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By R. L. Orr, J. D. G. Masse, Ralph Hultgren

The relative partial molar enthalpies of gold and tin in liquid Au-Sn alloys have been measured from Xsn = 0.474 to 0.510 at 696°K, slightly above the melting point of solid AuSn. Within an average precision of 6 cal per g-atom, the data are represented by two smooth curves, which satisfy the Gibbs-Duhem relationship and which do not show any anomalous behavior in the range of composition studied. The results give no support to the hypothesis that atomic associations in the equiatomic liquid alloy resemble those in solid AuSu. LITTLE has been firmly established as to the nature of atomic distribution in liquid metallic phases. A favored hypothesis assumes the existence of atomic groupings in the liquid phase which are similar to those in solid phases occurring at lower temperatures. Beginning with this hypothesis, it is often possible to adjust the values of certain parameters (such as degree of association) so that approximate agreement is achieved with certain features of the X-ray diffraction pattern of the liquid, even though many other possible structures might satisfy the data equally well. Thus, in this manner, the structure of liquid tin has been described as a dispersion of fragments of gray tin in a matrix of metallic tin.1 Four X-ray diffraction studies2"5 have been made of the liquid alloy of composition AuSn at temperatures slightly above the melting point of the solid. Each investigator concluded, on somewhat different grounds, that the liquid consisted to a large extent of arrays of atoms similar to the solid, with admixture of more disordered arrays. Solid AuSn has the nickel arsenide crystal structure: each tin atom has six nearest neighbors, all gold atoms; and each gold atom has six tin and two gold atoms as nearest neighbors. It remains highly ordered to the melting point. The liquid alloy has a large exothermic (?H700° K = -2700 cal per g-atom6) enthalpy of formation, favoring ordering and making the hypothetical molecular association not unreasonable. The possible existence of such solidlike arrays, or of a high degree of order that occurs preferentially at a specific composition in a liquid alloy, might also be revealed by thermodynamic behavior somewhat analogous to that in highly ordered solid alloy phases. The latter often exist over wide composition ranges, within which the highest degree of order occurs at the ideal composition for which the atomic fractions are equal to the fractions of sites which are "right" for each kind of atom. On departing from the ideal composition, the excess atoms occupy "wrong" positions, raising the internal energy and making it progressively easier for additional atoms to occupy "wrong" positions. Thus, on either side of the ideal composition, there should be a pronounced rise in the entropy and enthalpy, which would be shown particularly by the change in the relative partial molar enthalpies, ?Hi, since they depend strongly on d?H/dx. In the one case where accurate measurements have been made, the solid AuCu ordered phase, the structure becomes much less ordered as the composition deviates from the ideal, and relative partial molar enthalpies change sharply as shown by the data6 given in Table I. This suggests the possibility of finding similar pronounced changes in the relative partial molar enthalpies of gold and tin in liquid alloys near the composition AuSn if the postulated solidlike ar-

Jan 1, 1967

By O. W. Ellis

THE writer has dealt with the effect of various methods of melting copper upon the gas content of the metal.1 The copper referred to in his in his earlier paper was melted in the foundry both in the oil furnace and the electric furnace. As the metal, did not measure up to conductivity FIG. L -INGOT OF OVERPOLEP COPPER. standard, the term "casting copper" was applied to the material in the title of the paper. It was thought that some information in regard to the gases in a sample of overpoled copper might also be of interest, and through the courtesy of C. R. Stevens, superintendent of the copper mill of the Westinghouse Elec. & Mfg. Co., such a sample was obtained. The metal was chill-cast in the form of an ingot about 7 in. long, 2 ½ in. deep (from the base to the raised surface of the ingot) and from 1 3/8 to 1 7/8 in. wide. A photograph of part of the ingot is shown in Fig. 1. The effect of overpoling on the surface of the metal is here quite clearly shown.

Jan 1, 1929

By R. Schuhmann, O. W. Moles

at temperatures of 1150°, 1250°, and 1350°C for liquid copper sulphides ranging in composition from saturation with Cu to about 21.5 pct S. From the experimental data, activities of Cu, S, and Cu2S in the melts were calculated. Also, the results furnish a new determination of the location of the curve showing the compositions of Cu-saturoted sulphide melts in the CU-S constitution diagram. THE "white metal" made as an intermediate L product in converting copper matte to blister copper is a matte approximating Cu2S in composition. It has long been known that liquid Cu-S mattes can exist at a given temperature over an appreciable composition range, with S:Cu ratios ranging up from a lower limit corresponding to equilibrium of the matte with a liquid Cu phase. The Cu-saturated matte has somewhat less S than Cu2S, although previous measurements of the compositions of Cu-saturated mattes are not in good agreement.'" As the S:Cu ratio approaches and slightly exceeds that for Cu2S, the partial pressure of sulphur gas over the liquid matte rapidly approaches atmospheric pressure,5 so that Cu-S melts with much more S than Cu2S can be made and handled only in pressure apparatus. Accordingly, the liquid copper sulphides of interest in copper smelting and readily studied experimentally fall in a relatively narrow composi- tion range about Cu2S. The freezing points of Cu-S mattes show a maximum of 1129°C near the composition Cu, dropping to 1105oC for Cu-saturated mattes having less S and dropping under 1100°C for higher S mattes.' Estimates of the sulphur pressure and other thermodynamic properties of liquid Cu,S were made by Kelley; based on extrapolations from equilibrium measurements on solid Cu,S. More recently, Cox and coworkers' studied equilibria in the reaction: Cu,S + H, e 2Cu + H,S over the temperature range 700" to 1250°C. They measured equilibrium H2S:H2 ratios presumably with both the sulphide and the metal phase present, so that their data above the melting point of Cu,S should measure the S pressure of Cu-saturated sulphide melts. The sulphur pressures of liquid copper sulphides of several S:Cu ratios at their freezing points can be estimated from data given by Posnjak, Allen, and Merwin." However, beyond these few data, no systematic study seems to have been made of the relations of sulphur pressure and other chemical properties of liquid copper sulphides to composition and temperature. The measurements of the sulphur pressures of liquid copper sulphides reported in this paper represent a first step in the quantitative study of the chemistry of mattes. Similar work is planned on

Jan 1, 1952

In the Philippines, where distances are spoken of in terms off fight time, the Sipalay copper mines are two flight hours southeast of Manila on the island of Negros. After landing at the airport in Bacolod, it is then 170 km (106 milers) by surface transportation to Marinduque Mining and Industrial Corp.'s expanding copper operation. While copper deposits were discovered in the area in 1936-and one mine, the Binulig, began operations soon after-it wasn't until 1956 that stripping at Sipalay and construction of a 4000-t/d (4400-stpd) mill began. The mill went into operation in May 1957, and the first shipment of copper concentrate was made three months later.

Jan 8, 1978

By Reynold Q. Shotts

The small domestic underfeed stoker as now designed is unusually sensitive to the coking and plastic properties of coals, and when the attempt is made to burn the high rank coking and caking coals of the Appalachian fields, serious trouble may occur. Part of the trouble may be caused by the ash content and clinkering characteristics of the particular coal in use, but more often it is the result of an excessive ac-in of coke in the form of ''trees,, or masses in the fuel bed. Often the zone of burning becomes so restricted that the fire goes out, and in extreme cases the fire may be lifted completely out of the fuel bed and away from the air ports. Even if the fire is preserved, excessive coking may cause response to subsequent heat demand to be slow and irregular. Coke trees seem to grow most readily during periods of hold-fire operation, so that in order to preserve the fire in mild weather it is often necessary to set the timer for such a long operating period each hour that much unneeded and unwanted heat is developed, causing discomfort. During demand periods the fire may pick up so slowly that the intense burning which develops just before stoker cut-off causes a serious overshooting of the thermostat. Stoker coal performance tests which have been made in a number of labora- tories1,2,3,4,5 are one method of approach to the problem Of selecting stoker coals- As yet these tests have not been standardized and they are expensive and time-consuming. The value of the results probably increases with the length of the test. Sherman and co-workers at Battelle Memorial Institute believe that even a one-week test is not too reliable a trial2 and it is quite likely that Others will agree. A great advantage of such tests is that characteristics of coals, other than the tendency to form coke masses, may be evaluated from them. The selection of stoker coals would be greatly facilitated if there existed some simp1e measure Of the tendency Of a a to form coke in a fuel bed. Although possessing all Of the disadvantages Of any small-scale laboratory test, the test for the free-swelling index of coal has been found useful for evaluating the probable effects Of swelling properties upon combustion.7 Ostborg, Limbacherand Sherman, have shown that the test can Predict, roughly, the tendency Of coke to accumulate in the fuel bed Of a domestic stoker. They also gave instances of its value in predicting combustion behavior in some large installations. The use of the test for free-swelling index has become well established and has been adopted as a standard by the American Society for Testing Materials.8 When domestic stoker coal investigations began at the State Mine Experiment Station in the summer of 1944, it was decided

Jan 1, 1949

APPROXIMATELY 90 per cent of the steel that is melted and refined in the United States and poured into ingots is made in basic open-hearth furnaces, as shown in Table 1-1. The annual ingot capacity of the steel industry reported January 1,1950, by the American Iron and Steel Institute8* was 99,040,160 tons, of which the basic open-hearth process accounted for 85,896,580 tons, 86.7 per cent of the total. The capacity of the individual furnaces varies over a wide range, a large majority falling within limits of 50 to 200 tons (Fig 1-1). Most of the units constructed [ ] since 1942 are in the larger size groups, between 175 and 225 tons capacity.

Jan 1, 1951

By F. Milton Lewis, Roshan B. Bhappu

The methods for preparing operating cost estimates for a proposed mining venture are outlined. The procedures for estimating the direct and indirect operating cost for proposed mining and ore processing facilities are reviewed. Profits from the by-products are credits to the total operating cost, direct plus indirect, and are subtracted to obtain the total net operating cost. The non-operating costs which are a part of the total expenses are defined but are not considered in this manuscript. A method for developing the operating cost for a typical copper concentrator in the southwest is described in detail.

Jan 1, 1978

Discussion of the paper of WALTHER MATHESIUS, presented at the New York meeting, February, 1915, and printed in Bulletin No. 99, March, 1915, pp. 539 to 555. JOSEPH W. RICHARDS, So. Bethlehem, Pa.-This paper answers. partly the difficult questions which have come up as to why it is not economical to use higher blast temperatures in the smelting of Mesaba ores, such as the high temperatures used in European practices, and the answer is very plain that the ores will not stand the higher temperature. But the paper does not go into detail as to what special difficulties were found with the higher temperature of blast, and I would ask the author to kindly specify them. W. A. FORBES, New York, N. Y.-A large part of the troubles that furnace men experienced in using high-blast heats in smelting Mesaba ores in the early days of using Mesaba ores, was clue to the attempt to use these soft ores on furnaces having the same lines as the furnaces used in smelting the hard Old Range ores. As the result of observation and study, the dimensions of the lower part of the blast furnaces have been changed and the difficulties of the blast-furnace men in operating with a large percentage of Mesaba ore and high-blast temperatures have been largely overcome. The changes I refer to in particular are: (1) steepening the angle of the bosh; (2), decreasing the height of the bosh; (3) increasing the diameter of the hearth. JOSEPH W. RICHARDS.-Mr. Forbes's answer is quite satisfactory, and the moral which it points is that when the furnace is run with a higher temperature in the smelting zone, the furnace lines which were adapted for the lower temperatures are not necessarily those best suited for the higher hearth temperatures. If. enriched blast were used in a furnace, and higher temperatures run, it would be found necessary to further modify the lines of the furnace to meet the new conditions and to get the maximum output with economy. J. E. JOHNSON, JR., New York, N. Y.-It seems to me this is one of the few papers which could well have been a little longer. The data which Mr. Mathesius has given us, I think should be considered in connection with the paper which Mr. Brassert read before the American Iron and Steel Institute last spring, in which he described how they had obtained remarkable results with furnaces with steep but very short boshes; the angles have been raised to 80°, and the boshes made so short that they no longer appear as a conspicuous part of the shape of the furnace.

Jan 5, 1915

By W. D. Robertson, A. S. Tetelman

The technique of decorating dislocations was employed to investigate deformation and fracture resulting from Precipitation of hydrogen in Fe-3 pet Si single crystals. It is shown that cracks are produced on (100) planes inside crystals, as a consequence of the precipitation of hydrogen gas, either when crystals are quenched from a hydrogen atmosphere at elevated temperatures or cathodically charged with hydrogen at room temperature. Plastic deformation in the vicinity of cracks, observed as arrays of decorated dislocations, is in conformity with the calculated stress distribution about a crack containing an internal pressure, and the observations provide information permitting a detailed analysis of the mechanics of crack growth. The fracture characteristics of crystals containing internal cracks were evaluated at 25o and -196°C and the results are related to the mechanism of hydrogen embrittlement in terms of the growth of preexisting cracks. HYDROGEN in bee iron or steel produces two characteristic changes in mechanical properties: I), a decrease in ductility (macroscopic strain at fracture) that depends on temperature and strain rate, and 2), spontaneous fracture under static load that depends on time and apparent stress. Resolution of these phenomena into the microscopic processes that combine to produce the macroscopic effects is especially difficult in the Fe-H system in which the active component cannot be directly observed and only maintained in equilibrium with great difficulty in the temperature and pressure range in which embrittlement phenomena appear. As a result of these complications, verification of the numerous hypotheses'-5 that have been proposed to explain the microscopic mechanism of embrittlement depends on self-consistency with measured changes in macroscopic properties that are averaged over the volume of a specimen. It is obviously important to obtain a more direct evaluation of the microscopic processes that combine to produce embrittlement. Accordingly, the present investigation was designed to identify and observe, as directly as possible, the microscopic effects of introducting hydrogen into a bee crystal. It was concluded from a previous investigation6 of X-ray line broadening, produced by introducing hydrogen into pure iron at room temperature, that the only effect that could be associated with the introduction of hydrogen was plastic deformation; in particular, dilation of the lattice was not observed, within ± 0.01 pet, and no evidence was found that could be interpreted to support the idea7'* that hydrogen occupies tetrahedral interstitial sites in the iron lattice. The absence of lattice dilation is consistent with the extremely small solubility of hydrogen in bee iron9,10 (0.015 at. pet at 900oC and 1 atm pressure), and the evidence of plastic deformation is consistent with the fact that hydrogen, introduced by cathodic charging, eliminates the carbon yield point.11-13 Following this investigation, the immediate problem was to devise a method by which plastic deformation could be observed directly. The technique employed by Hibbard and Dunn14 to observe the movement of dislocations during bending and subsequent polygonization of Fe-3 pet Si single crystals was adopted and modified for the present purpose to include the observation of dislocation arrays in the volume of the crystal, and their association with the fracture process. EXPERIMENTAL PROCEDURE Single crystals of a high purity Fe-3 pet Si alloy, containing 0.007 pet C, were grown in vacuum by

Jan 1, 1962

By William E. Bruce

In recent investigation of drilling processes, the U.S. Bureau of Mines measured the operating characteristics of two percussive drills. Basically, this entailed measuring maximum piston velocities while drilling. The maximum piston velocity is not necessarily the same as the striking velocity. The latter is usually somewhat lower1 because most commonly used drills provide an air cushion which slows the piston just before it comes in contact with the drill rod. Penetration rates for the two drills were determined in nine rock types, and the physical properties of the same nine rocks were measured and tabulated. Then the penetration rates were plotted against the individual properties to determine the general relationships on which methods for predicting drilling rates could be based.2

Jan 1, 1970

By Huntington Adams

The arrangement of a flow of cyanide-pulp through Pachuca tanks in agitation, so as to permit a continuous process, instead of alternate filling, agitation, and emptying, has been proposed by various writers within the last two years, and more particularly by A. T. Grothe, agent for the Brown patents on Pachuca tanks in Mexico. It was first put into practice, I believe, by M. H. Kuryla at the Esperanza mine in El Oro, Mexico. The starting of agitation in Pachuca tanks after filling may offer no serious difficulties with ores which do not settle rapidly in such tall tanks; and the adaptation of the tanks to continuous agitation under such conditions may give simply a somewhat more convenient method of treatment and greater agitation-capacity for a given number of tanks, because of the saving of time lost in filling and discharging. But in the treatment of pulp which tends to settle rapidly, as in the cyaniding of concentrates or of the whole pulp of ores containing heavy sulphides, the packing of the slime at the bottom may cause much trouble. The use of the radial air-pipe attachments near the top of the cone and of the air-valve outside of the air-lift tube at the bottom may obviate the difficulty to some extent; but the action of the radial air-pipes on the cone-sides is that of a sand-blast, and their continuous use cuts through the tanks. Moreover, even when these pipes are used, some pulps will pack tightly below them in the cones. Under such conditions the use of Pachuca tanks with intermittent filling and discharging becomes a troublesome process. Time is lost in starting agitation; large quantities of compressed air are wasted; pulp is blown over the tank-tops; and not infrequently it may be necessary to dig out the bottoms of tanks by hand. This trouble is the only important one occurring in the use of Pachuca tanks; and, since it is caused by intermittent filling, the arrangement of a continuous flow of pulp from tank to tank,

Jan 1, 1912

By Hoyt Gale

RECENT work on borate deposits near Kramer, in the extreme southeast corner of Kern County, California, is of special interest to those who are making a study of the mode of origin of the borate minerals colemanite and ulexite. A valuable clue to the mode of origin of colemanite in its present known deposits is given in a paper by W. F. Foshag1, of the United States National Museum. Colemanite is found in or near original deposits of ulexite, from which it is supposed to have been derived by a change in the rate of movement or the character of the ground water. Indications that an alteration of this sort had produced colemanite were first recognized by the writer' in specimens collected in the Kramer district in 1920, and sent to W. T. Schaller, at U. S. Geological Survey, for identification. The identity of the two borate minerals in these specimens was not at once determined, but the relations of the minerals as seen in the specimens afforded a manifest clue to the origin of the deposits. Similar specimens were obtained by the writer from deposits in death Valley soon after he had examined the deposits near Kramer. After studying the specimens submitted to him Dr. Schaller wrote as follows: "I have finally positively identified the boron minerals you sent me with your letter of Sept. 27. The `white fibrous mineral like ulexite' is ulexite; the harder nodules' in the clay are colemanite, apparently formed from the ulexite as a result of leaching, with recrystallization in place-a theory that Foshag is working on." The present paper is a report on the facts observed at. the deposits near Kramer, and some general observations on the geological relations noted, which, unfortunately, still form only a very incomplete record.

Jan 2, 1926

By E. B. Thornhill

Discussion of the paper of E. B. THORNHILL, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 104, August, 1915, pp. 1653 to 1670. D. B. HUNTLEY, Oakland, Cal.-About 15 years ago it chanced to be my lot to cyanide some mill tailings, assaying about $5 per toll in gold and, a few cents in silver. It was in southern Idaho, a. desert region where costs are nearly as large as in central Nevada. We knew that we had a lot of tailings that had been amalgamated and contained about 1 lb. of quicksilver per ton. We knew that we would dissolve some of the quicksilver when we cyanided them with say 0.25 per cent. cyanide solution. We figured (optimistically) that the cyanide would dissolve all of the quicksilver, and we thought to capture all of that, 1 lb. per ton; and we figured out profits as partly gold, partly silver, and partly quicksilver from the recovery in working those tailings. Actually, however, we did this: We had a battery of three large, old-fashioned silver-mill retorts. We retorted our zinc-dust precipitate, recovering about ¼ lb. of quicksilver per ton treated. That was only a loss of 75 per cent. of what we originally had, but still it was profitable by virtue of the conditions. I mention it partly to call attention to the crude old way of doing it, and partly to call attention to how chemical methods for recovering quicksilver have developed in the last 15 years.

Jan 12, 1915

By E. M. Elkin, J. H. Schloen

All known methods of treating and recovering the various components of copper refinery slimes are discussed. The slimes treatment processes presently used by five copper refineries are described and flowsheets are given. A bibliography is appended. THE recent increase in anode copper production at the Noranda smelter placed an additional load on the Montreal East plant of Canadian Copper Refiners Limited. The consequent increase in the amount of anode slimes led to a careful consideration of the various methods of slimes treatment. A critical review of these methods is presented here in the belief that it would be of interest to copper refiners. No such review has yet been published, although a number of individual flowsheets have been described. To make the information of greater value, a questionnaire was sent to all copper refineries. While the overall response to the questionnaire was not entirely satisfactory, the foreign refiners gave much detail in their answers and expressed willingness to cooperate further if needed. Although the data below do not cover all refineries, it is thought that examples of all flowsheets currently in use are included. A comparison of these flowsheets should prove of interest. The paper is divided into two parts. One part deals with a discussion of all known methods of treating and recovering the various components of the slimes. The second describes the processes now in use at various copper refineries for the treatment of raw slimes up to the production of Doré bullion. A brief description of the two main electrolytic methods of parting Doré bullion is appended. Since the first commercial application of electrolytic refining of copper by J. B. Elkington in 1865, the treatment of anode mud or slimes has undergone many changes. The object of treating slimes has always been the recovery and separation of precious metals. With the passage of time, increasing attention has been paid to improvement in recovery and quality of byproducts, mainly selenium and tellurium. The original methods of treatment were crude, although relatively direct. For example," the slimes were fused on a dolomitic clay bed in a reverbera-tory furnace; the slag was removed and the resulting metal cupelled to silver and gold. In another process, the dried slimes were oxidized and scorified on the lead bath of a cupelling furnace. Later, these pyrometallurgical methods were modified by sulphuric acid leaching, followed by fusion with niter in a reverb eratory furnace. A preliminary oxidizing roast improved the leaching step. Straight hydro-metallurgy has not found practical application. No matter what method is employed, the result is Dorb metal—a silver-gold alloy, with or without the metals of the platinum group. Characteristics of the Slimes Anode slimes are made up of those components of the anodes which are not soluble in the electrolyte. They contain varying quantities of copper, silver, gold, sulphur, selenium, tellurium, lead, arsenic, antimony, nickel, iron, silica, etc. The color of raw slimes is grayish black and the particle size is —200 mesh. However, Baraboshkin and Gaev (Ref. 1, p. 37), describe light gray colored slimes from the electrolysis of secondary copper which are composed predominantly of sulphates and of basic salts. In anode furnace practice primary and secondary metals are not usually segregated and such slimes do not commonly occur. Copper in the slimes originates to a large extent in the cuprous oxide of the anodes and is therefore dependent on the oxygen content of the latter: Cu2O + H2SO4 + CuSO4 + H2O + Cu [I] Opinions have been expressed that some of the copper is formed by decomposition of cuprous to cupric sulphate Cu2SO4 ? CuSO4 + Cu PI The product of either reaction is very finely divided. Depending on the slimes composition, much of the copper is combined with sulphur, selenium, tellurium, etc. The balance of the copper is in the free metallic state.

Jan 1, 1951

By J. Marshall Downey

The most fortunately situated U. S. potash producer-whether in New Mexico, California, or Utah--once simply took from the ground a mixture of sodium chloride and potassium chloride, crushed it to a maximum of 10 mesh, and separated the two salts by physical methods. He piled the sodium chloride on the desert and sold the potassium chloride to fertilizer mixing companies. Seven companies in the Carlsbad basin of New Mexico now use at least three basic processes for making the separation and at least three more processes have been or are under investigation. In addition, two companies outside the basin use two methods for taking KC1 from natural brines

Jan 12, 1958

By R. H. Marshall, J. Welchner, E. S. Rowland

THIS paper presents results on an exten¬sion into the realm of high-carbon steels of some work recently published' on the effects -of time at temperature, quenching temperature and prior structure on the hardenability of one 0.20 and four 0.40 per cent carbon alloy steels. It was shown at that time that unless the conditions of time, temperature and prior structure are substantially the same in performing the hardenability test as in conducting harden¬ing of parts in production, the correlation of hardenability information with the [ ] hardness and properties of production parts is often not of satisfactory accuracy. The general effects of these variables on the austenitic grain size, distribution of excess carbides and critical cooling rate have been known for many years and one or more have been investigated by Shepherd ,2 3 Davenport and Bain,4 Digges,5,6 Digges and Jordan,7 Post and associates' and Roberts and Mehl,9 to mention only a few. There has been no systematic investigation, however,' into the quantitative variations produced on the hardenability of commercial high¬carbon steels by changes in these factors of time, temperature and prior structure. PROCEDURE A plain carbon hypereutectoid steel, S.A.E. 52100 and Graph-Mo, a molyb¬denum-bearing high-carbon steel contain¬ing some graphite, were chosen for this investigation. The chemical analyses of these electric-furnace steels are given in Table I. [ ] The procedure used was exactly that reported previously,' hence the details will not be repeated here. Normalized (1650°F.) and spheroidized prior structures were utilized on all steels with hot-rolled and quenched (1600°F. oil) prior conditions added for the plain carbon steel. The end-quench test developed by Jominy10 was selected for use in this investigation and, with the noted exceptions, the American Society for Testing Materials standard. procedure was followed. The effect of time at temperature was examined at intervals of 0, 10 and 40 min. and 4 hr., and a few i6-hr. tests were run. Salt-bath heating of the specimens was employed to control and minimize the

Jan 1, 1944

By Edward Saibel

The object of this study is to investigate the effect of prior tensile strain on the fracture stress of a metal. This is done in a theoretical manner starting from the point of view developed by the author in his thermodynamic theory of the fracture of metals. The results are compared with experimental findings and a rational interpretation is given to work that shows the variation of fracture stress with prior tensile strain. Theory op Fracture In the thermodynamic theory of the fracture of metals developed earlier,' it was shown that a critical strain energy per unit volume exists. This is characteristic of the material and may be calculated from basic thermodynamic data. When the area under the flow curve reaches this characteristic value, fracture occurs. The general criterion for fracture is expressed in the form « ± u. = JLJW/V [r] where L, is the latent heat of melting of the unit volume, AV/V is the ratio of the change in volume of the unit volume to the original unit volume on passing from the solid to the liquid state, uo is an initial energy density, and J is a conversion factor, which changes energy from heat to mechanical units. As a first approximation, it will he assumed that the stress-strain curve is the straight line that extends from the point of maximum load onward, extrapolated back to the axis of zero strain, for example, line AC of Fig. I. If the point of intersection of the straight line with the axis of zero strain is represented by v., and the slope of the straight line is p, the analytic form of the flow curve is a = (To + pd [2] and the strain energy per unit volume evaluated from Jud6 becomes (u,6 + pa2/2). When this latter term reaches the critical value JLbVIV (designated hereafter by M), it is assumed that fracture occurs. This leads to the following expression for the fracture stress: a; = V«r.2 + iMp [3] The strain at fracture may be calculated from Eqs 2 and 3. It is assumed in this paper that the initial energy density is either zero or that it may be neglected. Furthermore, the complicated states of stress and of strain existing in the necked region of the tensile specimen after "necking" has occurred will also be neglected for the present, so that average conditions will be assumed to prevail. Flow and Fracture Curves LudwigZ attributed to materials two fundamental properties: (I) a resistance to flow and (2) a resistance to fracture. He reasoned that at each instant the

Jan 1, 1948

By Edward Saibel

The object of this study is to investigate the effect of prior tensile strain on the fracture stress of a metal. This is done in a theoretical manner starting from the point of view developed by the author in his thermodynamic theory of the fracture of metals. The results are compared with experimental findings and a rational interpretation is given to work that shows the variation of fracture stress with prior tensile strain. Theory op Fracture In the thermodynamic theory of the fracture of metals developed earlier,' it was shown that a critical strain energy per unit volume exists. This is characteristic of the material and may be calculated from basic thermodynamic data. When the area under the flow curve reaches this characteristic value, fracture occurs. The general criterion for fracture is expressed in the form « ± u. = JLJW/V [r] where L, is the latent heat of melting of the unit volume, AV/V is the ratio of the change in volume of the unit volume to the original unit volume on passing from the solid to the liquid state, uo is an initial energy density, and J is a conversion factor, which changes energy from heat to mechanical units. As a first approximation, it will he assumed that the stress-strain curve is the straight line that extends from the point of maximum load onward, extrapolated back to the axis of zero strain, for example, line AC of Fig. I. If the point of intersection of the straight line with the axis of zero strain is represented by v., and the slope of the straight line is p, the analytic form of the flow curve is a = (To + pd [2] and the strain energy per unit volume evaluated from Jud6 becomes (u,6 + pa2/2). When this latter term reaches the critical value JLbVIV (designated hereafter by M), it is assumed that fracture occurs. This leads to the following expression for the fracture stress: a; = V«r.2 + iMp [3] The strain at fracture may be calculated from Eqs 2 and 3. It is assumed in this paper that the initial energy density is either zero or that it may be neglected. Furthermore, the complicated states of stress and of strain existing in the necked region of the tensile specimen after "necking" has occurred will also be neglected for the present, so that average conditions will be assumed to prevail. Flow and Fracture Curves LudwigZ attributed to materials two fundamental properties: (I) a resistance to flow and (2) a resistance to fracture. He reasoned that at each instant the

Jan 1, 1948

By F. R. Brotzen, L. D. Whitmire

Single crystals of high-purity molybdenum were de-formed at temperatures from 195°to 473°K, and the effect of deformation on the electrical resistivily was deler-mined. To separale the resislivity components of point and line defecls some cryslals were annealed at 473°K. The vale of resislivily increase wilh strain was nearly linear and was strongly dependent upon the deformation temperature. Point dejects are annealed out without any effect on the flow stress. At low temperatures the flow stress is a linear function of the square root of the resistivity increase attributable to dislocations. ELECTRICAL-resistivity measurements have been used successfully to gain information on structural changes in metallic materials. During plastic deformation the electrical resistivity rises because of electron scattering from newly created lattice defects. Such measurements lend themselves, therefore, to corroborating results from direct observation of lattice defects and, to a certain extent, to correlating defect densities and distribution with mechanical properties. Published information on research with single crystals of the bcc metals of Group VI, particularly molybdenum, is still limited. Yet, molybdenum single crystals of relatively high purity can be readily prepared by electron-beam-melting techniques. Furthermore, some valuable information on the defect structure of deformed crystals by direct observation is available. Lawley and Gaigher,1 for example, have examined dislocation configurations in deformed molybdenum crystals by means of transmission electron microscopy. Their results revealed that the dislocation density and distribution were strongly dependent upon the deformation temperature. These findings differed from those by Keh and weissmann,2 who found that the average dislocation density in polycrystalline iron deformed between 138° and 298°K depended only on the degree of strain and not on the deformation temperature. Martin3 and peiffer4 showed that point defects introduced in polycrystalline molybdenum by cold work can be eliminated by annealing at a relatively low tempera-ture. In view of their work it became apparent that resistivity measurements of suitably annealed crystals could disclose changes in their dislocation structure and contribute to the understanding of the work hardening of molybdenum crystals. EXPERIMENTAL PROCEDURE Crystals were grown by electron-beam zone melting5,6 of 0.062-in.-diam molybdenum rods (99.99 pct) supplied by General Electric Lamp and Wire Division, Dover, Ohio. The crystals, about 4 in. long, were prepared by using five zone-refining passes at a speed of about 6 mm per min in a vacuum of about 5 X l0-6 Torr. The resistivity ratio of the crystal, p(4.Z°K)/p(273°K), was generally near 10-3. These crystals were used as tensile specimens of uniform diameter in the "as-grown" condition. They were oriented for maximum shear on the (011)[111] slip system (Schmid factor >0.49). The specimens were held in spherically seated Templin-type grips so as to minimize bending. Samples were deformed on an Instron machine at a strain rate of about 5 X 10-5 sec-1 in an isopentane bath with dry ice at 195°K, in ice water at 273°K, and in a vegetable-oil thermostat at 373° and 473°K. The temperature in the latter was maintained constant within +2°K. Resistance measurements were carried out with a Kelvin double bridge. The resistance of the potential leads was kept low by using large-diameter wires outside the low-temperature bath. Many of the resistance data were checked by measurements made with an ac bridge. Current and potential leads were spot-welded to the specimens. The distance between the potential leads, about 3 in., was also considered to be the gage length for the strain measurements. Diameter and gage length of the samples were measured optically with an error of less than 2 pct. These measurements were used also to insure that the deformation had been uniform over the gage length of the specimen. Resistivity changes were then determined from the resistance measurements at 4.2°K assuming constancy of volume. In the course of a test, the crystal diameter, gage length, and resistance at 4.2°K were determined first in the initial state and subsequently for various amounts of elongation.

Jan 1, 1968

By R. V. Lundquist

Leaching manganese-bearing materials with NaOH to remove caustic-soluble silica has been demonstrated as a method for upgrading manganese. Those materials containing opaline varieties of silica respond most readily. Spent leach liquors are regenerated by treatment with lime to precipitate calcium silicate and to reactivate the NaOH for leaching. ALL of our larger domestic deposits of manganese are very low grade, but estimated tonnages in these deposits are large enough to constitute a potential strategic reserve of manganese for emergency periods, provided these ores can be upgraded sufficiently to meet industrial specifications. Many types of processes have been suggested for upgrading these ores, several have been studied in pilot plants, and a few have attained limited commercial production for special purposes. The hydrometallurgical process to be described below proposes a leaching operation for removing caustic-soluble silica and other gangue minerals and consequently upgrading a manganese ore or flotation concentrate to a commercially acceptable moduct. It is known that some forms of silica and some silicate minerals are soluble in NaOH solutions under suitable conditions. This new process proposes to use NaOH for removing the soluble materials from manganese ores or concentrates and, as a result, upgrade the manganese content. Since spent leach liquors are not efficient leaching agents the liquor must be treated with lime to precipitate calcium silicate and reactivate the NaOH. Experimental Procedure Manganese-ore samples ground to —35 mesh were leached in iron containers into which the ore sample and appropriate NaOH solutions were placed. Flotation concentrates were already ground to —200 mesh. The slurries were then placed on a hot plate or into a pressure digester and stirred continuously during the period of digestion. Where the- digestion was performed at atmospheric pressures, water lost by evaporation was replaced at regular intervals to maintain approximately a constant volume of slurry. In the pressure digester, volume changes were not controlled. After digestion, the slurry was allowed to cool enough for easy handling, but it was filtered hot, 50" to 70°C, on a Buechner filter. Filtration under these conditions was satisfactory. The resulting filter cake was washed and dried. In most instances, a single leach would not produce maximum extraction of silica from the ore sample; consequently, the dried tailing was treated again in the same manner with a fresh solution of NaOH to obtain an additional extraction of silica. This procedure was repeated a number of times to get the maximum extraction of silica. Usually three or at most four stages of leaching were adequate for this purpose. This leaching procedure was used for obtaining the data reported in this paper on the effects of NaOH concentration, pulp dilution, temperature, and time of digestion on the efficiency of extraction of silica from the ore sample. The experimental procedure does not match industrial methods. consequently tests for counter-current leaching were set up. Data from these tests are not yet complete, but in a qualitative way they indicate that thickeners between stages of leaching will be satisfactory and that the quantity of silica in a leach liquor moving forward to a new solid has only a minor effect on the quantity of silica extracted from the new solid. A pilot plant is now being designed for operation in the near future to test and evaluate the merits of this process.

Jan 1, 1954