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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 A. Ghosh, T. B. King

The kinetics of the discharge reaction: 20'- (in silicate melt) = O,(g) + 4e- at a platinum anode in lithium silicate melts have been studied al 1350°C by galvanostatic methods. Plots of the sleady-state overpotential, q, as a function of the logarithm of the current density, i, showed injlections and were linear only at high current densities. The value of the overpotential was influenced by bubbling gas through the electrolyte. The ocer potential was also studied as a function of time. The rise and decay of overpotential were very slow processes. At low current densities transport is the likely rate-controlling process but at high current densities passivation of the electrode, Presumably by an oxide film on the surface, seems to be a contributory functor. IT is well-established that molten silicates behave as electrolytes'5 and, except in a few cases,6 conduction is entirely ionic. Moreover, it is supposed that a possible, and perhaps predominant, mechanism for phase boundary reactions between metals and slags is similar to that in corrosion whereby anodic and cathodic processes occur at unrelated sites, the metal serving to conduct electrons.1'8 Thus electrochemical studies of some slag-metal reactions would seem to be a useful way to diagnose the rate-controlling steps in the overall reaction. The electrochemical method is, in principle, a better diagnostic tool than the direct chemical method for the following reasons: 1) The partial electrochemical reactions, which are simpler than the overall reaction, may be studied individually. 2) The rate of reaction can be controlled at will and independently of the concentrations of reactants. 3) Fast reactions can be studied by relaxation methods.' Esin and his coworkers5'10"12 have pioneered such studies in silicates and have deviloped some ingenious techniques. Not all of their findings, however. can be accepted without a good deal of further work. In this investigation, the kinetics of the oxygen discharge reaction: 202- (in silicate melt) = Oz(g) + 4e- [I] at a platinum electrode were studied by both steady-state and transient galvanostatic techniques. Interest in this reaction was first developed as a result of the findings of Fulton and chipman13 that the reduction of silica, in a silicate slag, by carbon, dissolved in liquid iron, is a very slow reaction. Subsequent work, for example, by Rawling and ~lliott,'~ has demonstrated that the reaction under these conditions must be slow, because the rate is limited by diffusion of oxygen in the iron to the metal-crucible phase boundary at which a CO bubble may be nucleated. Further work by Tarassof,'~ in which the reduction of silica by aluminum dissolved in copper was studied, has shown that under these conditions, where carbon monoxide evolution is not involved, control of the reaction rate resides in diffusion of silica in the slag phase. However, there is no practical way of inducing sufficient convection in the system to make it clear that the phase boundary reaction is indeed fast. The overall reaction of silica reduction involves the discharge of silicon ions at cathodic sites and oxygen ions at anodic sites. In the examples cited, the discharged ions are dissolved in a liquid metal. In the present study of oxygen ion discharge, gaseous oxygen may be evolved at high current densities or oxygen may simply dissolve, possibly as oxygen molecules, in the silicate at very low current densities. The discharge of an oxygen ion at an anode must, in silicates less basic than the orthosilicate composition, be preceded by a reaction in the vicinity of the electrode, such as: which makes oxygen ions available. Platinum was chosen as the working electrode since it is comparatively inert to oxygen and is, therefore, expected to come rapidly into equilibrium with the electrolyte and with gaseous oxygen. Minenko, Petrov, and Ivanova16 have measured the electromotive force at a platinum electrode in molten silicates as a function of the partial pressure of oxygen in the atmosphere, the concentration of oxide ions in the melt, and the temperature. They found platinum to behave as a reversible oxygen electrode. At two different oxygen pressures, Po2 (I) and Pq (11). the electromotive force is given by: where F is the Faraday constant, equal to 23,060 cal per v equivalent, indicating that the electrode reaction is as written in Eq. [I.]. Platinum has been similarly used in molten silicates by other inve~ti~ators. "'~~ In this investigation platinum was used only as an anode, since a current deposits other elements on its surface and changes its characteristics.

Jan 1, 1970

By R. D. Pehlke, J. V. Gluck

A study was made of the effect of small additions of metallic solutes on the thermodynamic activity of zinc in dilute solution with molten bismuth in the range 450o to 650°C. The experimental measurements were made in a multielectrode galvanic cell using. a fused LiCl-KCl electrolyte. The activity of zinc in binary solution exhibited a strong positive deviation from Raoult's law and obeyed Henry 's law to at least 0.050 mole fraction. The ternary addition of lead, gallium, or indium increased the activity of zinc. Cadmium or tin additions slightly decreased the zinc activity. Copper, mercury, silver, or antimony caused moderate decreases, while gold strongly decreased the zinc activity. The results are expressed in terms of Wagner's interaction parameter ejZn and a second-order cross-interaction parameter. The interactions for copper, gold, silver, and antimony showed a linear dependence with reciprocal absolute temperature, while the other interactions were essentially independent of temperature over the experimental range. Since tin and antimony decreased the zinc activity, the hypothesis of a purely periodic variation with atomic number was rejected. A semiquantitative explanation was possible with a free-electron model when relative electronegativities were used to express changes in the electron/atom ratio caused by the solute addition. Random solution and quasi-chemical models correctly predicted the majority of the interactions for which binary data were available to apply them. A knowledge of the thermodynamic interactions in liquid (and solid) metallic solutions is of considerable theoretical and experimental interest in the formulation of quantitative thermodynamic relations for metallurgical processes. The approaches to defining the interactions may be either phenomenological (i.e., "What mathematical function adequately describes observed behavior and permits extrapolation to new situations?") or theoretical, such as a specific model

Jan 1, 1968

By D. H. Baldwin, R. E. Reed-Hill

DURING the course of experiments involving oxygen equilibrations with a high-purity Pd-5 at. pct Rh alloy, the appearance of a subscale was noted. Most of the heat treatments in a pure oxygen atmosphere were performed at 900°C. The presence of the subscale was noted when the oxygen partial pressure was in excess of approximately 95 mm, up to 1 atm, the highest pressure used. According to available thermodynamic information' on the free energy of formation of Rh2O3 (the only reliably reported solid oxide of rhodium), this oxide should not be stable under these conditions, nor, of course, any oxide of palladium. Extraction of the subscale from the matrix was affected by treatment with aqua regia, and the resulting X-ray diffraction powder pattern is shown in Table I. This pattern is not that of Rh2O3, nor that of any known rhodium or palladium oxide. It can be indexed on a hexagonal lattice with a. = 5.22Å and co = 6.0Å. In addition to this unknown material, there was a weak Rh2O3 pattern. An X-ray fluorescence analysis of the powder gave 3214 palladium counts per sec and 5381 rhodium counts per sec, thus indicating the likelihood of a double oxide of palladium and rhodium. In view of the fact that the above result was obtained on a single sample, it is perhaps best not to insist upon the above ratio of about 0.6, but possibly to tentatively assume 0.5 or 1/1. The small amount of Rh2O3 in the X-ray pattern might have occurred on cooling, and it seems possible that the double oxide, below some temperature level, is not as stable as Rh2O3. To examine this point, some of the extracted double oxide was heated on a sheet of pure palladium in air at 900°C, and allowed to furnace-cool over a period of several hours. The X-ray diffraction pattern of the powder showed approximately the same intensity of Rh2O3 and the "hexagonal" oxide as before, but, in addition, a rather faint pattern of another crystalline species made its appearance. This finding again suggests partial transformation of the major (double) oxide to other oxides on cooling from 900°C. Application of the phase rule shows that only one equilibrium oxide (subscale) could have been present at temperature. Vacuum-fusion, oxygen analysis of the extracted subscale showed 7.7 ± 0.7 pct O. Combining this information with that of the X-ray fluorescence analysis suggests the formula PdRhO. This compound should have an oxygen content of 7.07 pct, which is within the range of error of the oxygen analysis. However, until a more careful stoichiometric study is made, it is suggested that the formula be written

Jan 1, 1965

By O. D. Gaither

This paper is an analytical study of the flow of fluids through small vertical conduits. Small conduits are defined as 11/4-in. nominal diameter tubing size and smaller, and approximately twice this area for annular conduits (i.e., 1- X 21/2-in. annulus and smaller). Experimental data are presented for the 1-X2-in. and 11/4- X 2%-in. annuli, and the I-in. and 11/4-in. tubing, since these represent the small conduit sizes and configurations generally encountered in oilfield applications. Data have been gathered for these conduits for single-phase water, single-phase gas and two-phase water-gas mixtures, with particular emphasis on high gas-liquid ratios. Water rates in excess of 2,000 BID and gas rates in excess of 2.5 MMcf/D, and two-phase flow ratios in between these two, represent the scope of the data gathered. Existing equations have been applied to predict flowing pressures and compared with experimental data. New correlations have been developed. INTRODUCTION The increased economic pressure on the domestic oil industry in the United States has constantly required the use of new techniques and equipment designed to reduce the cost of finding and producing oil and gas. Since tangible items are most readily apparent in economic analysis, the advent of lower-cost well completions was inevitable. One of the methods used to reduce costs which has received widespread attention is the slim-hole completion technique where tubing is used as the well casing and in which small conduits are used for tubing if necessary. Small conduits, defined by Kirkpatrick1 as "11/4-in. diameter nominal tubing and smaller for tubing flow and less than twice the 11/4-in. diameter nominal tubing internal flow area for annulus flow", have also found widespread usage as siphon strings for de-watering gas wells and as "kill" strings in deep high-pressure oil and gas wells. The growing use of small-diameter tubing has resulted in an increased need for development of improved methods to measure or predict flowing bottom-hole pressures since the physical dimensions generally preclude the use of subsurface-recording pressure gauges. Even in the cases where small bombs are available, the relatively high velocities encountered at nominal flow rates make it necessary to use excessive weight bars or special hold-down devices. Attempts to use recognized correlations to accurately predict flowing or gas-lift performance in wells equipped with small conduits have been generally unsuccessful. Insufficient field data were available to allow the development of a correlation on this basis, and an experimental approach was applied in an attempt to obtain a workable relation. The experimental approach used to obtain the data presented in this paper was actually a compromise between a field installation and a laboratory study. A test well 1,000 ft in length was used to obtain flow data on single-phase liquid, single-phase gas and two-phase water-gas flowing mixtures. Liquid rates up to 2,200 B/D and gas rates up to 3 MMcf/D were used in the single-phase flow studies. Two-phase flow rates from 100 to 600 B/D with gas-liquid ratios from 500 to 8,000 cu ft/bbl were recorded. Experimental data were obtained for single- and two-phase flow through 1-in and 11/4-in. nominal tubing, and through the annuli between 1- and 2-in. and 11/4- and 2%-in. nominal tubing strings. Experimental results for the two-phase flow are compared to the Poettmann-Carpenter correlation2 which is widely used as a comparative standard for development of multiphase flow predictions in flowing and gas-lift wells. Correlations developed by Tek,3 Baxendell and Thomas" were also investigated. The experimental data recorded herein fell in between the two flow regimes as defined by Ros," and this correlation also failed to yield satisfactory results. The fact that existing correlations failed to confirm the experimental data led to the need for development of a new correlation. Although a two-phase flow study was the primary objective of this investigation, data were also recorded for single-phase flow of water and gas, and constants were developed relating to pipe roughness and equivalent diameters for annular flow. These single-phase studies assisted materially in the development of certain of the two-phase flow results. Considerable previous work has been published which presented relationship of surface measurements to bottom-hole condition. The works of Buthod and Whiteley,6 Jones,' Poettmannb and the Texas Railroad Commission" are classic examples of the successful use of mathematical relationships which allow acceptable predictions of subsurface pressures, when gas is the flowing fluid. Darcy and others have derived relationships which may be used with minor modifications to predict subsurface flowing conditions in injection and water-supply wells. As previously stated, the application of the single-phase flow relationships

By Myron K. Rodgers

In rock- or ore-crushing tests all data, in order to be valuable for study and comparison, should be obtained and tabulated under conditions as uniform as possible. The results of many such tests have no value for comparison, because of incomplete data and the lack of uniform conditiops, screens and scale of sizing, etc. The purpose of this paper is to suggest a form of standard specifications which may be developed by the Milling Committee and approved by the A. I. M. E. for rock-crushing tests. It is not intended to discuss any theories of rock crushing. Reports of rock-crushing tests should include the following details: 1. Description of the machine employed (jaw or gyratory crushers, rolls, stamps,tube mills, Chilean mills, etc.), 2. Method and material (timber, concrete, etc.) of foundation. Much power is dissipated in the vibration of poor foundations. 3. Locality from which the rock or ore was obtaincd, and geological, mineralogical, and physical characters of the material. 4. The power consumption of the machine running with no load and with full load, the unit of power being 1 hp. per 24 hr, 5. The capacity of the machine in tons (of 2000 Ib.) per 24 hr. 6. The duty in tons per horsepower-day. 7. The screen analysis of feed and product by the proposed A. I. M. E. standard screen scale. On the foregoing statement, the following remarlrs are offered. Toughness of Rock Table P shows the relative crushing duty of the same machine on three different characters of rock, all other crushing conditions being the same. This table indicates that the specific resistance of the rock to crushing, may affect the crushing duty of a unit of power as much as 300 per cent. Perhaps this quality may be called toughness. It is not a function of hardness only. For comparison of tests, rocks should be divided into

Jan 1, 1916

By David B. Dill, Edgar R. Lea

The zinc deposits of the Balmat-Edwards Division of the St. Joseph Lead Company in northern New York State provide some 10 per cent of the domestic zinc produced annually within the United States. These complex ore deposits are contained within marbles of the Precambrian Grenville series, in a repetitive sequence of dolomites and silicated units. The Balmat ore bodies are localized at various intervals throughout some 1800 feet of the stratigraphic column on the northwest side of a band of gneiss that has continuity to the Edwards area, some 10 miles to the northeast. The Edwards ore bodies are located to the southeast of this gneiss. The marble formations are thought to have included repetitive intervals of marine sedimentation that provided mineralized source "beds" and were subsequently folded, flooded, and injected with melts at great depth and were sheared, recrystallized, and reconstituted. Detailed structural and stratigraphic studies throughout the northwestern Adirondacks, in the Balmat-Edwards district, and at each mine in particular indicate the close dependence of the ore deposits on the enveloping structure whether it be local, district-wide, or regional in scope. Primary folding has developed a northeast regional trend with northwest dips. Secondary folding has been developed by an almost horizontal northeast-southwest-oriented shear couple in the plane of the regional trend. The secondary folding has produced crossfolds that intersect the regional northeast trend and plunge north to northwest at various angles. The ore bodies are found within certain stratigraphic horizons where repeated alternation of competent and incompetent beds encouraged unusually complex folding. Analysis of individual mine structures indicates that the location of each deposit is controlled by structural crossing of primary and secondary folding. The ore bodies, which are tabular, lenticular, or pod-like in form, have features that suggest parallelism to true bedding or modified flow banding, developed by northeast-southwest shearing stresses related to the development of the crossfolds. The ore deposits in general follow both structural and recrystallization trends within the wall rocks. Mobilization of the pre-metamorphic ore minerals is believed to have involved a combination of plastic flow under stress and solution of the sphalerite, minor galena, and pyrite. The ore fluids are thought to have been guided by secondary shearing and microbrecciation into structurally prepared areas where reprecipitation took place. The presumed premetamorphic mineralization now exhibits epigenetic high-temperature features related to late-stage metamorphism.

Jan 1, 1968

By J. Chipman, N. J. Grant, R. Rocca

D. E. Babcock (Republic Steel Corp., Youngstown, Ohio)—With reference to eqs 7 and 8, at what temperature do they apply John Chipman (authors' reply)—That was 1600°C. Dr. Babcock—You have l x 10-4 as the component for the lime and 1 or 4x10-. Now, is it by dividing one into the other you get the 400? That is assuming equivalent activity on the part of oxygen, sulphur, and magnesia. Dr. Chipman—Yes, they are calculated for 1600. Now, the first one for CaO was calculated before we had a glimpse of Dr. Rosenqvist's paper." If you take his calculation you get 14,000 cal which is very good agreement, but our calculation would be superseded by Dr. Rosenqvist's new data. Dr. Babcock—The state you assume those to be in is the liquid state, as near as you can measure? Dr. Chipman—Naturally it is based on the solid CaS, but if you add the effect of fusion on both sides it just about balances out, so the ratio would be about the same. B. M. Larsen (U. S. Steel Co., Kearny, N. J.)—If we knew the activity of sulphur in the slag instead of merely the percentage, we might be able to find some conflicting factors that balance one another out, and find that the FeO or oxygen pressure effect is really present over the whole range. Dr. Chipman—I am fairly sure we would. The activity of sulphur in the slag and the activity of CaO in the slag, if we just knew those quantities, would enable us to save a lot of this computation and assumption and all the approximations we are doing now. Mr. Larsen—Two other points perhaps should be included: 1—an independent effect of manganese in helping the desulphurization; and 2—the number of mols of constituents or number of mols of ions or whatever there is in the slag could vary with these compositions in such a way that you get dilution effects. Dr. Chipman—You can figure all that in if you want to and it might improve the degree of approximation a little bit. Maybe enough to justify the labor of calculation, inaybe not, but we did not do it. L. S. Darken (U. S. Steel Co., Kearny, N. J.)—The authors have tackled a very complicated problem in trying to tie together in one picture the desulphurizing problem over the wide range of basicity and oxidation level from that of the open hearth to that of the blast furnace. At the present state of our knowledge of slags such an ambitious undertaking necessarily involves the adoption of numerous hypotheses. Their formulation (eq 11) for the higher FeO range

Jan 1, 1952

By E. G. Deane

THE CHAIRMAN (P. G. BECKETT, Globe, Ariz.).-The mining of large orebodies has in the last few years been such a big factor in the copper output of this State, and, in fact, of the whole country, I feel that we should have some valuable discussion this evening on the various mining methods described in the papers which are to be read; and I hope you will start a discussion on Mr. Deane's paper. J. A. EDE, La Salle, Ill.-I would like to ask whether, the timbers being left in, they have any fires owing to that fact? E. G. DEANE.-No, we do not. The timbers in the mat seem to lose life. I cannot tell you exactly what change takes place, but they do not burn readily. There is undoubtedly a chemical change in them-a change that makes them lose all strength. I , spoke of the strength of the sills. When we first started, we put in 4 by 8 sills, but those sills had no more strength in 6 months than a 2-in. plank would have. .J. P. HODGSON, Bisbee, Ariz.- I would like to ask Mr. Deane if the central supply raise in the- center of the block has been satisfactory; and also whether in extracting the ore they put small raises up so that wheelbarrows are not used in the stope?

Jan 12, 1916

By G. R. St. Pierre, R. D. Blackburn

Oxygen contents of' liquid-iron alloys saturated with oxides are analyzed. Minimum points observed in particular Fe-X-O systems can be predicled by a simple extension of first-order interaction methods. If minimum oxygen content occurs at N; where r is the ratio of metal to oxygen in the oxide phase. RECENTLY, wisher' reported on solubility measurements of A1203 in liquid iron at 1580°C which support the earlier work of d'Entremont, Guernsey, and chipman2 and Gokcen and Chipman. Swisher's diagram is reproduced in Fig. l. Minimum points in oxide solubilities have also been found in the Fe-Cr-0 system,4 Fig. 2, and the Fe-Ti-0 system,' Fig. 3. Minima positions can be used to confirm approximately the measured first-order interactions, &, cgr, and E&~, in liquid iron and to deduce compositions of components of constant activity in the oxide phases. Consider the solution of Alz03 in liquid iron: for which an equilibrium constant can be written as: differentiating Eq. [2] with respect to Na~, the atom fraction of &l in the metallic solution, and noting that If the activities of Al and 9 are expanded by a first-order interaction model, then:

Jan 1, 1969

By W. N. Tanner

The wire-rope hoisting conditions at the mines of the Anaconda Coppcr Mining Co. in Butte, Mont, are very severe because of the conditions under which it is necessary to operate. A study was made, in the fall of 1919, for the purpose of changing these conditions in order to obtain longer rope and sheave life. There are at present in Butte hoisting engines equipped with wire rope as follows: 9 main hoists using flat ropes. 7 main hoists using 1 1/2-in. rope. 5 main hoists using 11/4-in. rope. 6 shafts using 11/8-in. rope. 2 chippy hoists using 11/4-in. rope. 9 chippy hoists using 11/8-in. rope. 15 shafts using 1-in. rope. 7 shafts using 7/8-in. rope. 1 shaft using 3/4-in. rope. In addition, there are a number of sinking engines wing 5/8-in, 3/4-in., 7/8-in., and 1-in. (15.9, 10, 22, and 25 mm) rope. THe flat ropes run from 1/2 by 71/2 in. (12.7 by 1905 mm.) to-3/8 by 4 1/2-in (9.5 by 114 mm.) and are used on the older hoisting engines, which arc set comparatively close to the shaft. Because of swelling and moving ground at some of the shafts, these ropes present certain difficulties ill operation that are more pronounced than with round ropes; they are, therefore, being superseded by round ropes as newer engines are being installed. They are, however, much more easily inspected and repaired than round ropes. In general, the practice in Butte is to use hoisting engines equipped with 12-ft. (3 7 m.) cast-iron drums, smooth faced, for 11/2-in. rope and 6-ft. cast-iron drums, smooth faced, lagged with 3/8-in. steel plate for 11/4 l1/8 and 1-in. (31.7, 28.6, 25 mm.) rope in main and chippy shafts. Cast-iron head sheaves, 12, 10, and 6 ft. in diameter, with grooves

Jan 1, 1923

By W. N. Tanner

The wire-rope hoisting conditions at the mines of the Anaconda Coppcr Mining Co. in Butte, Mont, are very severe because of the conditions under which it is necessary to operate. A study was made, in the fall of 1919, for the purpose of changing these conditions in order to obtain longer rope and sheave life. There are at present in Butte hoisting engines equipped with wire rope as follows: 9 main hoists using flat ropes. 7 main hoists using 1 1/2-in. rope. 5 main hoists using 11/4-in. rope. 6 shafts using 11/8-in. rope. 2 chippy hoists using 11/4-in. rope. 9 chippy hoists using 11/8-in. rope. 15 shafts using 1-in. rope. 7 shafts using 7/8-in. rope. 1 shaft using 3/4-in. rope. In addition, there are a number of sinking engines wing 5/8-in, 3/4-in., 7/8-in., and 1-in. (15.9, 10, 22, and 25 mm) rope. THe flat ropes run from 1/2 by 71/2 in. (12.7 by 1905 mm.) to-3/8 by 4 1/2-in (9.5 by 114 mm.) and are used on the older hoisting engines, which arc set comparatively close to the shaft. Because of swelling and moving ground at some of the shafts, these ropes present certain difficulties ill operation that are more pronounced than with round ropes; they are, therefore, being superseded by round ropes as newer engines are being installed. They are, however, much more easily inspected and repaired than round ropes. In general, the practice in Butte is to use hoisting engines equipped with 12-ft. (3 7 m.) cast-iron drums, smooth faced, for 11/2-in. rope and 6-ft. cast-iron drums, smooth faced, lagged with 3/8-in. steel plate for 11/4 l1/8 and 1-in. (31.7, 28.6, 25 mm.) rope in main and chippy shafts. Cast-iron head sheaves, 12, 10, and 6 ft. in diameter, with grooves

Jan 1, 1923

By B. A. Rogers, K. O. Stamm

BECAUSE it is the basis of the economically important operation of hardening steel by quenching, the A3 transformation in iron has been the subject of numerous investigations. Although the contributions to this subject are interesting, no general review will be given here. Readers who care to follow the matter further are referred to the comprehensive summary by Cleaves and Thompson,1 which covers the literature to about 1935. Their references to 53 papers on the subject suggest that further investigation is hardly justifiable. However, considerable interest has developed recently concerning the reversibility of the transformation. From thermodynamic considerations, the transition ought to occur at the same point on heating or cooling, if the change of temperature is sufficiently slow. Yet all of the earlier investigators found a difference of several degrees. Burgess and Crowe,2 who used thermal methods, obtained average temperatures of 912° for Ac3 and 900°C. for Ar3 on electrolytic iron. Their data indicate a considerable range of temperature over which the change occurs, both on heating and on cooling. Terry3 measured the susceptibility in the critical range and estimated from the steepest parts of his curves that Ac3 came at 9180 and Ar3 at 903°C. Ishiwara4 was one of the first investigators to report a shorter interval between the temperature of the change in the two directions. He measured the change of susceptibility of kaolin-coated samples of steel, in a hydrogen atmosphere, at rates of heating and cooling so low that about 3 or 4 hr. were required for the transformation to complete itself. His results show some variability between samples, but indicate that the difference between Ac3 and Ar3 is in the vicinity of 6°C. Roberts and Davey5 measured the space lattice in pure iron in the vicinity of 900°°C. and concluded that a change occurs reversibly between 907° ± 3° and 9100 ± 3°C., probably between 907° and 910°C. Wells, Ackley, and Mehl6 made dilatometric determinations of the Ac3 and Ar3 points in samples of hydrogen-treated carbonyl iron maintained under a vacuum. They used three rates of heating and cooling: 2°, '1/2°, and 1/8°C. per min. and found the spread between the two points decreased with low rates. At the slowest rate, the Ac3 transition occurred at 909° to 909.5°C. and the Ar3 change at 907°C. in three of the samples believed to contain the lowest percentages of alien elements. They concluded that if the rate of temperature change and the content of alien elements were low enough, the A3 transformation would be completely reversible at 909.5° ± I°C. The question of reversibility is an interesting one and when some iron with especially small percentages of alien elements became available the opportunity to conduct an investigation was welcomed. This iron was prepared by the Division of

Jan 1, 1941

By J. Kucera, J. Vreštál

DIFFERENT authors1 ' have been engaged in meas-uring the vapor pressure of pure cobalt. The results of their measurements satisfy the expected temperature dependence of vapor pressure and are in mutual agreement, with the exception of the results by De Dyk Man and ~esmejanov.~ The latter authors, by using the effusion method, have achieved considerably higher values than other workers. By using the isotope exchange method they obtained much lower values than other authors. The determination of thermodynamic functions of the binary Ni-Co system was carried out, as far as we know, only by De Dyk Man and Nesmejanov.4 This determination was based on extremely low values of vapor pressure over pure cobalt obtained by the isotope exchange method. Therefore we considered it useful to repeat these measurements. Furthermore, the reliable values of thermodynamic functions should complement the migration characteristics, the inner magnetic field data obtained by Miissbauer effect measurements, specific heat data, and the K effect and positron annihilation characteristics that have been achieved for the Ni-Co system in the Institute of Metallurgy of the Czechoslovak Academy of Sciences in Brno.5-9 The measurements in this paper were performed by the isotope exchange method. In this method, as has been shown by analysis,10-'3 the vaporization rate, w, can be calculated from the relation w = k/1oSw [1] i0Sw) [1] where L, is the activity per unit mass of the source, S is the area of evaporation, k is the tangent at the point t = 0 to the curve giving the radioactivity de-pendence of the target vs annealing time, t, and wis the probability for the tracer atom condensation on the target surface. The value for cc. can be obtained from the equation w = a + 2P(l-a) [2] where P is Clausing's coefficient and a is the condensation coefficient. In the present work the cylinder shaped containers for annealing the samples were used, characterized by the ratio 1:d = 1.06. Here 1 is the length and d the diameter of the container. For this ratio P = 0.514 and w =0.5, and w is independent of the condensation coefficient. The vaporization rate is related to the vapor pressure p by the relation where R is the gas constant, T is the absolute temperature, and M is the molecular weight of the component investigated. Measurements of the vapor pressure of the i component over the pure metal, p!, and the alloy, pi, at the given temperature and composition enable one to calculate the thermodynamic activity of this component from the equation ai=pi/pi [4] is and the activity coefficient ri=ai/xi [5] xi where xi is the molar fraction of the investigated alloy component. EXPERIMENTAL Evaporization rate measurements were carried out with pure cobalt and eight different Ni-Co alloys, which were kindly delivered by the Centre National de Recherches Me'tallurgiques Liege, Belgium. The composition of the alloys is given in Table I. The cobalt used in these alloys contained the following impurities: 0.016 wt pct Fe, 0.014 wt pct Cu, 0.01 wt pct Mn. Other elements were present in much lower concentrations. From the melts, samples in the form of small cylinders of 12 mm in diam were ma-chined. The thickness of the targets and sources was 2.5 and 1.2 mm, respectively. The lower thickness of the sources was chosen to make their over-all ac-tivity as low as possible. Sources were activated in

Jan 1, 1970

By R. E. H. Pomeroy

The statistical data given in this paper are taken from the actual performance of the No. 2 reverberatory furnace of the Nevada Consolidated Copper Co., Mc Gill, Nev., for a period of four months, from April to July, 1914. The principal furnace dimensions are: Length, 132 ft. % in. at the skim-line level; average width, 18 ft., 10 in. at the skim-line level. The roof is 7 ft. above the skim-line level at the firing end. The average area in the uptake flue is 36 sq. ft., and the area above the skim line under the vulcatory arch is 24.3 sq. ft. Fig. 1 shows a diagrammatic plan and sectional elevation of this furnace. The furnace is equipped with two 400-b.h.p. Stirling waste-heat boilers set in parallel. California crude petroleum is used for fuel and has a specific gravity of 16.5" B., flashing in open test at 199" F. The oil is heated to about 200" F. in a steam heater before going to the burners, requiring about 9 b.h.p. per furnace day to heat it from the line temperature to the burning temperature. Measurement is made by oil meter, checked daily by reservoir readings. The oil is fed by gravity (34 Ib. static pressure) to seven low-pressure blast burners of the Steptoe type (Fig. 2). The blast for these burners is supplied at about 40-08. pressure by a motor-driven Connersville blower of 42 cu. ft. capacity per revolution. The air supplied by the blower through the burners for atomizing the oil amounts to about 10 per cent. of the theoretical air necessary for complete combustion of the oil. The remainder of the necessary air enters the furnace through the burner openings in the firing wall. No checker holes are provided, and the charge holes in the roof are equipped with slide gates and " dog houses" to minimize air leakages. The combustion of the fuel, as shown by gas analysis at the front of the furnace, is practically complete, the carbon monoxide in the gases being less than 0.5 per cent. The draft at the firing end of the furnace is 0.18 in. of water. At the throat or in the uptake above the "verb" the draft is about 1 in.

Jan 1, 1915

Abel, Charles Edwin, Student, Univ. of California Los Angeles, Cal. '81 Ames, Marshall B., Blaine-Republic Co Republic, Wash. "81 Anderson, Norman John, Student, South Dakota School of Mines Rapid City, S. D. '82 Angst, Robert A., Jr., Student, Michigan College of Min. & Tech Houghton, Mich. '82 Apgar, James William, Student, Lafayette College Easton, Pa. '83 Armstrong, John R. Box 274, Neosho, Mo. '81 Armstrong, Robert H., Student, Lafayette College Easton, Pa. '81 Arnot, Paul H. 608 S. Acacia St., Compton, Cal. '81 Asel, Philip R., Student, Colorado. School of Mines Golden, Colo. '82 Atkins, William Robert, Student, Michigan College of Min. & Tech Houghton, Mich. '82 Augenthaler, Robert L., Student, New Mexico School of Mines Socorro, N. M. '82 Augustine, Robert W., Student, Alaska School of Mines College, Alaska. '82. Avery, Eugene A., Student, Montana School of Mines Butte, Mont. '82 Babcock, Norwood N., Student, South Dakota School of Mines Rapid City, S. D. '82 Baer, Jerome S., Student, Michigan College of Min. & Tech Houghton, Mich. '81 Baker, Robert C., Student, Pennsylvania State College.. 112 E. Beaver Ave., State College, Pa. '82 Baldwin, William C., Student, Univ. of Illinois Urban, III. '81

Jan 1, 1932

By T. F. Kassner

The dissolution kinetics of type 304 stainless steel in the Bi-Sn eutectic alloy have been investigated under the well-defined hydrodynamic conditions produced by the rotating-disc sample geometry. In addition, the mutual solubilities of iron, chromium, nickel, and manganese from 304 stainless steel in the eutectic alloy were determined over the temperature range 450" to 985°C. The convective -diffusion model for mass transport from a rotating disc was used to interpret the experinlental dissolution data. The dissolution process was found to be liquid-diffusion-controlled under specific conditions of temperature and Reynolds number. Liquid penetration into the 304 stainless steel resulted in a reduction of the di,ffusion-controlled mass flux and thus precluded the calculation of the diffusion coeficients of the four components from 304 stainless steel in the Bi-Sn eutectic alloy. The convective-diffusion model for diffusional limitations of electrode reactions and mass transport at the tationssurface of a rotating disc set forth by Levich 1,2 has found wide applicability in the investigation of electrochemical and dissolution phenomena in aqueous systems. Riddiford 3 and Rosner have reviewed the model and also include numerous references on work of this nature. More recently the rotating-disc system has been applied to the investigation of hetereogeneous reactions in liquid-metal systems. Shurygin and Kryuk 5 have measured the dissolution rates of carbon discs in molten Fe-C, Fe-Si, Fe-P, and Fe-Ni alloys. Shurygin and shantarin6 also studied the dissolution kinetics of iron, molybdenum, chromium, and tungsten, and the carbides of chromium and tungsten in Fe-C solutions with a rotating-disc sample geometry. In these systems it was possible to distinguish between diffusion and reaction control mainly through experimental confirmation of the velocity dependence of the dissolution rate predicted by the model. However in the absence of dependable solubility data and the virtual lack of diffusion data in these systems, a quantitative check of the magnitude and the temperature dependence of the rate was not possible. In many instances, estimates of the activation energy for solute diffusion and the diffusion coefficient based upon the experimental dissolution data are not credible. A recent study by this author7 has resulted in a critical test of the model in a liquid-metal system. The solution rates of tantalum discs in liquid tin were measured over a wide range of temperature and velocity conditions. In addition, the solubility and diffusion coefficient of tantalum in liquid tin were determined as a function of temperature. The latter data were used with the model to predict both the magnitude and the temperature dependence of the dissolution flux. In that work it was also deemed necessary to reevaluate the solution to the convective diffusion equation to incorporate the effect of the lower range of Schmidt numbers encountered in liquid-metal systems. Good agreement between the model and the experimental dissolution data in the region of diffusion control was obtained in the Ta-Sn system. The Bi-Sn eutectic alloy is used as a seal between the reactor head and the reactor vessel in the Experimental Breeder Reactor-11. The alloy is fused periodically prior to fuel-handling operations. In that connection, it was necessary to investigate the compatibility of the liquid alloy with the type 304 stainless-steel containment material. The results of a rotating-disc study in this multicomponent system are presented. EXPERIMENTAL METHOD The 5.08-cm-diam discs were machined from 0.317-cm-thick plate. Chemical analysis information for the type 304 SS material is given in Table I. The discs were ground flat on metallographic paper and given a final polish on Linde B abrasive. A thin support rod was threaded into the disc and the region around the threads was fused under an inert gas. The support rod was fitted with a quartz protection tube and then was attached to a supporting shaft which passed through a rotary push-pull vacuum seal. The disc and supporting shafts were dynamically balanced prior to insertion into the furnace tube. The apparatus is shown schematically in Fig. 1. The 58 pct Bi-42 pct Sn eutectic alloy melts were prepared from 99.995 pct pure Bi and Sn by fusing the components in a 7-cm-ID Pyrex crucible. The system in which the melts were made was evacuated to a pressure of 1 x 10-6 Torr and back-filled with purified argon several times before melting the charge. The ingot was reweighed and placed in a slightly larger-diameter Vycor crucible used in the dissolution runs. A run was started by lowering the disc into the liquid

Jan 1, 1968

By R. A. Graham, R. W. Rohde, J. R. Holland

In a shock wave compression study of a martensitic Fe-30 pct Ni alloy, Graham, Anderson, and Holland' found a region of unusual compressibility extending from a few kilobars up to about 20 kbars. This region was characterized by a continuously decreasing shock wave velocity with increasing stress. In this note, we report the results of a study initiated to determine the source of this unusual compressibility. In earlier shock-loading experiments on martensitic Fe-30 pct Ni, Loree et a1.' determined that a phase change occurred at about 80 kbars. Subsequently, Bowden and elly found that samples of a similar material shock-loaded at about 100 kbars experienced a martensite-to-austenite transition. Their crystal-lographic analysis showed the transition was a direct reversal of the established martensite system to the austenite phase. The shock loading in the present experiments was accomplished by precisely controlled plane impact between two discs of the sample material. This configuration created a state of uniaxial strain in the two the front of a projectile which was accelerated to various velocities. Planarity between the impacting discs was controlled to 5 x 10-4 rad, and impact velocities were measured to 0.5 pct. From a knowledge of the Hugoniot relationships of the material and the impact velocity, the shock-wave stress can be calculated. Samples were shocked at 18, 50, 70, and 100 kbars. The specimen discs shocked at 18 and 50 kbars were instrumented with quartz gages to observe the stress time profile. A more detailed description of the experiment has been given previously.4 The shock-loaded specimens were recovered intact by decelerating them in a catcher filled with soft wood. Discs of Fe-30 pct Ni nominally 12.7 mm thick and 64 mm in diam were cut from bar stock. Chemical analysis of the material provided the following composition in weight percents: 29.5 Ni, 0.50 Mn, 0.21 Si, and 0.10 C, with traces of Cr, Cu, Mo, Al, and Co. The discs were austenitized at 650° C for 2 hr at a pressure of less than l0-' torr, and furnace-cooled. Martensite was then produced by quenching the discs at -196" and holding 168 hr. The initial martensitic structure formed is shown in Fig. l(a). Typical microstructures of samples shock-loaded at 18 and 100 kbars are shown in Figs. l(b) and l(c). The banded structure with the austenite regions running parallel to the shock propagation direction was characteristic of samples shock-loaded at all stresses. No such banding was found in samples that were not shock-loaded. Comparison of Figs. l(b) and l(c) shows that, although under the optical microscope the two microstructures are quite similar, the martensite plates of the specimen shocked at 100 kbars etched in a distinctly different manner. This unique etching behavior of martensite in samples shock-loaded above the 80 kbar transition point has also been observed by Leslie el al.' These investigators determined from X-ray and electron microscope studies that fcc martensite, similar in appearance to normal bcc martensite, had been formed under shock loading. A quantitative determination of the amount of austenite present after shock loading was made by X-ray techniques. Both the methods of Lindren' and Miller' were utilized. The results are shown in Table I. The error limits are those experimentally observed from two independent analyses of each sample and represent the precision of the experiment. The absolute error, which should be similar for each sample, is believed to be about 10 pct. It is seen that as the shock stress increases the amount of austenite present also increases. On the basis of the X-ray and microscopic observations, we conclude that shock loading below the 80 kbar ersal will initiate a martensitic reversal: the amount of reversal that occurs increases with in-

Jan 1, 1969

By J. W. Downey, M. V. Nevitt

The phase boundaries for the 950" isothermal sections in the ternary systems Zr-Co-0 and `Zr-Ni-0 have been determined for the composition range from 50 to 100 at. pct Zr. The two systems show very similar phase relations, having no extensive solid solution phase fields. Each contains a ternary phase. These phases are apparently isostructural, but their structure has not been determined. Some aspects of the phase relations are discussed in terms of the alloying behavior of transition metals. THE work described in this paper is the outgrowth of a recent study of the occurrence of phases having the Ti2Ni-type structure (structure-type E9,) in certain ternary systems involving Ti, Zr, or Hf with another transition metal and O.", In the Zr-CO-0 and Zr-Ni-0 systems no Ti2Ni-type phases were found to occur. However, there are several interesting aspects of the phase relations in the two systems which have significance from the point of view of the alloying behavior of transition metals. The results of this investigation may also have some importance in studies of the oxidation of Zr-Co and Zr-Ni alloys. In both the Zr-Co-0 and Zr-Ni-0 systems only the 950" isothermal sections were investigated and, as a further restriction, the study was limited to the composition range from 50 to 100 at. pct Zr. A tentative Zr-Co binary diagram has been published by Larsen, Williams, and Pehin. In the composition range pertinent to the present work they report a eutectic at 980°C and 75.9 at. pct Zr, the products of which are the terminal solid solution based on /3 Zr and the compound Zr2Co, and a eutectic at 1080" and 64.8 at. pct Zr whose products are Zr,Co and ZrCo. The solid solution based on /3 Zr is shown to decompose eutectoidally at 826°C into a Zr and Zr2Co. The limits of solubility of Co in a and /3 Zr have not been established. The structure of Zr2Co is not identified in the publication just cited. Dwight has reported that ZrCo has the CsC1-type strcture. The Zr-rich portion of the Zr-Ni diagram has been determined by Hayes, Roberson, and Paasche." The phase relations are very similar to those of the ZrCo system. A eutectic reaction whose products are /3 Zr containing 2.9 at. pct Ni and Zr,Ni occurs at 961°c, and a eutectic between Zr,Ni and ZrNi is found at 985". The solid solution based on /3 Zr decomposes eutectoidally at 808°C. The solubility of Ni in a Zr is not known accurately but is believed to be very small. Smith, Kirkpatrick, Bailey, and Williams7 have found that Zr2Ni has a tetragonal structure of the A1,Cu-type and that ZrNi is orthorhombic. Domagala and McPherson8 have published a constitution diagram for the system Zr-ZrO,. At 950" their diagram indicates that the solid solution of 0 in 0 Zr is stable from 0 to 0.5 at. pct while the phase field of 0 in a Zr extends from 6 to 29 at. pct. These solubility limits were adopted in the present study and no binary Zr-0 alloys were made. No previous data on the phase diagrams of the ternary systems are known to exist. EXPERIMENTAL PROCEDURE The experimental details involved in the preparation of alloys in this laboratory by arc melting have been described in several previous papers"3 and they will not be repeated here. Information concerning the purity of the metals used is given in Table I. Oxygen was added in the form of reagent grade ZrO,. All of the cast specimens in both alloy systems were annealed in air-atmosphere tube furnaces at 950 3' for 72 hr and water quenched. The specimens were protected from oxidation by wrapping them in Mo foil and sealing them in quartz tubes that had been evacuated at room temperature to a pressure of 1 x 10B mm of Hg. The phase boundaries were determined by metallography, and identification of the phases was accomplished primarily by X-ray diffraction methods which employed a powder camera having a diameter of 114.6 mm. The diffraction techniques which are in use in this laboratory have been previously described.' An etchant that proved satisfactory for most of the alloys consisted of 5 pct by vol of AgNO

Jan 1, 1962

Jan 1, 1924