the examination for an officer of engineers.

Jan 11, 1918

By Richard W. Smith

Why are we losing our liberties? (1) . . . because our local chambers of commerce come to the National Chamber&apos;s annual meeting, vote for a policy on federal economy, and then go to Capitol Hill and ask for a federal project for their area. (2) ... because our mining men ask for a subsidy to mine submarginal deposits that can&apos;t be economically mined in a free economy. (3) . . . because 18,000 men and organizations all over the country recently wired or wrote a Congressional committee asking that the Army Engineers be exempt from the President&apos;s power to reorganize the Executive Branch of the government under the recommendations of the Hoover Commission.

Jan 1, 1949