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By J. D. Corbett

Mining geophysics in 1967 continued to expand with greater application in the exploration and development of mineral deposits. Moreover, geophysical activity increased without the particular emphasis of a Pine Point or Timmins discovery to spur interest. This trend is expected to continue through 1968 as geophysics more and more becomes an integral part of a mineral exploration program. This past year saw the "little black box" of the old-fashioned "doodlebugger" pushed further into the background, replaced by increasingly sensitive equipment of sophisticated design. The trend also is away from the one man geophysical operation wherein the same individual is responsible for the development, design and operation of the field gear, the planning and execution of a survey and analyzing and interpreting the data. In today's technology a staff of specialists, electronics engineers, mathematicians, physicists-to name but a few- are required to back up the exploration geophysicist in the development of new methods and techniques, in the reduction of the voluminous amount of field data and in the interpretation of the anomalies which can be enhanced by various high-speed computer techniques. Obviously a full back-up staff of these varied abilities is impractical to most exploration companies. However, the equivalent function is provided to the lone staff geophysicist by the many competent geophysical contractors and individual consultants.

Jan 2, 1968

By John W. Pack

AT present the manufacture of metallic zinc, or spelter, in Missouri, is carried on only at the establishments located at Carondelet, or South St. Louis. Although the development of the industry has not yet reached that fulness which it has attained elsewhere in the United States, still the commanding advantages of position of these establishments are so evident that the prospective importance and magnitude of spelter manufacture in this State, and especially at this locality, can hardly be doubted. A study of the chemical and technical aspects of the business of these points cannot be without interest to the metallurgist as well as to the capitalist. I have endeavored to investigate, as far as was practicable, within the limits of a paper of this character, some of the problems connected with this industry, at the same time making a few comparisons of the results attained at some of the Carondelet works with those of other establishments with regard to which information could be obtained. In the prosecution of these studies I have been kindly aided by the managers of Carondelet establishments, and by Prof. Charles P. Williams, Director of Rolla School of Mines. To the latter I am especially indebted for assistance in regard to methods of analysis. To all these gentlemen I return my thanks for their valuable aid. Other sources of information will be duly credited in their proper places.

Jan 1, 1875

By B. Blumenthal

THE present investigation was planned as a survey of the lead-rich portion of the ternary lead-antimony-silver system by thermal analysis. Since, however, a rigorous application of the conventional thermal analytical method is time consuming, an attempt was made to speed up the investigation by reducing the time required for a single thermal analysis. This was done by increasing the rate of cooling to 12° to 18°C. per minute, since such a rate does not permit even an approach to equilibrium conditions, the melt was stirred vigorously by a stirrer operating at the high rate of 665 r.p.m. This proved to be effective in obtaining cooling curves with distinct points of arrest and of excellent reproducibility, which satisfactorily compare with those obtained at a rate of 1" to 2°C. per min. with or without slow stirring (Fig. I). By this method the lead-rich end of the lead-alltimony system and a series of ternary alloys in sections parallel to the lead-antimony side of the ternary system were investigated and it was observed that the two branches of the liquidus curve of the binary alloys did not intersect at the euteotic temperature. An equivalent effect mas observed in the ternary system. The eutectic temperature of the binary lead-antimony system was found to be 252.0°C., which confirms the recent in- vestigation by Pellini and Rhines,1 who determined the eutectic temperature to be 2 51.5°C. The observation that the curves of primarY crystallization of the lead-antimony system do not intersect at the eutectic temperature was previously made by Dean.2 Dean explains the phenomeilon by assuming the existence of a compound Sb4pb. He felt that supercooling was not the cause of the phenomena because he was unable to influence them by inoculation. The X-ray investigation by Solomon and Morris-Jones,3 the metallographic investigations by Stead,4 Charpy,5 Gontermann,6 and Dean, Zickrick and Nix,7 and the numerous investigations of physical properties, definitely disprove the occurrence of any compound. The work of Dean was not confirmed by Broniewski and Sliwoski,8 whose experiments did not show any irregularity and who report a eutectic composition of 13 per cent antimony and a eutectic temperature Of 2500 to 252°C. at a rate Of coo1ing of about 6°C. Per min. Abell Redlich and Adler9 then report a eutectic composition of 12.1 per cent upon reviewing the previous publications and adding a few of their own cooling curves. In 1934 Quadrat and Jiriste10 found from careful analyses of the bottom portion of slowly cooled hypereutectic melts that the eutectic only 11 .4 to 11.5 per cent antimany. (Previous analyses by Stead4 .in 1891 gave 13 per cent.) Weaver,ll however, reported in 1935 that cooling cunres indi-

Jan 1, 1944

By J. S. Bryner

In the study of metallographic specimens in the electron microscope, there is need for a method of locating the same field in both the light microscope and the electron microscope. This need arises chiefly from the fact that in the electron microscope the magnification and degree of resolution are so much higher, and the field so much smaller than in the light rnicroscope that it is often difficult, if not impossible, to identify positively what is being observed. The difficulty is increased by the fact that, because a transparent film replica of the metal surface must be used in the electron microscope, micro-constituents can be identified not by their color but only by their texture and contours. For these reasons it is desirable to obtain a series of photographs showing the same field in both microscopes in order that the appearance of common microstructures and micro-constituents in the electron microscope may be identified and catalogued for future reference. The need for a method of locating the same field in both microscopes arises also when it becomes desirable to enlarge in the electron microscope for more detailed study a particular interesting structure observed in the light microscope. Using the standard polystyrene-silicalJ replica technique, in which the silica film replica is fished from the ethyl bromide on a 1/8 in. diam zoo-mesh specimen screen, the possibilities of locating a particular area on the film in the electron microscope are rather remote. The desired structure may be obscured by the wires of the specimen screen or unrecognizable at the high magnification. A solution to the problem would be provided if a specially designed specimen screen, containing an opening which could be absolutely identified and quickly located in the electron microscope, could be fastened to the silica film replica in such a position that the desired field on the specimen would be located at the identifiable opening in the specimen screen. The design for such a specimen screen, a method for producing it, and a technique for fastening it to the silica film replica are described below. Description OF Method The Specimen Screen A simple design for a specimen screen containing an opening easy to identify and locate in the electron microscope is one with two lines of openings at right angles in the form of a cross. Such a screen is shown in Fig I. The opening at the center of the cross is identified easily and can be located quickly in the light microscope and in the objective image of the electron microscope. The specially designed specimen screens for this work were produced in quantity by electroforming. On both sides of a polished strip of copper I X 3 X 1/8 in., twenty patterns of the cross of openings were punched with a diamond point micro-hardness tester, using a load of magnitude

Jan 1, 1949

By L. S. Castleman, H. A. Froot

A study was made of the growth kinetics of B-brass layers in a-brass us y-brass diffusion couples in which both phases were saturated in the 6 phase. It was found that useful estimates can be made of the difhsion coefficients at the ß-phase interfaces from interface displacement data, which are relatively easy to measure experimentally; also, a useful estimate can be made of the mean heat of activation for diffusion from layer growth data. The effects of pressure on layer growth kinetics were explored and found to be consistent with a vacancy model for diffusion in 6 brass in both the disordered and ordered temperature range. 1 HE study of multiphase diffusion receives relatively little attention in comparison with that devoted to diffusion in homogeneous materials. Of the hundred or so papers on diffusion written each year,' only a few are devoted to the subject, and it is the rare review article2,3 that devotes any space to multiphase diffusional phenomena. This is unfortunate, since the metallurgist frequently encounters practical situations involving cementation processes such as cladding, protective coating of metals, and so forth in which he needs guidance of a fundamental nature. The investigation of multiphase diffusion phenomena is complicated by the fact that one must consider reactions at phase interfaces as well as the migration of atoms within the individual phases; these reactions cause the interfaces to be displaced within the diffusion zone. The relative displacement of two adjacent interfaces corresponds to the growth of an intermetallic layer, and it is not difficult to determine experimentally the kinetics of layer growth. In the past few years it has been pointed out4,5 that valuable fundamental information may be gained about diffusion coefficients and the concentrations at interfaces through a study of their motion. Accordingly, it is the purpose of this paper to report the results of an investigation of interface motion in a simple multiphase binary system. In the work reported herein, attention was focussed on the growth of a 6 -brass layer in a diffusion couple prepared from a- and y-brass compositions saturated with respect to the 6 phase. This particular system was chosen for a number of reasons. First, the bcc ß-brass phase is disordered for all compositions at temperatures above 468°C and becomes increasingly long-range ordered for all compositions at temperatures below 454° C;6,7 thus, the effects of a variation in order on interface displacement could be determined. Second, diffusion coefficients have already been obtained as a function of temperature in the ß phase both in the ordered and disordered Re- and a theoretical picture of the mechanism of diffusion in this and other ordered solutions is emerging.11'12 Third, some thermodynamic data are available for the a-, ß-, and ?-brass phases,13,4 and these data could be used to gain insight into questions of phase equilibria and concentrations at phase interfaces.

Jan 1, 1963

By Henry J. Welge

The approximate methods which are now in use for calculating oil displacement from reservoirs by gas-cycling or gravity-drainage at constant gas pressure, or by water flooding, make use of fundamental relationships derived by Leverett' and Buckley and Leverett.2 The mathematical equations needed are derived by applying Darcy's law to the flowing phases, and by material balance considerations. ln general, any treatment of this type gives. for any particular exploitation time considered, a plot of oil saturation against distance in the reser-voir. The oil recovery must then be obtained by integrating in some manner the area under the plot. A useful analytical method has been derived for computing the average saturation, and hence the oil recovery. Use of this method simplifies the calculations because it makes unnecessary any numerical integrations. and even the saturation distribution plots are not needed. A further advantage of the method is that knowledge of the relative permeabilities is required only for a limited and intermediate saturation range. In both the Buckley and Leverett method and the method discussed here, a linear sand section is assumed, and in the case of gas drive the gas pressure is assumed sufficiently constant both with respect to reservoir position and time so that changes in gas density. solubility, or reservoir volume factor are negligiklle. Thus, the exploitation contemplates oil displacement as by an immiscible phase. Examples are given to illustrate how the new method can be used. INTRODUCTION AND THEORETICAL BACKGROUND This paper treats a simplified method for computing oil recovery when the oil is displaced, from the reservoir sand by a fluid which, within the limits of accuracy desired, can be assumed to be incompressible and immiscible with the oil. The method makes use of two basic relations originally developed for the case of water displacing oil. However, the case of gas displacing oil saturated with gas at a constant (or nearly constant) pressure may also be considered a displacement by an immiscible fluid. This is possible for the reason that the concentration of the gas in the oil never changes if tile pressure is fixed. consequently, any additional free gas must remain undissolved in the oil, and so must act essentially as an immiscible phase. For convenience, the cape of gas drive will be considered first. Both of the two basic relations needed refer to a linear reservoir, or one which may be somewhat idealized so that a constant cross-section is exposed to fluid flow. Further, the displacing phase is injected at one end, or face; of the reservoir, while the produced fluids are understood to emerge at one point only. which is the opposite face of the reservoir. As indicated in Fig. 1, the reservoir may he inclined by some angle 8. The first of the required equations may be derived by applying Darcy's law to both displacing and displaced phases, and subtracting the two equations. The result for water drive has been given previously, as Equation (13) of the reference by

Jan 1, 1952

By B. Blumenthal

THE present investigation was planned as a survey of the lead-rich portion of the ternary lead-antimony-silver system by thermal analysis. Since, however, a rigorous application of the conventional thermal analytical method is time consuming, an attempt was made to speed up the investigation by reducing the time required for a single thermal analysis. This was done by increasing the rate of cooling to 12° to 18°C. per minute, since such a rate does not permit even an approach to equilibrium conditions, the melt was stirred vigorously by a stirrer operating at the high rate of 665 r.p.m. This proved to be effective in obtaining cooling curves with distinct points of arrest and of excellent reproducibility, which satisfactorily compare with those obtained at a rate of 1" to 2°C. per min. with or without slow stirring (Fig. I). By this method the lead-rich end of the lead-alltimony system and a series of ternary alloys in sections parallel to the lead-antimony side of the ternary system were investigated and it was observed that the two branches of the liquidus curve of the binary alloys did not intersect at the euteotic temperature. An equivalent effect mas observed in the ternary system. The eutectic temperature of the binary lead-antimony system was found to be 252.0°C., which confirms the recent in- vestigation by Pellini and Rhines,1 who determined the eutectic temperature to be 2 51.5°C. The observation that the curves of primarY crystallization of the lead-antimony system do not intersect at the eutectic temperature was previously made by Dean.2 Dean explains the phenomeilon by assuming the existence of a compound Sb4pb. He felt that supercooling was not the cause of the phenomena because he was unable to influence them by inoculation. The X-ray investigation by Solomon and Morris-Jones,3 the metallographic investigations by Stead,4 Charpy,5 Gontermann,6 and Dean, Zickrick and Nix,7 and the numerous investigations of physical properties, definitely disprove the occurrence of any compound. The work of Dean was not confirmed by Broniewski and Sliwoski,8 whose experiments did not show any irregularity and who report a eutectic composition of 13 per cent antimony and a eutectic temperature Of 2500 to 252°C. at a rate Of coo1ing of about 6°C. Per min. Abell Redlich and Adler9 then report a eutectic composition of 12.1 per cent upon reviewing the previous publications and adding a few of their own cooling curves. In 1934 Quadrat and Jiriste10 found from careful analyses of the bottom portion of slowly cooled hypereutectic melts that the eutectic only 11 .4 to 11.5 per cent antimany. (Previous analyses by Stead4 .in 1891 gave 13 per cent.) Weaver,ll however, reported in 1935 that cooling cunres indi-

Jan 1, 1944

By George Mixter

MINING, in contrast to manufacturing, deals with a wasting asset. That which is taken out of the ground is gone, the property is depleted to that extent, and will eventually become exhausted of profitable ore. So the life of a mining company is dependent upon the ability of its management to develop improved methods to permit extraction at a profit of the lower-grade ores which remain, to extend by intelligent exploration the limits of its known ore bodies, and to find and acquire new properties to take the place of those that, for one reason or another, are no longer operated. Its history is a story of constant change, of the working out of properties here and the acquisition and development of properties there, to maintain the vitality of the whole. It is a story of estimating with the tools and the knowledge available the location and extent of hidden ore bodies and of devising the means of extracting

Jan 1, 1948

By D. H. Henley, F. F. Craig, W. W. Owens

The oil recovery performance of systems producing entirely by bottom-water encroachment has been experimentally determined in a series of scaled laboratory-model tests. The effects of well spacing, fluid mobilities, rate of production, capillary and gravity forces, well penetration and well completion techniques on the oil recovery performance have been investigated. The laboratory tests were performed using two uniform, un-consolidated sand-pack models. The models have ratios of the interwell distance to the formation thickness of 12 and 2, respectively. Tests at constant total fluid production rate were performed simulating a range of uniform reservoir characteristics and operating conditions encountered in field operations. The performance was determined by material balance and by observation of the encroachment of dyed fluids into the models. The results of the model tests agreed with those obtained mathematically when the conditions previously considered in theoretical studies were simulated, that is, when the oil and water are of equal density and no capillary forces exist. The model study of bottom-water drive indicated that certain variables can aoect the oil recovery performance to a greater degree than can be predicted by present analytical methods. In one comparison, the oil recovery at a water-oil ratio of 20 (obtained at a wide well spacing) varied as much as threefold, depending upon the system's properties and the production rate. Lesser effect of mobility ratio and no eflect of capillary forces over the range studied were observed. The test 'results also showed that the deeper the well penetration into the oil column, the greater the total water production to a producing WOR of 20. However, the ultimate sweep efficiency, and so the oil recovery to this level of WOR, did not vary significantly with well penetration. Horizontal fractures at the top of the formation did not significantly change the sweep characteristics of the reservoir models when values of radius and fracture capacity encountered in actual reservoirs were used. Impermeable pancakes at the bottom of the well moderately increased the oil recovery efficiency both at water breakthrough and at high water-oil ratios. A method is outlined by which the oil recovery performance of other uniform bottom-water drive systems can be estimated from the information obtained in these model tests. INTRODUCTION When oil is produced from a well which partially penetrates an oil zone completely underlain by water, the water rises directly beneath the well in a symmetrical cone when the system is uniform. Two different flow mechanisms can cause the water cone to form—coning and bottom-water drive. In coning, the aquifer is relatively inactive and the cone is formed beneath the well by the pressure gradients associated with the oil flow to the well. The oil can be produced by a solution-gas drive, an edge-water drive or other driving forces in the interwell area. In a bottom-water drive, the driving force for oil production comes from an upward encroachment of the underlying active aquifer. Two papers have analyzed the theoretical performance characteristics of bottom-water drive reservoirs. In the initial mathematical investigation, Muskat' established the equations which determine the pressure distribution in this type of reservoir and solved these equations for certain conditions. Specifically, it was assumed that the water and oil had equal mobilities and equal densities, there were no capillary forces, the pressure throughout the oil zone remained above the bubble-point pressure, a constant pressure existed at the initial water-oil contact and the oil was completely displaced by the encroaching water. These assumptions were used in obtaining analytical solutions. In general, Muskat found that the sweep efficiency to initial water breakthrough to the well was larger for the thicker oil zones, the closer well spacings, the lower ratios of vertical to horizontal permeabilities, the smaller the penetration of the well into the oil zone and the smaller the bore size of the well. The production history after water breakthrough was expressed as a volumetric sweep efficiency at a given producing water-oil ratio. The results indicated that cumulative oil production at producing water-oil ratios of 10 is less affected by the well spacing than is the water-free production history. Muskat studied well spacing which today would be regarded as close. The maximum value of his dimensionless well spacing (ratio of interwell distance to formation thickness) was 4.3. This would require the development of a 50-ft-thick oil sand on less than 10-acre spacing if the vertical and horizontal permeabilities were equal, with

By G. V. Jere, C. C. Patel

Chlorination of the various constituents of ilmenite by different chlorinating agents in presence of various reducing agents, have been considered on the basis of the standard free energy and standard enthalpy changes as a function of temperature. The standard free energy change considerations show that it is beneficial to chlorinate ilmenite by chlorine in the presence of carbon and also that iron constituent of ilmenite can be preferentially chlorinated by clzlorine, titanium tetrachloride or their mixture. These findilzgs have been corroborated from the published work. METALLURGICAL processes involving the use of titanium tetrachloride have gained in importance because of the use of the latter in the manufacture of titanium metal. Since ilmenite is more abundant in nature than any other titanium mineral, the future of the metallurgical processes depends on the utilization of ilmenite for the production of titanium tetrachloride. In these laboratories, investigations have been carried out on the chlorination of ilmenite under a variety of conditions.1'2 During these studies, it was noticed that 1) preferential chlorination of iron was effected at low temperatures (400° to 600°C) and at low carbon content (6 to 7 pct), 2) carbonyl chloride retarded the chlorination of iron oxides and titania perceptibly, while 3) carbon-tetrachloride, compounds of sulphur and some other catalysts favored the chlorination. Moles3 has found that oxides of iron are chlorinated in preference to titania at high temperatures, while wilcox4 has claimed the preferential chlorination of titania between 1200" and 1500°C. It has been shown in this paper that preferential chlorination of titania claimed by Wilcox is not likely to occur. Daubenspeck and coworkers5,6 have claimed the preferential chlorination of iron by chlorine or by a mixture of titanium tetrachloride and chlorine between 700° and 1050°C in the absence of carbon. Even when plain titanium tetrachloride is employed as the chlorinating agent, pascaud7 noticed the preferential chlorination of iron and other oxides. The purpose of this paper is to explain from thermodynamical considerations, the various chlorination reactions studied so far. ILMENITE CONSTITUENTS AND THEIR CHLORINATION PRODUCTS Although the general composition of the ilmenite mineral is represented as FeTiO,, most of the ilmenites found in nature have variable quantities of TiO2 (44.6 to 64 pct), FeO (4.7 to 36 pct) and Fe2O3 (6.9 to 28 pct).8 The higher content of ferric iron in ilmenites was attributed by Millerg to the presence of arizonite (Fe2O3.3TiO2). But the X-ray studies by Overholt, Vaw, and odd" have shown that arizonite is a mixture of haematite, ilmenite, anatase, and rutile. Except for the anatase, similar views have been advanced by Lynd, Sigurdson, North, and Anderson8 from magnetic, X-ray, and optical and electron microscope studies. The ilmenite ores can, therefore, be assumed to consist of mineral aggregates of ilmenite, rutile and haematite. From the free energy of formation of ilmenite (FeTiO3), it has been shown by Kelley, Todd, and King11 that ilmenite is stable even up to its melting point (1367°C) and would not undergo decomposition into its constituent oxides. Schomate, Naylor, and Boericke12 have found that in the presence of a reducing agent the iron constituent of ilmenite is selectively reduced. The reaction of chlorine with ilmenite in presence of a reducing agent can, therefore, be synonymous with that of the reaction of chlorine with the constituents of ilmenite, viz., TiO2, FeO, and Fe2O3. Most of the reaction products of chlorination of ilmenite in the presence of reducing agents will be in equilibrium with their dissociation products, depending on the temperature. The titanium tetrachloride is, however, quite stable up to 1500°C due to its covalent nature. The equilibrium for the ferric chloride system has been investigated by Kangro and Bernstorff, 13, schafer14 and Kangro and petersen,15 and the results are summarized in Fig. 1, curves a, b, and c respectively. From these results, it is clear that the ferric chloride disociates as follows: 324° to 700°C FeaCl6(g) ?2FeCl2(c) + Cl2(g) [1] 324°to 900°C Fe2Cl6(g) =2 Fe Cl2 Reaction [I] (curve a) occurs in the forward direction to about 6 pct at 400°C but falls off very rapidly with increase in temperature and beyond 600°C, it is practically negligible, perhaps due to the formation of the stable monomer, FeC13(g). As the temperature is further increased, the amount of FeCl,(g) in-

Jan 1, 1961

By A. R. Troiano, E. A. Steigerwald, F. W. Schaller

D. N. Williams(BatteZle Memorial Institute)-The authors have presented an extensive collection of arguments pertaining to the role of stress in hydrogen embrittlement. The basic assumption of these arguments is that stress is essential as a driving force for diffusion of hydrogen. However, in view of the rapid diffusion rate of hydrogen in steel at low temperatures as evidenced by the ability to alloy with hydrogen by electrolytic charging, it seems unlikely to me that stress acts in this manner. Instead, I would like to suggest that stress may be essential for the nucleation of hydrogen in steel. I believe that such an assumption would equally well satisfy the experimental data presented by the authors. I should also like to comment on the interpretation of the data presented in Figs. 5 and 6. Fig. 5 shows the effect of hydrogen content on ductility in a rupture test. The curve as drawn by the authors indicates an abrupt transition from ductile to brittle behavior at about 0.001 amp per sq in. (5 ppm). The data points would equally well support a gradual transition from ductile to brittle behavior extending over the range from 0.0008 to 0.02 amp per sq in. (4 to 8 ppm). A gradual transition would be the ex-

Jan 1, 1962

By G. R. Love, M. L. Picklesimer

Aboue 950°C the Nb-Zr system consists of a completely miscible bcc solid solution, commonly called the phase. Between 950 and 600°C, and between 20 and 85 pct Nb, the phase deconlposes, after sunciently long times, into two bcc solid solutions. The pct Zr alloys are conveniently descibecl with T-T-T (time-temperature-transformation) curves having a nose at about 2 hr at 700°C. The reaction rate varies only slowly with zirconium content and negligibly with oxygen contanzination; it is speeded up by a factor of 10 to 15 by 90 pct cold ulork and slowed dou by n factor oj 10 to 30 by a two-hundrecljold increase in grain size. Nb-r alloys with compositions between 40 and 85 pct Nb have been the basis for the majority of commercially important superconducting materials. In part because of their commercial promise, more is known about these alloys than about most other high-field superconducting materials. At the same time, there is considerable disputed or incomplete metallurgical information. For example, although Rogers and tkins&apos; indicate a monotectoid reaction at approximately 600°C and a two-phase 01 + 0, field extending between 20 and 85 pct Nb and to a maximum of 95OGC, erhout&apos; has reported that this entire region would be a single homogeneous B were it not for oxygen contamination. Again, although it has been shown that relatively short-time heat treatments in the vicinity of 700CZ significantly improve the ability of short wire samples to carry high currents in high magnetic fields at 4.2K, these observations have never been fully correlated with the structural change or changes occurring during the anneal. We intend to investigate in detail the effect of metallurgical variables, including heat treatment, on the superconducting properties of hard superconductors. To verify that our experimental techniques are valid and to establish a relative standard against which other materials may be measured, we feel it advisable to know the behavior of the Nb-Zr alloys under a variety of processing conditions. As an initial step toward this goal, we have determined in detail the kinetics of the transformations in Nb-Zr alloys. EXPERIMENT A number of problems had to be solved before beginning any fruitful work on the reaction kinetics in this system. While solving some of these problems, either by chance or by design, small amounts of information were obtained about alloys containing 40, 50, 60, 65, 67, 70, and 75 pct Nb, bal. Zr. In addition, a large range of grain sizes and a range of temperatures considerably greater than the range indicated by Rogers and Atkins phase diagram were examined. We will, however, report in detail only the results obtained for the Nb + 33 pct Zr and Nb + 25 pct Zr alloys at three grain sizes, two levels of oxygen contamination, and the temperature range 550 to 950°C. These data are most complete, but the other data are sufficiently complete to indicate the kind and magnitude of the variation of the transformation kinetics outside this range. The first and most difficult problem encountered in this inquiry was one of sample homogeneity. When Nb-Zr alloys are arc- or electron-beam-melted on a cooled copper hearth, solidification is sufficiently slow that there is appreciable coring in the cast structure and a large variation of grain size across the button thickness. Both these factors significantly affect the apparent reaction rate in the system. A two-step solution to the problem was attempted; an arc-melting and drop-casting technique has been developed by conald that greatly reduces the as-cast grain size and virtually eliminates coring segregation. Ingots made in this way exhibited no detectable (3 pct maximum) zirconium segregation. Before it was evident just how good this technique was, we attempted to supplement it with rather long-time, high-temperature annealing of the cast ingots. This annealing was carried out in evacuated and sealed (seal-off pressures < 1.0 x 106 torr) quartz capsules lined with tantalum foil at 1400 to 1450 C for 8 to 72 hr. There were two principal effects of this treatment: the grain size increased to a fairly uniform 150 p, and the surface and all grain boundaries near the surface acquired a film of a second phase, tentatively identified as an oxide (possibly additionally contaminated with silicon). There was no evidence that this 1400 C treatment had affected the zirconium segregation. High-temperature annealing was subsequently used only for grain-size control, but anneals of longer than 4 hr at temperatures greater than 1000°C were performed in dynamic vacuums (pressure no greater than 1.0 x lo torr). Any contamination resulting from these treatments was well below the limits of detection of our techniques. All samples, as cast, were cold-swaged to at least 85 pct reduction in area. The samples called cold-worked were tested as swaged. The minimum re-crystallization anneal for these alloys was about 12 hr at 1050 C; this produced an equiaxed grain diameter of about 4 to 8 P. Annealing for 4 hr at 1450°C produced a grain size of about 80 to 150 p; and annealing for 4 hr at 1650aC, close to the melting point of many of these alloys, produced a grain size of 0.5 to 1.0 mm. At all temperatures, the larger grain size was

Jan 1, 1967

By F. Louis Grammer

The rapid advances on the mechanical side of blast-furnace practice have not always been accompanied by a proper appreciation of the metallurgical requirements. This is illustrated occasionally by the improper use of automatic barrow chargingdevices and bins (introduced at the expense of accuracy in weight), with ores of irregular composition or ores that have been poorly graded. The 100-ft. blast-furnace has not always been advantageous, and in many instances the increase in the number of tuyeres, from 8 or 12 to 20, has resulted in decreased output. The data pertaining to this division of blast-furnace practice are now sufficiently complete to allow inferences to be made. The use of fine ores has indicated the manner in which large outputs could be obtained, as it has emphasized the fact that intimacy of contact. between gases and ore, and coke and air, were more important than the time of exposnre. It was reasonable to suppose that if more points of contact were made between the air and the coke, their union would occur in a shorter period of time, and the coke would be burned more rapidly in the same-sized hearth, and an increased output thereby obtained. In consequence of this theory, many furnace men upon relining a furnace increased the number of tuyeres from 8 or 12 to 20, or even more, frequently with unfortunate results. If the number of tuyeres in an old furnace is

Jan 1, 1904

By J. R. Low

The brittle fracture of a Tic-lnconel cermet at room temperature is shown to occur primarily as a result of the cracking of the larger carbide particles (at a tensile strain of approximately 0.3 pct), followed by cracking of adjacent, smaller carbides and, finally, by the rupture of the lnconel matrix between cracked carbides (at a strain of-1.2 pct). No evidence was found for separation at the interface between carbide and matrix at any point in the fracture process. MATERIAL used in this study was a Tic-Inconel cermet prepared by infiltration (50 pct Tic, 50 pct Inconel: designated as TC66-I). A thin section of this material was brazed to a piece of low carbon steel and then mounted in lucite for metal-lographic preparation." After grinding, polishing, Deformation and fracture of the specimen was accomplished by bending the specimen as a simply supported, centrally loaded beam, in a bending fixture which could be placed in the stage of a microscope, with the tension side of the bend specimen under the microscope objective.? This method of deformation and observation has the advantage that the surface under examination is the most severely deformed portion of the specimen. The procedure followed was to deform the specimen a small amount, scan the surface at Xl OOO for any evidence of deformation or cracking, deform another small increment, scan the surface again, and so on until a

Jan 1, 1957

By H. F. Dawes

In China all minerals are, theoretically at least, the property of the Emperor, and the Imperial permission must be got from him for the privilege of working them. A direct tax is levied on this privilege, and by simple command, the Emperor can close a mine at any time. Occult geomantic influences are a large factor in determining the opening or the arbitrary closing of a mine. The location with reference to points of the compass, graves and natural objects, may be really or professedly considered as indicating that those influences are favorable or unfavorable. The consequence, is, of course, that for the authorization and encouragement of any considerable enterprise, friends&apos; at court, practical politics, and more or less bribery, are required. As a result, most Chinese mining is illicit, and is carried on in a small way only. Often along a single vein, or over a small section of mining country, a few individuals obtain rights over all the openings, most probably by loaning money to the head-men of the operators and holding the mines as security for the debt. In such cases, perhaps, for better security, all the ore is reduced in the works established by the creditors, who also handle all silver produced..As the head-men are, for the most part, improvident, and the laws and customs for the collection of&apos; debts are stringent and peculiar, the " officemen" or creditors acquire in time what is practically an ownership of

Jan 1, 1892

By George A. Morrison

THE Columbia Chemical Division of the Pittsburgh Plate Glass Co. is at Barberton, Ohio, 35 miles south of Cleveland. For many years large tonnages of limestone have been brought to the Barberton plant from distant points. The stone is here burnt in vertical kilns, the resultant product then hydrated and the hydrated lime used in chemical processing. To eliminate the expense of these shipments, the company decided to investigate a limestone bed known to exist on company property at Barberton, where the stone is used. The bed lay at a depth of more than 2000 ft. and was known locally as the "Deep Lime." Chemical analyses of sludge from churn-drill holes made some years ago proved that the limestone was of sufficient purity to warrant diamond-drill exploration. Four diamond-drill holes were put down at well-spaced intervals, to represent fairly an area of four miles by one mile. Cores logged as to chemical and physical conditions were found to compare closely, and to corroborate the earlier evidence that the limestone was of superior quality for chemical use. A plant of 300 tons per hour was subsequently decided upon. SITE The yard at the chemical plant was already so congested that location of the projected mine within its area could not be considered. Eventually a site was selected 2 miles northwest of the plant, near the main line of the Erie Railroad. Here 412 acres were owned outright by the company and stone rights were obtained on 250 additional acres. This location required a transportation line of nearly 2 miles (8800 ft.), crossing two major highways, and to avoid interruption of deliveries to the plant, overpasses were planned. GEOLOGY The limestone in the immediate vicinity lies about 2200 ft. below the surface. Geologists* identify this stone as Delaware of Devonian age. It is overlain by 18 ft. of unconsolidated (sand and gravel), 100 ft. of water-bearing sandstone, and finally 2080 ft. of shale into which sandstone in thin layers is interbedded. The contact of shale and limestone is abrupt, flat-lying and very pronounced. Berea sandstone, often found at 520 ft., is absent, but Euclid sandstone was encountered, together with a seepage of oil and a small amount of methane gas. The limestone bed itself is 345 ft. thick, and overlies 200 ft. of gypsum. The lower part becomes dolomitic as it approaches the gypsum. A detailed study of the drill cores indicates that the upper 50 ft, are highest in lime and reasonably low in silica. The physical make-up shows several separating cherty layers. These occur at definite horizons and cause distinct partings, which become horizontal planes of

Jan 1, 1943

By W. W. Little

At the United Verde mine the 9-2D stope on the 4050 ft level is located within the north sulphide mass lying some 800 ft north of the main sulphide ore body. In 1948 it was estimated that this block contained 85,000 tons of ore at 4% copper and 9.2% zinc. The north ore body is a lenticular replacement deposit in the black schist, extending from about 100 ft above the 3750 level to a distance below the 4500 level yet to be determined. Although the mineralized zone approaches 1000 ft in length, only 300 ft is of economic importance. In width it varies from a maximum of 60 ft to about 3 ft at the north end, and is characterized by pinching and swelling in the ore zone. One of these larger swells is being mined as the 9-2D stope. Mining costs at greater depth, together with the expected grade of ore after dilution, necessitated a low cost mining method to permit profitable stoping operations. Based on the results obtained in a number of Canadian mines, it was decided to develop the ore body for stoping by the Aldermac or bench method of diamond drill blastholes; however, this plan was subsequently changed and the radial or ring method adopted. Such a method seemed to offer the advantage of large tonnages at low cost, and obviate the necessity of waste fill. This latter point was of particular importance, since the present waste system does not extend below the 3000 level.

Jan 4, 1950

By R. Bakish, M. A. Badiali, N. W. Kirshenbaum

One pound of ultra pul-e molybdenum has been produced containing both metallic and nonmetallic impuvities close to or less than the limits of detection. various purification methods were investigated; althouglz the use of move than one purification step was consideved, it was found that a single, caefully-controlled sublimation of MoCl5 yielded a highly puvified product without prior treatment or recourse to repeated sublimation. Hydrogen reduction of MoC1, to metal was attempted at atmospheric pressure; however, reduced pressure was necessary to obtain substantial yields. The tubular deposits of metal were consolidated into bulk fovm by electron beam melting undev high vacuum yielding a very low gas content. Boblems involved in monitoring the puvity of these materials and analytical results obtained are also presented. THE pronounced effect of even trace amounts of impurities upon fundamental properties of materials is well known to metallurgists and solid-state physicists. Consequently, groups interested in basic studies of metals have in recent years immensely stimulated the preparation and production of numerous ultra-pure metals. Increased demand by scientists for these high purity materials has necessitated development of facilities to prepare them in significant quantities; the procedures reported here were devised to produce significant quantities of ultra-pure molybdenum. Previous work performed in the field of vapor phase purification and hydrogen reduction of several other refractory metal chlorides had demonstrated valuable techniques applicable to molybdenum.&apos; Various purification and reduction steps were individually investigated. Those procedures which showed the most favorable results with respect both to attainment of high purity and to ease of operation were then incorporated in the process utilized to produce the metal.&apos; STARTING MATERIALS It is well known that because of differences in volatility, chlorides may be separated by fractional distillation. It was presumed that distillation of molybdenum pentachloride offered a simple and straightforward method of purification due to its relatively low boiling point. Alternatively, sublimation of the solid chloride also appeared feasible since MoC15 has both a reasonably narrow temperature range in which it exists as a liquid (a property typical of refractory metal chlorides) and a low enthalpy of sublimation. Pertinent thermochemical data of MoC15 are given in Table I. It should be noted that this compound must be handled with care as it is extremely hygroscopic. Anhydrous MoC15 was obtained from the A Metal Climax Co. METHODS OF PURIFYING MOLYBDENUM PENTACHLORIDE Distillation. It was expected that distillation methods, while affording an efficient purification, would prove simple to control and would have a higher production rate than sublimation processes. Also considered was the possibility of effecting a high degree of purification by using both these volatilization methods in conjunction—possibly a distillation followed by sublimation of the solidified condensate. Distillation of MoC15 was investigated using a single stage distillation column packed with chemically resistant glass beads. Heating coils were wound around the column and collection tube (condenser). As-received MoCl5 was charged into a flask connected with the column using a side loading arm under an argon flow. After the column and condenser were brought to about 270" and 210°C, respectively, the apparatus was lowered until the flask was fully immersed in a constant temperature fused salt bath maintained at about 285 °C. Distillation was continued for about 10 or 15 min until 50 to 70 g of distillate had been collected. Analyses of these distillations indicated that several elements, e.g., Cu, Fe, Ni, Cr, and Mg, were lowered in quantity although not all were removed to the same extent. The occurrence of Na, B, Si, and A1 in the distillates appeared to be due to contamination, possibly from corrosion of the pyrex glass. An improved distillation system of larger capacity and longer distilling column was built. Improvements were effected in lowering the amounts of such impurities as B, Mn, Ni, Na, Mg, Cr, Cu, and Fe. These studies were pursued concomitantly with efforts to purify by sublimation; it was subsequently found that although improvements in purity were obtained by distillation, sublimation processes were simpler to control and effected a high degree of purity.

Jan 1, 1963

By B. C. Allen

Grain boundary grooving has been studied in chromium, molybdenum, and tungsten under a variety of conditions using high vacuum techniques and tantalum -gettered argon. The average surface free energy of solid chromium, and the chromium-liquid silver interface free energy were respectively found to be 2200 ± 250 and 500 i 130 ergs per sq cm from groove formation kinetics and estimates of pertinent volume difffusion coefficients. The results for chromium were unffected by variations in interstitial content ranging from 0.003 to 0.09 pct C, or 0.003 to 0.03 pct O. Surface diffusion is the primary mechanism of groove formation in chromium under 1 atm argon at 1200" to 140O°C, and is essentially unaffected by 0.003 to 0.09 pct C, 0.003 to 0.03 pct O , metastable nitrogen contents up to -0.01 pct, and up to 2 torr Ag vapor. At higher temperatures, the major mechanism is volume diffusion in argon or evaporation-condensation in stutic vacuum. Surface diffusion occurs in molybdenum at 0.5 to 0.96 and in tungsten at 0.5 to 0.9 of the absolute melting tempera -ture by a single mechanism, possibly by the migration of single adatoms or vacancies. Results were slightly affected by up to 23 tory Sn vapor, and in molybdenum were essentially unaffected by 0.5 Ti or carbon in the range 0.002 to 0.02 pct. Volume difffusion through the liquid is the mechanism of groove formation in chromium-liquid silver at 1200" to 1400°C and in molybdenum-, Mo-0.5Ti-, and tungsten-liquid tin at 1200" to 2000°C. The solid-liquid interface free energies involved were estimated from grooving kanetics. WHEN a grain boundary intersects a solid surface, a groove tends to form along the line of intersection at temperatures above about half the absolute melting point (0.5 TM). The groove progressively grows by preferential atomic migration either by diffusion or evaporation. Establishment of a groove angle occurs in accordance with the grain boundary and surface free energies involved. The motivation for groove formation is a reduction in the total surface free energy of the system. This study is a continuation of previous work on thermal grooving of chromium, molybdenum, and tungsten.&apos; The temperature ranges were extended, and the effect of metallic and interstitial impurities was evaluated. The results were such that certain interface free energies and surface self-diffusion coefficients were deduced from the grooving kinetics. EXPERIMENTAL WORK Materials and Preparation. As indicated in Table I, the 0.05-0.08-cm-thick chromium, molybdenum, and tungsten sheet used was nominally 99.99 pct after recrystallization. Two lots of molybdenum with about the same analysis, Mo-0.5Ti,* and tungsten were ob- *Alloy compsitions are expressed in weight percent . tained commercially. Extruded chromium rod,&apos; prepared from iodide process crystals, was warm rolled to sheet at 700°C. Sheet of three Cr-0 impurity alloys containing up to 0.03 pct 0 was prepared by warm rolling arc melted, extruded, and swaged rod. Two Cr-C impurity alloys containing up to 0.09 pct C were made by equilibrating unalloyed chromium with a known amount of CH4 for 24 hr at 1150°C in previously evacuated quartz capsules. Chromium containing nominally 0.015 and 0.06 pct N was similarly prepared by equilibration with NH3. The sheet was recrystallized to give a stable grain size about equal to the sheet thickness. Molybdenum and Mo-O.5Ti were recrystallized in a tantalum resistance furnace 1 hr at 1 x lo-5 torr at 2300" and 220O°C, respectively. Tungsten was similarly annealed for 1 hr at 2500°C. Chromium and its impurity alloys were outgassed at 1100°C and recrystallized 1 hr at 1700°C under 1 atm Ar. Except for nitrogen, the impurity content stayed roughly constant. Nitrogen in both alloys was reduced to <0.001 pct. In fact, over 80 pct of the added nitrogen was lost after outgassing at llOO°C and annealing sheet 1 hr at 1300°C in argon in the presence of tantalum. Such a rapid loss can be rationalized since -2 torr N are required for equilibrium with 0.04 pct N in solution,3 while the equilibrium pressure is ~10-5 torr over tantalum at 1300°C.4 The recrystallized sheet was cut into small coupons which were metallographically ground and polished on one side with a minimum of grain boundary relief. The surface roughness was on the order of 0.01 µ. The tin and silver used were nominally 99.999 spec-trographically pure. After being outgassed at 1100°C and equilibrated in a molybdenum crucible for 0.5 hr at 1800°C in argon, the tin contained 3 ppm 0, <0.3 ppm N, and 0.1 ppm H. Following outgassing at 900°C and equilibration in a chromium crucible 1 hr at 1400°C in argon, the gas content of the silver was 1 ppm O, <0.5 ppm N, and 0.3 ppm H. Grooving Under Argon or Vacuum. All specimens were placed in unsealed containers made from rod or sheet of the same alloy, thereby enabling the polished surface to achieve gas-solid equilibrium. The annealing fixtures are shown in Fig. 1. The specimen was placed in a resistance furnace with a tantalum or Ta-10W heating element plus tantalum fixtures or radiation shields. Chromium was outgassed at 1100°C, and molybdenum and tungsten were outgassed at 1900°C to 1 x l0-5 torr or at the grooving temperature, whichever was lower. In vacuum anneals, the specimen was then heated directly to the intended grooving temperature. In argon anneals, 99.996 Ar was admitted

Jan 1, 1970

By E. V. Potter

For a nurnber of years, it has been known that manganese made by electro-deposition under certain conditions is ductile while under other conditions it is very brittle. The ductile metal is gamma manganese normally stable only between 1100 and 1138°C1; the brittle metal is alpha manganese, stable up to 727OC. The ductile metal is not stable, but gradually changes to the brittle form; the time required to complete the transfornlation is about 20 days at room temperature. Other observations have indicated that the transformation is completed in 10 to 15 min. at about 125°C, while at — 10°C, no appreciable change occurs in 9 months. The properties of gainma and alpha Illanganese in the pure state are ordinarilj difficult to determine because the gamma structure cannot be retained by normal quenching procedures and alpha manganese is so brittle, it is difficult to obtain specimens free from flaws. In a recent investigation2 some properties of gamma and alpha manganese were determined by studying the ductile electrolytic metal and determining the changes in its properties as it transformed to the brittle alpha form. These investigations provided an excellent opportunity for following the progress of the transition and studying its mechanism. The results of a series of such investigations are reported in this paper. Procedure Various properties of manganese were determined starting with the metal in the original ductile gamma form and following the subsequent changes in its properties as the metal transformed to the brittle alpha form. These observations were made at various temperatures, the data providing information regartling the mechanism of the transformation as well as the effect of temperature 011 the transition rate. Structure and resistivity values gave the most significant results, so this paper is concerned primarily with them. The structure was studied microscopically as well as by X ray diffraction. The resistivity was determined on strips of the metal by measuring the potential drop across a given length of the specimen. Current was passed through the specimen by wires soldered to its ends, and the potential connections were made by wires looped around the specimen near its center. The current was determined by the potential drop across a standard resistor connected in series with the specimen, the potential drop being measured on a potentiometer. In the temperature range from room temperature to 100°C an ordinary drying oven was used to heat the specimen. This was entirely satisfactory except at 100°C, where the time required to heat the specimen was long compared to the transition time, making the initial section of the resistivity curve unsatisfactory. To overcome this limitation, at 100°C and higher a thermostatically controlled oil bath was used to heat the specimens. The block on which the specimen was mountetl was plunged into the hot oil at the start of each test. The heating time was thereby reduced from 5 min. to about 6 sec, and dependable resistivity values could be obtained through 160°C. At this point the whole transition, including the warm-up time for the specimen, required only about 20 sec and it was not considered worth while trying to extend the temperature range further. Aside from the heating problem, the problem of making a sufficient number of accurate resistivity determinations became more and more difficult as the temperature was raised. Using the manually operated potentiometer, 100°C was about as far as it was possible to go. At this temperature and above, a self-balancing photoelectric recording potentiometer was used. Its response was quite rapid, and it proved to be entirely satisfactory all the way through 160°C, where the tests were stopped because of the specimen heating problem rather than any limitation of the potentiometer recorder. The metal used in these tests was prepared at the Salt Lake City laboratory of the Bureau of Mines. The method of preparation is discussed in a paper by Schlain and Prater.3 The sheets were about 2 3/8 by 5 3/16 in. and varied from 10 to 16 mils in thickness. They could be cut readily into pieces suitable for the various tests. X ray and microstructure determinations were made on pieces about 1/8 to 1/4 in. wide and about 1 in. long, while resistivity measurements were made on strips as long as possible and about 55 in. wide. The thickness of each sheet was not uniform over all its surface. This had no bearing on the X ray and microstructure determinations, but sections as nearly uniform and free from flaws as possible were chosen for the resistivity determinations. The gamma manganese was electro-deposited at 30°C, the time of deposition ranging from 5 to 12 hr for each sheet. Whenever possible, the tests were started directly after the metal was stripped from the cathode; otherwise the sheet was placed immediately

Jan 1, 1950