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By Arthur F. Taggart, T. C. Fitt, A. W. Thomas

IT was noticed early by operators that high recoveries and flocculation of the sulphide minerals were closely correlated in agitation-froth flotation. Later, this readily visible flocculation was found almost invariably to be due to the binding together of the oiled sulphides by minute air bubbles, and is now known to be characteristic of pulps in which at least one of the mineral species is coated with an insoluble collecting oil. In 1930 it was reported1 that in differential flotation a correlation exists between Brownian movement of particles in the pulp and their nonfloatability, and that Brownian movement and dispersion are likewise correlated, whence it would appear to follow that dispersion of a mineral particle in a flotation pulp denotes a particle condition unfavorable to flotation. In 1934 it was postulated2 that Brownian movement, dispersion and nonfloatability all flow from the condition of the surface of the dispersed particles. It was also postulated at that time that the surfaces of dispersed particles are ionized, the ionized compound being a product of reaction between a component of the particle and a. component of the pulp, of a mass solubility of the general order of a fraction of a milligram to 15 to 20 mg. per liter. It was then further asserted, and has since been confirmed by Bankoff,3 that sulphides so conditioned with soluble collectors as to be floatable flocculate without the intervention of air bubbles as binding media. The present paper comprises an inquiry into the nature of the bound and counter ions in zinc sulphide dispersed by sodium arsenate. A part of its findings was mentioned in the 1934 paper above cited.2 The tests show that: I. When powdered granular zinc sulphide is immersed in aqueous solutions of sodium arsenate, arsenate ion is abstracted from solution and anchored to the solid surface, while sulphate and lower sulphoxy ions are concurrently displaced therefrom in substantially stoichiometric quantities. 2. The ion counterbalancing the anchored arsenate ion is zinc. 3. Dispersion and Brownian movement of zinc sulphide are concurrently maxima at an arsenate-ion concentration lying between 0.01 and 0.001-molar sodium arsenate. 4. Any condition or reaction that tends to remove the zinc arsenate coating from the zinc sulphide particles decreases dispersion and Brownian movement concurrently. EXPERIMENTAL Three samples of zinc sulphide were used. Lot I was C.P. zinc sulphide, washed well beyond absence of chloride, as shown by test with silver ion. Lot 2 was prepared by precipita-

Jan 1, 1943

By Ralph W. Marsden

The natural iron ores of the Lake Superior Region in the United States are being replaced by iron-ore concentrates produced from magnetite- or hematite-rich horizons in the Precambrian cherty iron formations. The production of natural ores will soon be less than one-half of the total ore shipped annually. The tonnage of natural ore produced will continue to decline until it is a minor percentage of the ore shipped. The natural ores include (1) soft ore, (2) hard ore, ( 3) conglomerate ore and ( 4) siliceous ore. The soft ores are the important ore type and are sometimes termed "Lake Superior type ore". These ores are in situ deposits of hematite and limonite formed by the leaching of silica and other gangue materials in the iron formations. The leaching is believed to have been done by downward moving surface waters. In deep ore deposits, generally over 1000 feet below the present surface, circulation and leaching action may have been assisted by hydrothermal activity. Hard ore deposits occur on the Vermilion and Marquette ranges where hematite or magnetite has replaced the silica (and possibly some silicates) in cherty iron formation. These ores commonly occur in structural situations favorable for the movement of hydrothermal waters. The ores are believed to be the result of hydrothermal action with iron, possibly from the iron formation, transported by hydrothermal waters to areas favorable for the replacement of silica by iron oxides. Certain stratigraphic horizons of the Lake Superior Precambrian cherty iron formations contain sufficient iron as magnetite or hematite, with a grain size and texture that will give adequate mineral liberation, to yield an ore-quality product after grinding and concentration. The magnetite-rich deposits are termed magnetite taconites. These ores occur on the Mesabi, Gogebic, and Marquette ranges. Magnetite taconite ores are unenriched cherty iron formation and are the result of the sedimentary deposition of the iron formation and the metamorphic history of the rock. The commercial quality hematite-rich iron formations in Michigan are termed jasper ores. The jasper ores are being mined on the Marquette and Menominee ranges. These ores are composed of specular or granular hematite associated with quartz and iron silicates. The jasper ores appear to be recrystallized iron formations in which iron, prior to recrystallization, occurred as hematite.

Jan 1, 1968

By J. G. Thompson

Determinations of the hydrogen content of irons and steels invariably are subject to two serious difficulties: (I) the determination of amounts of 0.001 per cent or less of any constituent requires an analytical procedure of unusual precision and accuracy, and (2) the hydrogen content of many samples is dccidedly not stable; i.e., there is no assurance that the content at the time the analysis is made is the same as it was when the sample was taken or at some previous time in the history of the piece. In respect to both the precision and speed of the determination, the vacuum-extraction procedure for the determination of hydrogen possesses advantages over the vacuum-fusion procedure, which has been the recognized standard for the detcrmination of other gaseous elements in sted-— oxygen and nitrogen for example. The basic facts upon which the vacuum-extraction procedure is based—i.e., the evolution of gas from solid steel when it is heated in vacuum, and the fact that the evolved gas is rich in hydrogen—were observed by Graham1 many years ago. Subsequent investigations have shown that hydrogen exists in steel chiefly as interstitial solid solution (i.e., in atomic dispersion) and perhaps to some extent as hydridcs that are unstable and decompose to form atomic hydrogen. In either case practically all of the hydrogen in steel at elevated temperatures exists in the atomic condition and consequently is able to diffuse readily through the metal. In contrast to this, other gaseous elements, such as oxygen and nitrogen, normally are present in steel chiefly in the form of relatively stable compounds such as oxides or silicates and nitrates; i.e., the oxygen and nitrogen atoms are fixed in stable combinations and are not free to migrate. The only oxygen or nitrogen that can diffuse in steel is the small amount in solution (atomically dispersed) and the rate of diffusion of these atoms is much less than that of hydrogen because of their greater atomic volume and lower mobility. Consequently, it is possible to extract most or all of the hydrogen from solid steel in a reasonable time at moderately elevated temperatures, but the procedure is not applicable to the determination of oxygen or nitrogen. It is only within the last decade that these observations have been developed into an analytical procedure for the determination of hydrogen. Apparatus and Procedure The apparatus used at the National Bureau of Standards,6 for the determination of hydrogen by the vacuum-extraction procedure, is shown schematically in Fig. I. The specimen, freshly cleaned and dried,* is suspended on a fine wire within the quartz furnace tube that is connected to the reservoir system and analytical train.

Jan 1, 1945

By M. C. Leverett

KNOWLEDGE of the theory underlying the behavior of mixtures of fluids in reservoir rocks is essential to the proper solution of certain types of problems in petroleum pro-duction, but is as yet incompletely devel-oped. The object of this paper is to show the application of well established thermody-namic and physical principles to these prob-lems, and thus to assist in the development of the basic theory. For convenience the problems to be considered here may be divided into two groups: I. Static problems, involving only the static balance between capillary forces and those due to the difference in densities of the fluids; i.e., gravitational forces. 2. Dynamic problems, involving analysis of the motion of mixtures of immiscible fluids in porous media under the influence of forces due to gravity, capillarity, and an impressed external pressure differential. CAPILLARY EQUILIBRIUM IN SANDS Under this heading the static type of problem will be discussed and the results of experimental investigations on the capillary properties of unconsolidated sands will be presented. Although the discussion of this section is, in a sense, prefatory to the treat-ment of problems of mixture flow, the con-cepts developed here have considerable intrinsic importance apart from their ap-plication to flow problems. For, it is reason-able to postulate that the reservoir fluids are, owing to their long existence in undis-turbed mutual contact prior to exploitation, in substantial equilibrium. It follows that their distribution in the reservoir at the time of tapping should be entirely predict-able from the theory of capillary equi-librium, provided certain experimentally measurable properties of the reservoir rock are known. Knowledge of the distribution of the several fluids in the reservoir is, of course, helpful in the estimation of reserves and in other problems. It is to be emphasized that throughout the discussion of capillary statics it is as-sumed that the fluids are in equilibrium from the capillary standpoint. Thus, water, where it is referred to as being in a reser-voir, will be understood to be interstitial water, present at the time of drilling the reservoir, commonly termed "connate" water. The theory developed here is perfectly general for any porous solid, whether a carefully prepared unconsolidated sand or a natural sandstone from an oil reservoir. At present, however, only problems in-volving clean, unconsolidated sands can be made to yield numerical solutions, since only such sands have been adequately in-vestigated experimentally. Experimental evaluation of the pertinent properties of natural reservoir rocks will permit the ex-tension of the numerical treatment to prob-lems involving these materials. We shall now consider in some detail the static equilibrium of fluid mixtures in porous solids; that is, the manner in which the reservoir fluids are distributed vertically when the forces due to capillarity are just balanced by those due to gravitation.

Jan 1, 1940

By S. W. Parr

FRom a study of sulfur with reference to its specific combination in coal, published as University of Illinois Bulletin No. 111, 1919, it is now possible to determine the various forms of this constituent with a good degree of accuracy. This fact suggests two questions: (1) Are the same analytic methods applicable to coke? (2) Is there any correlation between the forms of sulfur as it occurs in coal and the residual sulfur found in the finished coke? The answer to the second question might be helpful in answering a still further question as to what chemical route the sulfur travels during the carbonization process. While the special studies along these several lines are by no means complete, a few preliminary statements are herewith presented. They may, at least, prove suggestive of further possibilities from a continuation of research along these lines. There is no reason, chemically, why the analytic methods devised for coal should not apply to coke and a fair amount of experience in connection with such use affords confirmation of this statement. The procedure in the case of coal may be briefly outlined as follows: Combinations of sulfur as sulfate, or sulfides other than FeS2, are readily dissolved without disturbing either the pyrite sulfur or the sulfur that is in organic combination by means of dilute hydrochloric acid— 1 part of concentrated HC1 to 10 parts of water or approximately 3 per cent. acid. Digestion at 60" C. for 24 hr. insures the complete removal of the sulfur thus combined. In freshly mined coal the amount of such sulfur is very small; weathering processes, however, may very materially increase the amount of sulfate present. Sulfur in the form of iron pyrites, or marcasite, may be quantitatively removed without oxidation of the organic sulfur as follows: A dilute solution of nitric: acid is prepared having 1 part of concentrated HNO3 to 3 parts of water or with an approximate specific gravity of 1.12. The coal sample, ground to 100 mesh, is digested with this solution at room temperature for 3 or 4 days, filtered and evaporated to dryness, taken up with water, and acidified with hydrochloric acid. It is now ready for precipitation with barium chloride in the usual manner. If sulfate is present in the original sample to an appreciable amount, it should be removed by the procedure outlined above. It is not necessary here to give the methods for determining the two

Jan 1, 1920

By F. L. Bosqui

A. L. BlomFIeld, Denver, Col. (communication to the Secretary.*) — Mr. Caldecott says on p. 67: "The Dorr thickener shown, while a useful device when crushing with cyanide solution for removing surplus solution from slime pulp prior to air-lift agitation or vacuum filtration, is not adapted to effect as complete a separation of water from settled slime as the ordinary intermittent settlement and decantation." This statement might have passed muster in this country several years ago when. the Dorr thickener was a new device, but its use in hundreds of mills in the United States has demonstrated that as thick a product is being discharged from it as was obtained from the intermittent settling which it has supplanted. • It is interesting to note that recent investigation, especially the work of 11. 6. Coe and G. H. Cleveilger,' in the March Bulletin of the Institute, under the title: Laboratory Method for Determining the Capacities of Slime Settling Tanks, has developed the general theory of settlement and explains the results obtained in practice. Just as free settlement is a function of surface area, so thickening after the zone of free settlement is passed is a function of time. The time required is obtained by the capacity or volume provided in the settler for this thickening zone. Each pulp is a problem in itself, both in regard to free settlement and to time required to reach a commercially finished thickness. Some pulps require 48 hr. and more to reach a density of 40 per cent. solids; others no coarser to the screen test reach a density of 65 per cent.' solids in a fraction of that time. In thickening any pulp a point is reached where the increase in density is so slow as to be commercially unprofitable. When any part of the pulp has reached this point it should pass on for treatment—its place in the thickener should be occupied by pulp which has not yet reached the commercial limit. By doing this the whole volume of the settling tank is kept in active use. Thus the continuous thickener keeps the whole tank at work to its commercial limit, while the intermittent settler has much of its volume occupied at times by pulp which is either quite finished thickening or at least thickened past the commercial point. The mechanical efficiency of the continuous thickener can be the only argument for limiting this statement. In my own experience I have never

Jan 1, 1916

By D. Turnbull, J. H. Hollomon, J. C. Fisher

UNDERSTANDING of the diffusion problem has recently been furthered by the analysis of Birchenall and Mehl.1 They pursued the problem of the variation of the diffusion coefficient with composition for non-ideal solid solutions. Their analysis follows the tradition of Wagner,2 Jost,3 Dehlinger,4 and Darken,' who assumed the net flux of dif¬fusing material to be proportional to the gradient of a quantity related to free energy. The basic assumption in Birchenall and Mehl's formulation of the problem is that the net flux of diffusing material is proportional to a thermodynamic activity gradient. To estimate the applicability of the derived relations, they corrected the diffusion coefficients of carbon in austenite by utilizing Smith's' activity data for carbon, and the diffusion coefficients for zinc in copper with activity data computed from the vapor pressure measurements of Hargreaves.7 The corrected coefficients for carbon were virtually independent of carbon concentration. For the diffusion of zinc in copper a moderate variation of diffusion coefficient with concentration remained after the correction. The problem of diffusion can be formulated in another way than that used by Birchenall and Mehl. The method is that of chemical rate theory and has been used by Eyring and his coworkers8,9 as well as by Eyring and Zwolinski10 in a discussion to Birchenall and Mehl's paper. As yet the method has not been applied to substitutional solid solutions. On the basis of their assumptions, Eyring and Zwolinski derived a relation between the diffusion coefficient and activity that is identical with that of Dehlinger and Darken but which does not correct for the variation of the diffusion coefficient with concentration as well as does the relation derived by Birchenall and Mehl. It was thought that the theory of diffusion would be more complete if the inconsistency between the two analyses could be rationalized and if diffusion in substitutional alloys were analyzed on the basis of the concepts of the chemical rate theory. CHEMICAL RATE THEORY According to the theory of absolute reaction rates8 the reaction [A,+A2+ ... +.A;->X,+X2 +...+X; EqI] is viewed as taking place in two steps. First the reactants A1, A2, . . . A[i] combine to form an activated complex M with which they are in equilibrium; [A, + A2 + .. . + Ai = M. Eq 2] Second the activated complex decomposes to give the products X1, X2. . .. X[j]; [M->X1+X2+ ... +.X;. Eq3] It has been shown8 that the number of activated complexes decomposing per unit volume per unit time is given by the expression† [kT]

Jan 1, 1948

By Tasuku Fuwa, John Chipman

Equilibrium data on the reactions of gases with carbon and oxygen dissolved in liquid iron are reviewed and correlated. A source of error in oxygen analysis of graphitic samples is exposed. New experimental data on the oxygen content of high -carbon iron in equilibrium with carbon monoxide indicate that the activity coefficient of oxygen is decreased by additions of carbon. The carbon-oxygen product decreases slightly with increasing carbon content. In recent years a number of investigations have been reported dealing with the equilibria between carbon and oxygen in liquid iron and gases containing carbon oxides. The laboratory study of these reactions dates back to 1931 with the publication of a paper by Vacher and Hamilton' on "The Carbon-Oxygen Equilibrium in Liquid Iron". The principal object of this study was to obtain data on the reaction shown by Eq. [3] below; their data and others by vacherZ permit evaluation of the other equilibrium constants as well. Subsequent studies have been reported by Matoba, Phragmen and Kalling and by Marshall and Chipman.5 The equilibria may be expressed by the following three equations: C + CO,= 2CO;Kl = Pc° [1] 0-+CO = CO,;K2=-P co, "0.PCO c + O = CO; K3 = In the equilibrium constants, ac and a0 are taken as equal to [% C] and [% 0] respectively in the infinitely dilute solution. At finite concentrations an activity coefficient is introduced such that ac =fc [%C], and so forth. It is to be noted that these equations represent only two independent relations, the third being derivable from any two. Richardson and Dennis have determined the conditions of equilibrium in reaction [I] at temperatures of 1560" to 1760°C. Their results have been confirmed by Rist and chipman7 who have shown how the data may be extended to cover the entire range of liquid compositions at temperatures from the eutectic up to 1760°C. An approximate confirmation has been reported by Fuwa and chipman.' These investigations also established the activity coefficient of carbon which was shown to increase rather rapidly with increasing concentration. For the very dilute solutions the value of Kl is expressed in the equation: log^i = - 7280/T+ 6.65 This equation leads to a value of Kl = 430 at 1540° C in excellent agreement with the average value of Marshall and Chipman.5 It is shown as line 1 in Fig. 1 together with the experimental observations. In the case of reaction [2] the direct experimental results can be supplemented by observations on the corresponding reaction with hydrogen, namely reaction [4]:

Jan 1, 1961

Page Foreword. By Edmund M. Wise..................... 3 A.I.M.E. Officers and Dircctors...................... 4 Institute of Metals Division Officers and Committees............ 7 Institute of Metals Division Annual Award Certificate............ 8 Institute of Metals Division Lectures and Lecturers............. 9 Photograph of E. H. Dix, Jr., Institute of Metals Division Lecturer...... 10 PAPERS Acceleration of the Rate of Corrosion by High Constant Stresses. By E. H. Dm, JR. (Institute of Metals Division Lecture, T. P. 1204).......... 11 Variation of Internal Friction with Grain Size. By Clarence Zener and R. H. Randall. (T.P. 1146, with discussion) .............41 Changes in Damping Capacity during Annealing of Alpha Brass. By John T. NoRton. (T.P. 1168, with discussion)................49 An Electron Diffraction Study of Anodic Films. By R. A. HarrinQton and H. R. Nelson. (T.P. 1158).....................62 Determination of Orientations by Etch Pits. By Charles S. Barrett .and L. H. Levenson. (T.P. 1171, with discussion).............76 Process of Precipitation from Solid Solution, I—A Crystallographic Mechanism for the Aluminum-copper Alloys. By Carl H. Samans. (T.P. 1186). . . 85 Age-hardening of Aluminum Alloys, IV — Discussion of the Theory. By WilTJam L. Fink and Dana W. Smith. (T.P. 1083, with discussion). . . 95 Structure of Aluminum after Compression. By Charles S. BaRREtt and L. H. evensonON. (T.P. 1104, with discussion)................112 Recrystallization Texture of Aluminum after Compression. By ChaRlEs S. BarRett. (T.P. 1141, with discussion)................128 Plastic Deformation and Recrystallization of Aluminum Single Crystals. By J. A. Collins and C. H. Mathewson. (T.P. 1145, with discussion) . . . 150 Recovery and Recrystailization in Long-time Annealing of 70-30 Brass. By S. E. Maddigan and A. I. Blank. . (T.P, 1166, with disonssion).....170 Correlation of Deformation and Recrystallization Textures of Rolled 70-30 Brass. By R. M. Brick. (T.P. 1144, with discussion).........193 Tensile Deformation of Critically Oriented Brass Crystals. By H. L. Burghoff. (T.P. 1149).............................214 Recrystallization of Lead. By Paul A. Beck. (T.P. 1101, with discussion). . 222 Simple Method of Thermal Analysis Permitting Quantitative Measurements of Specific and Latent Heats. By Cyril Stanley Smith. (T.P. 1100, with discussion).............................236 Metallographic Study of Internal Oxidation in the Alpha Solid Solutions of Copper. By Frederick N. Rhines. (T.P. 1162, with discussion). . . . 246

Jan 1, 1940

Page Foreword. By Edmund M. Wise..................... 3 A.I.M.E. Officers and Dircctors...................... 4 Institute of Metals Division Officers and Committees............ 7 Institute of Metals Division Annual Award Certificate............ 8 Institute of Metals Division Lectures and Lecturers............. 9 Photograph of E. H. Dix, Jr., Institute of Metals Division Lecturer...... 10 PAPERS Acceleration of the Rate of Corrosion by High Constant Stresses. By E. H. Dm, JR. (Institute of Metals Division Lecture, T. P. 1204).......... 11 Variation of Internal Friction with Grain Size. By Clarence Zener and R. H. Randall. (T.P. 1146, with discussion) .............41 Changes in Damping Capacity during Annealing of Alpha Brass. By John T. NoRton. (T.P. 1168, with discussion)................49 An Electron Diffraction Study of Anodic Films. By R. A. HarrinQton and H. R. Nelson. (T.P. 1158).....................62 Determination of Orientations by Etch Pits. By Charles S. Barrett .and L. H. Levenson. (T.P. 1171, with discussion).............76 Process of Precipitation from Solid Solution, I—A Crystallographic Mechanism for the Aluminum-copper Alloys. By Carl H. Samans. (T.P. 1186). . . 85 Age-hardening of Aluminum Alloys, IV — Discussion of the Theory. By WilTJam L. Fink and Dana W. Smith. (T.P. 1083, with discussion). . . 95 Structure of Aluminum after Compression. By Charles S. BaRREtt and L. H. evensonON. (T.P. 1104, with discussion)................112 Recrystallization Texture of Aluminum after Compression. By ChaRlEs S. BarRett. (T.P. 1141, with discussion)................128 Plastic Deformation and Recrystallization of Aluminum Single Crystals. By J. A. Collins and C. H. Mathewson. (T.P. 1145, with discussion) . . . 150 Recovery and Recrystailization in Long-time Annealing of 70-30 Brass. By S. E. Maddigan and A. I. Blank. . (T.P, 1166, with disonssion).....170 Correlation of Deformation and Recrystallization Textures of Rolled 70-30 Brass. By R. M. Brick. (T.P. 1144, with discussion).........193 Tensile Deformation of Critically Oriented Brass Crystals. By H. L. Burghoff. (T.P. 1149).............................214 Recrystallization of Lead. By Paul A. Beck. (T.P. 1101, with discussion). . 222 Simple Method of Thermal Analysis Permitting Quantitative Measurements of Specific and Latent Heats. By Cyril Stanley Smith. (T.P. 1100, with discussion).............................236 Metallographic Study of Internal Oxidation in the Alpha Solid Solutions of Copper. By Frederick N. Rhines. (T.P. 1162, with discussion). . . . 246

Jan 1, 1940

By W. A. Koehler, M. E. Hinkle

INTRODUCTION THE oxidation of pyrites and marcasite in coal-mine strata to produce discolored acid mine drainage has long been explained by chemical reactions occurring in three stages: I. The iron sulphide minerals are oxidized by air in the presence of water to produce a nearly colorless solution of fer¬rous (iron) sulphate and some sulphuric acid. 2. The ferrous sulphate and part of the sulphuric acid combine with additional oxygen to form ferric (iron) sulphate. 3. The ferric sulphate hydrolyzes to form a reddish-brown precipitate and additional sulphuric acid. Nevertheless, chemical data alone are not sufficient to explain all observed facts. The first stage seems to proceed more slowly in the chemical laboratory than in nature. The second and third stages nor¬mally occur to a marked extent within a few days with raw mine water. However, the visible discoloration that characterizes these latter stages will not develop for months if the mine water is sterilized. By means of bacteriological techniques, two organisms have been isolated from acid coal-mine drainage. These are believed to have a part in promoting the chemical reactions summarized above. One organism is considered to be Thio¬bacillus thiooxidans, which is known to be able to convert elementary sulphur or sodium thiosulphate to sulphuric acid. Its relation to the formation of acid mine drainage has not yet been established. Apparently it does not promote the oxida¬tion of ferrous iron compounds in mine, drainage to the ferric state. The second organism has not been identi¬fied by name but is described as "Gram negative, non-spore-forming rods approxi¬mately 0.4 micron wide by o.8 to 1.0 micron long." A pure culture of this when added to sterile mine water will cause the latter to become amber and develop the typical rusty precipitate. However, it has not been found to convert sulphur com¬pounds to sulphuric acid. Further research is planned to determine whether or not these microorganisms play a significant part in the first stage of oxidation whereby pyrites and marcasite minerals go into solution. Some of the conditions found in abandoned sections of coal mines, such as a reduced percentage of oxygen and increased percentage of carbon dioxide in the air, as well as the existing temperature and acidity ranges, will be tolerated by and may even be favorable to these organisms. ACID COAL MINE DRAINAGE Acid coal mine drainage has been the concern of coal mine operators, industrial¬ists, sportsmen and public officials for many years. The amount of acid flowing into our streams in the coal-producing areas varies considerably from mine to mine and from

Jan 1, 1948

By James Boyd

As our society grows in complexity, it becomes more urgently incumbent upon scientists and engineers to bring their experience to bear on the solution, not only of technical problems, but also on socio-economic difficulties. It is to this field that I have directed a large part of my energies. Raw Materials Basic to the Economic Process There are certain premises, frequently overlooked, which bear emphasis. As economics concerns the production, distribution, and consumption of goods, so our whole society is based on raw materials. Without the basic extractive industries of agriculture and mining, there would be no economic problems with which to deal. This principle has been expressed as: "All productivity is based on three factors: (1) natural resources, whose form, place, and condition are changed by the expenditure of (2) human energy (both muscular and mental), with the aid of (3) tools."*

Jan 3, 1967

By Geoffrey Purcell

Although the extractive metallurgist has not yet tackled the problem of getting blood out of a stone, he must, when faced with the mini- metal values of today's ores, believe that this ultimate miracle will soon be expected of him. Even assuming that some plausible professor at one of the few remaining minerals industry schools could persuade the National Science Foundation to sponsor such a sanguine research project, the funds might have to go begging for want of a graduate metallurgist. Falling enrollment in fields devoted to nonrenewable mineral resources, long a matter of grave concern to educators, is now recognized as a problem of great national consequence urgently needing a solution. While the law of supply and demand might eventually be expected to right the imbalance of engineers, time is not on our side and action to correct the shortage is required now.

Jan 1, 1970

By J. R. Cahoon, W. V. Youdelis

FOR the diffusion of copper in silver-rich alloys, there have been only two previous investigations, that of Seith and Peretti in 1936, and that of Sawatzky and Jaumot2 in 1957. Seith and Peretti obtained a value of 24.8 keal per g-atom for the activation energy of diffusion whereas Sawatzky and Jaumot obtained a value of 46.1 keal per g-atom. Admittedly, Seith and Peretti used relatively high concentrations of 2 at. pet Cu and polycrystalline diffusion couples, while Sawatzky and Jaumot investigated tracer diffusion in single crystals of silver. The difference in the results, however, seems too large to attribute solely to solute concentration, as a change of over 20 keal per g-atom in the activation energy suggests a change in the mechanism of diffusion. Therefore, in the present investigation the diffusion coefficient for copper in polycrystalline Ag-2 at, pet Cu alloy is re-established using conventional sandwich-type diffusion couples and electron-probe microanalyses, and the results are compared with those of the previous studies. The diffusion couples were prepared from high-purity silver (99.999 pet) and high-purity copper (99.999 pet). The silver disks, 1/4 in. long and 4 in. in diam, were machined from an ingot which had been solidified in a dynamic vacuum of 10-3 mm of Hg to eliminate oxygen absorption which otherwise would result in copper oxide precipitation in the weld zone. The alloy disks of similar dimensions were machined from an alloy ingot (nominal composition 2 at. pet Cu) which had been unidirectionally solidified to obtain a predictable solute concentration,3 and homogenized for 1 week at 800°C. Sandwich diffusion couples were made by pressure welding an alloy disk between two silver disks in an induction heating coil. The couples were diffusion-annealed at temperatures of 800°, 756°, 699°, and 630°C in tube furnaces in which the temperature was controlled to better than ± l°C. The diffusion couples were examined metallographically for weld defects, and couples showing even minute defects at the weld interfaces were rejected. Concentration penetration curves were established using an A.R.L. Microprobe analyzer. CuKO radiation was counted and converted to concentration using 0.5 and 1.0 wt pet Cu chemically analyzed standards. Initially, four continuous profiles were obtained, and averaged to obtain the final diffusion curve. The initial analysis was performed commercially and the welds were not located with respect to the profile. Therefore, the results were rechecked by the authors using the Mellon Institute A.R.L. probe. In the latter case, concentrations were obtained at 10-µ steps for four different traverses, and then averaged to obtain

Jan 1, 1968

By Klaus Schwerdtfeger, Leo Zwell

The equilibrium between Ir-Fe or Rh-Fe alloys, iron oxide (wüstite or magnetite), and CO2-CO atmospheres has been determined at 1200°C. The data are used to derive the activities in these binary solid solutions. Both systems show negative deviations from Raoult's law. The lattice parameters are given for the investigated Ir-Fe and Rh-Fe alloys. IRIDIUM and iron form a continuous series of fcc solid solutions at elevated temperatures.' Rhodium-rich Rh- Fe alloys have fcc structure.' In the medium concentration range an ordered bcc phase is stable at temperatures up to about 1300°C. Phase relations in iron-rich alloys are not well-known. No thermody-namic data are available for these alloys. EXPERIMENTAL METHOD The experimental method used was to measure the equilibria between a gas phase of known CO2/C0 ratio, the alloy, and iron oxide (wüstite or magnetite). In one series of experiments the alloys of known composition were heated in CO 2-CO gas mixtures. After treatment (usually 1 day) the sample was quenched to room temperature and its surface examined visually to determine whether an oxide tarnish had formed. The procedure was repeated at slightly higher CO 2/CO ratios until the CO 2/CO ratio of incipient oxidation was found. Subsequently, the CO 2/C0 ratio was lowered again in small increments until the tarnish was reduced. In other experiments mixtures of alloy and iron oxide powders were pressed into pellets and equilibrated with the CO2-CO gas phase. In order to ensure that equilibrium was attained, two specimens with different starting iron content were heated side by side; in most cases, equilibrium was approached in one pellet by reduction of iron oxide and in the other pellet by oxidation of metallic iron. The sample was quenched to room temperature, and the composition of the equilibrated alloy was determined by X-ray measurements of lattice parameters and comparison of these values with calibration curves obtained from alloys of known composition. The oxides present in the specimens were identified by comparison of their diffraction patterns with those in the ASTM Card File. It may be expected from the noble character of iridium and rhodium that no appreciable amount of iridium or rhodium is dissolved in wiistite and magnetite under the present experimental conditions. The activity of iron in the alloy is then equal to that established in the iron oxide by the COrCO atmosphere. The activities of iron in wüstite and magnetite, as a function of oxygen pressure, were taken from the work of Darken and Gurry,

Jan 1, 1969

By G. B. Craig, G. L. Montgomery

A simple technique has been developed which reveals glide dislocations in zone-refined aluminum as etch pits. The technique has been tested quantitatively by making dislocation counts on aluminum single crystals deformed in pure bending. The method has the advantage of being insensitive to the orientation of the surface under examination. A number of etchants which will reveal dislocations in annealed aluminum have been reported.'-' These etchants apparently depend on decoration of the dislocations by an impurity (probably iron) and cannot, therefore, be used to reveal fresh glide dislocations. In addition, it is unlikely that screw dislocations will be etched because of their small attraction for impurity atoms. Amelinckx6 has reported that glide dislocations located along slip traces can be revealed by fluo-rated aqua regia. This work indicated that dislocations themselves, irrespective of decoration by impurity atoms, are responsible for the etch pits. However, as a result of additional etching experiments, Wyon and Marchin7 concluded that dislocations alone are not sufficient to explain the localization of etch pits on slip lines in aluminum using chemical etch-pitting techniques. In addition, their results show that glide dislocations are revealed only on surfaces approximately parallel to a (100) axis and that not all slip systems are attacked. These observations have been confirmed by the present authors. The technique described in this article is insensitive to the orientation of the surface, and reveals dislocations on all glide systems. Fig. 1 shows a deformed region in the neighborhood of a scratch. Dislocations can be seen along three slip traces. In the present work, single crystals of zone-refined aluminum are polished for from 2 to 5 min in a chemical polishing reagent held at 100°C, as described by Herenguel and second:' H2Sol 60 pct H3PO4 30 pct HNO3 10 pet The samples are then coated with a thin oxide film by annealing in air at 450°C for 1 hr and cooling in the furnace. After deformation, dislocation etch pits are developed by immersing the specimen in the same polishing solution which is now held at a temperature of 50°C. The formation of small hydrogen bubbles indicates that etching has occurred. The sample is immediately removed from the solution. Prolonged etching results in enlargement of the pits and, in regions of high dislocation density, the overlapping and loss of resolution of individual pits. It is the experience of the authors that contact with iron will ruinously contaminate the reagent. With careful etching, dislocations separated by half a micron can be resolved optically and the method has been shown to be sufficiently sensitive to reveal dislocations produced during the pre-easy glide region of deformation, Fig. 2. A few examples of glide-dislocation configurations, as revealed by this technique, are shown in Figs. 1 to 4.

Jan 1, 1964

By Arthur F. Taggart, Nathaniel Arbiter

The fact that the floatability of minerals with fatty-acid collectors changes as the pH of a pulp varies was utilized in the early days of flotation, when sulphuric acid was used with oleic acid to float sphalerite and galena. from gangues which themselves float with fatty acids in alkaline pulps. Gaudin1 showed that this difference in floatability is a regular function of the extent of the change in pH. The present paper offers an explanation of the phenomenon, and on the basis thereof sets up recommendations for control of soap-flotation operations. Experimental Parallelism between floatability of a mineral in a given environment and its contact angle in that environment is so well established,2 and the contact angle is so readily and rapidly measurable, that contact angles have been used throughout the experimental work to indicate relative floatability. Experiments comprised contact-angle measurements on a number of representative minerals and metals, and a variety of subsidiary tests designed to check and to amplify the contact-angle indications. Contact-angle measurements were made by the method described in detail by del Giudice.3 Sequence of procedure for determination of the points of Fig. I was: I. Polish specimen. Most specimens yielded zero contact angle after polishing; a few showed a slight "cling." Cling is characteristic of specimens that pit on polishing; it is due to a residue of organic contamination, originally on the particle surface, which persists in the pits. The cling did not change total contact angle after conditioning, and is not, therefore, additive in the upper part of the curves of Fig. I. It may have broadened the bases of the curves for the affected minerals slightly. 2. The specimen was next conditioned in soap solution for 5 minutes. 3. The conditioned particle was transferred, under conditions that precluded surface drying, to an aqueous solution of the pH desired and contact angle determined. 4. The particle was thereupon transferred, again without surface drying, to water. The confirmatory tests will be described at the places pertinent in the argument. Discussion of Results Gaudin and Vincent4 have shown that contact angles with heptoic acid as a collector decrease for a given specimen when the concentration of collector present falls below a certain value. A similar reduction in angle occurs with collector-conditioned particles that are visibly slime-coated, and varies roughly with the extent of coating. Since in the last case the reduction in angle is certainly due to reduction in the proportion of total conditioned mineral surface presented to the bubble, the authors believe that the same condition prevails in the first case cited, and that similar reduction in angle and floatability will occur whenever starvation quantities of collector are present, whether by design or by reason of excessive consumption.

Jan 1, 1943

By Nathaniel Arbiter, Arthur F. Taggart

The fact that the floatability of minerals with fatty-acid collectors changes as the pH of a pulp varies was utilized in the early days of flotation, when sulphuric acid was used with oleic acid to float sphalerite and galena. from gangues which themselves float with fatty acids in alkaline pulps. Gaudin1 showed that this difference in floatability is a regular function of the extent of the change in pH. The present paper offers an explanation of the phenomenon, and on the basis thereof sets up recommendations for control of soap-flotation operations. Experimental Parallelism between floatability of a mineral in a given environment and its contact angle in that environment is so well established,2 and the contact angle is so readily and rapidly measurable, that contact angles have been used throughout the experimental work to indicate relative floatability. Experiments comprised contact-angle measurements on a number of representative minerals and metals, and a variety of subsidiary tests designed to check and to amplify the contact-angle indications. Contact-angle measurements were made by the method described in detail by del Giudice.3 Sequence of procedure for determination of the points of Fig. I was: I. Polish specimen. Most specimens yielded zero contact angle after polishing; a few showed a slight "cling." Cling is characteristic of specimens that pit on polishing; it is due to a residue of organic contamination, originally on the particle surface, which persists in the pits. The cling did not change total contact angle after conditioning, and is not, therefore, additive in the upper part of the curves of Fig. I. It may have broadened the bases of the curves for the affected minerals slightly. 2. The specimen was next conditioned in soap solution for 5 minutes. 3. The conditioned particle was transferred, under conditions that precluded surface drying, to an aqueous solution of the pH desired and contact angle determined. 4. The particle was thereupon transferred, again without surface drying, to water. The confirmatory tests will be described at the places pertinent in the argument. Discussion of Results Gaudin and Vincent4 have shown that contact angles with heptoic acid as a collector decrease for a given specimen when the concentration of collector present falls below a certain value. A similar reduction in angle occurs with collector-conditioned particles that are visibly slime-coated, and varies roughly with the extent of coating. Since in the last case the reduction in angle is certainly due to reduction in the proportion of total conditioned mineral surface presented to the bubble, the authors believe that the same condition prevails in the first case cited, and that similar reduction in angle and floatability will occur whenever starvation quantities of collector are present, whether by design or by reason of excessive consumption.

Jan 1, 1943

By Ronald C. Koo

SMALL additions of potassium, aluminum, and silicon as oxides (referred to as dope) to tungsten have been known for several decades to have a very large effect in raising the recrystallization temperature and altering the recrystallized grain morphology of heavily drawn wire. Previous investigations of this doping effect1 6 have led to various speculations but all failed to deduce unequivocally the physical state or the mechanistic influence of the dopant. Recently, walter7 has observed, by transmission electron microscopy, strings of "fine particles" in heavily rolled and annealed doped tungsten sheet and concluded that they were particles of mullite (Al6Si2013). His conclusion was inferred from the electron diffraction patterns of large particles ex-trated by carbon replication of fractured surfaces of slabs rolled from sintered ingots. That the strings of "fine particles" in heavily rolled and annealed sheet were also mullite was an assumption for which no evidence was presented. A similar investigation has been carried out in this laboratory over the past 2 years on a variety of tungsten wire: doped tungsten, and undoped tungsten, as well as 218 doped tungsten purchased from the Lamp Metals and Components Department of the G.E. Lamp Division. Although the electron microscope observations are similar to those reported by Walter, the writer has reached a different conclusion concerning the physical state of the dopant in annealed tungsten. The purpose of this communication is to present evidence that the strings of "fine particles" observed in transmission specimens are not mullite, but are voids. In the present investigation, tungsten wire, 0.88 mm in diam, was rolled into ribbon 0.2 mm by 125 µ thick. The ribbons were annealed in vacuo at a pressure of -1 x 10-5 Torr and then thinned electrolytically in a 2 pct KOH solution. Fig. 1 shows a typical transmissicjn electron micrograph of a sample annealed at 1700°C for 30 min which reveals rows of closely spaced voids having a light contrast (referred to as "fine particles" by Walter) aligned parallel to the working direction. Stereo micrographs (by D. Moon, Westinghouse Research and Development Center) have shown that these voids do not exist on the surfaces of the specimens as a result of thinning but are within the thin-foil specimens. The following experiments have been performed to verify that these are indeed voids. I) Effect of Annealing. Voids are absent in unannealed specimens and appear only after annealing. This behavior cannot be explained if they were solid particles such as mullite. Precipitation (in an unquenched specimen) upon annealing requires solute elements having decreasing solubilities with increasing temperature. Although the solubility of aluminum in tungsten does decrease with increasing temperature, precipitation requires a concentration in excess of 1.4 wt pct,8 which is at least two orders of magnitude higher than the aluminum content in doped tungsten. It is also unreasonable to assume that particles aligned in rows initially present in unannealed specimens were too

Jan 1, 1968

By C. W. Haworth, M. G. Hall

THE diffusion of copper in silver has been studied by Sawatzky and Jaumot1 and Cahoon and Youdelis.2 Sawatzky and Jaumot measured tracer diffusion in single crystal specimens but the 12.9 h half-life of CU64 limited the time of the diffusion anneal to about 50 hr, and in consequence the minimum temperature of the investigation was 716°C. Cahoon and Youdelis employed polycrystalline diffusion couples, and measured the interdiffusion coefficient over the range 0 to 2 at. pct Cu. These experiments were performed at temperatures down to 630°C and a discontinuity in the Arrhenius plot was observed at -700°C. The high D-values at lower temperatures were attributed to the effect of grain boundary diffusion. The present experiments were undertaken to investigate this anomaly and study the low temperature region of the diffusion of copper in silver. The method employed single crystal samples and a plated source of copper. Silver single crystals 2½ by 4 in. sq were grown from zone-refined silver bar (>99.99 pct Ag) by the Bridgeman technique, and $ in. thick slices were cut by spark machining. The specimens were electro-polished, and a 2 µm layer of copper was electroplated on to the planar surface at one end of each specimen using a potentiostatic voltage source. The following solution was used for plating: CuSO4 . 5H2O 125 gm H2SO4 (S.G. 1.8) 53 ml H2O 1000 ml The diffusion couples were sealed in capsules, in an argon atmosphere, and were annealed at either 701, 597, or 498°C. The temperature measurements were made to an accuracy of *l°C After the anneal, the penetration of copper into the silver was determined using an electron probe micro-analyzer. 100 sec scaler measurements of the intensity of Cu Ka! X-radiation were performed at 2 to 5 µm intervals along a line normal to the source, with a beam potential of 25 kv. Allowances were made for the background radiation, and the dead-time of the counting system in the normal way, and the intensity ratios were corrected to weight concentration by the method of Duncumb & de-Casa.3 For the analysis of the diffusion profiles, it was first observed that the copper layer did not completely dissolve in the host crystal for the specimens annealed at 498 and 591 whereas for the specimen annealed at 701°C, a single phase solid solution was formed. For the 498" and 597°C specimens, the concentration of copper in the silver at the interface was therefore constant throughout the anneal and the analysis for a

Jan 1, 1970