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By L. R. Velho, N. A. D. Parlee, J. Gani

THE unsteady-state type of gas-liquid metal diffusion cell1 has found considerable application.2"4 Cells of this general design can function as steady-state cells if allowed to operate long enough to reach steady state. This report tells of some success in the adaption of this type of cell for steady-state work, using the 0-Ag system in which the mass transfer of the gas "species" is basically controlled by diffusion in the liquid. The gas, e.g-., O2, is maintained in the cell tube'-3 at 1 atm pressure, Fig. 1, by buret and sensitive oil manometer. The gas, after diffusing through the stagnant metal, escapes at the annular metal surface around the tube at a lower constant partial pressure, in this case that of O2 in slowly flowing air, 1 atm.

Jan 1, 1970

By G. A. Vissac

In continental Europe the feldspar jig is used almost exclusively for cleaning the fine sizes of coal; it operates with an artificial bed, made up generally of pieces of feldspar or of any other hard and heavy rock with good cleavages. A primitive form of this machine requiring close supervision was used in this country years ago, but output was small. The modern machines are generally air-pulsated Baum-type jigs, with capacities up to 150 tph, and treat sizes from 3/s in. to 0, usually previously dedusted or deslimed. These jigs are equipped with very accurate and sensitive automatic controls insuring satisfactory operation even at low separating gravity and with feeds irregular in quality and quantity. This paper will deal more particularly with coal cleaning separation, but the technical studies apply equally to all minerals.

Jul 1, 1955

Although the 71 Minerals operation is now closed down and the operating data presented is almost five years old, it is well worth describing since it was the first heap leaching operation conducted on a primarily silver ore. Tombstone was discovered in 1877 by Ed Schieffelen; and it became one of the most famous mining towns in the West through the stories connected with Wyatt Earp, Doc Holliday, and the Clanton brothers. Like many silver deposits .in the western United States, the Tombstone ores were relatively shallow. Several million ounces of silver were recovered in the relatively few years the camp was active; but mining virtually ceased by the early 1900s and was only continued in a small way until the 19409, a history similar to that of Tuscarora. The 71 Minerals operation was started in May 1975 and continued until late 1978 within the city limits of Tombstone on waste dumps; one was the' Lucky Cuss, Schieffelen's discovery, which had accumulated from the old underground operations. This waste material was mostly less than 50 mm (2 in.) in size, although there was some larger lumps. The grade was about 34 g Ag and 0.5 g Au per mt (1.0 oz Ag and 0.015 oz Au per st). The Tombstone dumps contained approximately 1,000,000 tons. The dumps and patented claims were held by a single owner, Tombstone Development Company, thus sufficient leaching material could be acquired from one source rather than dealing with a number of individuals, as is usual in putting together leaching ventures in old mining camps. 71 Minerals Ltd. was formed and a lease of the properties obtained. A site was selected close to the major mine dumps not far from down- town Tombstone. Pads approximately 90 m (300 ft) wide and 180 m (600 ft) long with an 8-degree slope were prepared using compacted old mill tailings as a base sealant on the pads. Mining was done at a rate of about 2,000 tons per day with a dozer, two scrapers, a front-end loader, and 30 ton trucks. The ore was dumped by the scrapers as it came from the dumps with no screening or crushing in 460 mm (18 in. ) layers and trimmed with the loader. Based on bulk sampling and laboratory testing, the majority of thegold and silver values were recovered within 30 days of leaching.

Jan 1, 1981

By H. L. Talbot, A. J. Hall, R. S. Young

A METHOD for the chemical differentiation of oxidized cobalt from sulphide cobalt in complex mine and concentrator products is of considerable interest to a number of mining companies throughout the world. At Rhokana Corporation, in Northern Rhodesia, for instance, cobalt is found chiefly in the sulphide form, as carrollite, but a cobalt oxide mineral also occurs irregularly underground, and relatively small quantities in the mill feed from time to time are difficult to detect it visually at the concentrator. The oxide cobalt is not amenable to the sulphide flotation process used at Rhokana and nearly all of it passes into the tailing. The occasional. period when high tailing losses occur with no appreciable change in the cobalt content of the mill feed has naturally been disturbing to the concentrator staff, who had no means of determining whether an influx of cobalt oxide ore or laxity on the part of the mill flotation operators were responsible for these results. A procedure for determining oxidized copper minerals, based on their solubility in dilute sulphuric acid saturated with SO2, has been used for many years in the copper industry. In the presence of cuprite the procedure fails, but otherwise it gives results quite satisfactory for control purposes. Empirical methods for determining oxidized forms of zinc and lead have been proposed, but they are generally unsatisfactory except in isolated cases of a very simple ore. No published procedure for determining oxidized forms of cobalt or similar elements has come to the authors' notice. EXPERIMENTAL PROCEDURE There are obviously two alternatives in attacking a problem of this nature. One is to employ a solvent for oxide cobalt that will not dissolve cobalt sulphide. The other is, to find a substance capable of oxidizing the cobalt sulphide to sulphate, which of course is water-soluble and can then be leached from the water-insoluble oxide cobalt. A representative sample of Rhokana cobalt oxide ore was secured, ground to minus 200-mesh, and carefully rolled to furnish a standard sample for this work. The analysis of this material gave the following percentages: Co, 0.55; Cu, 1.64; Fe, 2.98; S, 0.08; SiO2, 41.42; A1203, 11.20; CaO, 13.82; MgO, 3.80. As a source of cobalt sulphide a similar large sample of carrollite was prepared, analyzing Co, 23.36 per cent; Cu, 27.32; and S, 31.13. This sample of course was not pure carrollite, but was the best obtainable in quantities sufficient for a standard intended for considerable work. It was a pure sulphide sample, microscopic examination showing only carrollite, a little bornite, and gangue, with no visible sign of oxidized ore present. A wide variety of reagents were used in an effort to selectively dissolve oxide cobalt or to oxidize sulphide cobalt to

Jan 1, 1946

By David B. Reger

The exhaustion of oil and gas in the United States is proceeding at a rapid pace. This is especially true in fields where the light oils that furnish the most fuel for internal-combustion engines arc found, leading to a late estimate by Arnold that the petroleum resources are 36 per cent. exhausted.l The further remark by Dr. David T. Day at the New York meeting of the Institute, in February, 1916, that the operators of the country are now scarcely able to supply the ever-increasing demand for gasoline, leads the writer to believe that a determined effort will soon be made to secure deeper producing horizons in those regions that now furnish high-grade oil, and in which pump stations and pipe lines offer convenient means for the economical handling of new production. A study of Arnold's table shows further that the States that produce paraffin oil exclusively are 45 per cent. exhausted, this figure being much higher than the average of paraffin and asphalt States altogether. The most extensive of all the paraffin-oil-producing areas is the Appalachian Field, extending with the Appalachian Geo-Syncline from western New York southwestward through western Pennsylvania, western West Virginia, Ohio, Kentucky, and Tennessee, where oil of high gravity is always secured. Of these States, Pennsylvania and West Virginia rank highest in the quality of their product. In West Virginia, the oil sands dip to a lower level than in any other locality in the Appalachian Geo-Syneline, the Pittsburgh Coal of the Pennsylvanian being only 50 ft. above sea level along the Nineveh Syneline at Wileyville, Wetzel County.² The very significant fact that the sands of the Mississippian and Upper Devonian Measures furnished the richest oil pools of the State along this

Jan 1, 1917

By Ronald L. Longwell

PROPERTY LOCATION Located in the Copper Creek area of the Galiuro Mountains, the Old Reliable is on ground first claimed for mineral value during the Civil War. The deposit was mined sporatically from 1880 to 1919 and again in 1953 and 1954, with a total of about 30,000 tons of ore removed. The ore body is a near vertical breccia pipe containing approximately 4,000,000 tons of 0.80% copper with mineralization occuring as chalcocite, chalcopyrite, malachite, chalcanthite, and chrysocolla. The host rocks are extrusive lavas of cretaceous age which were intruded and mineralized by Copper Creek Granodiorite, which is Laramide in age. The ore zone, which occurs on the toe of a ridge, is about 300 feet by 600 feet in plan, with the bulk of the deposit extending from the surface to a depth of 500 feet.

Jan 1, 1974

By W. G. Pfann

The simultaneous segregation of two solutes during the directional solidification of an ingot is treated mathematically on the basis of simplifying assumptions. Expressions are derived for the difference in concentration of two solutes, and for the location and concentration gradient of a pn barrier formed in a semiconductor by the segregation of a donor and an acceptor. THE problem of normal segregation of a single solute during the freezing of an alloy has been treated mathematically by a number of investigators. Gulliver' showed that coring increases the quantity of eutectic above that to be expected at equilibrium, for a system having limited solid solubility and, on the basis of simplifying assumptions, calculated the fraction of eutectic to be expected. Scheuer2 expressed composition of solid solution in terms of a distribution coefficient and the fraction solidified and compared experiment with calculation for the systems A1-Cu, Al-Zn, Cu-Sn, Cu-Zn. Hayes and Chipman,3 in a detailed study of segregation in a low carbon, rimming steel ingot, calculated distribution coefficients for a number of solutes in iron, compared calculated and experimental segregation curves, and discussed the effects of process variables such as rate of solidification and stirring. In the present paper a mathematical analysis is made of the simultaneous segregation of two solutes during the orderly freezing of a solid solution system, with particular emphasis on the difference in solute concentrations. Although the analysis is quite general and can be applied to the segregation of minor elements in alloys, it is directed in particular at the solidification of a semiconductor containing a donor and an acceptor. Normal segregation has unique aspects in a semiconductor, because of the ways in which donors and acceptors affect the electrical properties. The difference between two solute concentrations becomes of importance, as does also the gradient of the difference where the difference goes through zero, this being the concentration gradient of excess carriers at a pn barrier. A primary object of this paper is to extend the mathematical treatment of segregation to include these newer aspects which are of particular significance for semiconductors. One property of interest is the electrical conduc- tivity, which arises from the presence of donors 'or acceptors in solid solution. The conductivity may be either n-type or p-type depending on whether donors or acceptors, respectively, are in atomic excess. For both germanium and silicon, elements of Group V of the Periodic System, such as P, As, and Sb, are donors and elements of Group 111, as B, Al, In, and Ga, are acceptors.4-6 If a donor or acceptor is present alone in solid solution, the conductivity is proportional to its concentration." If both a donor and an acceptor are present, then the conductivity is proportional to the difference in their atomic concentrations. If the donor and acceptor segregate at different rates then a pn barrier in certain circumstances may form at some point in the ingot. Accordingly, equations are derived and illustrated which express the effect of segregation on: 1—the concentration of a single solute with a discussion of the assumptions; 2—the difference between two solute concentrations and means for minimizing its variation in an ingot; and 3—the location and concentration gradient of a pn barrier. The analysis is applicable to processes in which the entire charge is melted and then progressively frozen from one end. The method in which an ingot is solidified in a crucible7 and that in which a solidifying rod is pulled from the melt8 both fall into this category. Segregation of One Solute If a cylinder of molten alloy is caused to freeze slowly from one end, a normal segregation of solutes will usually occur, producing a lengthwise concentration gradient in the ingot. Depending on whether a solute raises or lowers the melting point of the solvent, it will become concentrated in the first or last regions, respectively, to freeze. If it is assumed that freezing is such that there is no diffusion of solute in the solid, complete diffusion in the liquid, and that k, the distribution coefficient, defined as the ratio of solute concentration in the just-freezing solid to that in the liquid, is constant, then the

Jan 1, 1953

By Cyril Smith

SOMEWHAT over ten years ago the author described studies1,2 on the constitution of the copper-silicon system. The copper-rich portion of this diagram is shown in Fig. 1. The experimental points freely dotted about the diagram seemed to justify an otherwise unconvincing diagram and for several years the curious reverse bend in the alpha-phase bound-ary was accepted as substantially correct, even by later investigators3,4 of the system who introduced changes in the high-silicon phases. The binary diagram has been used as a base for several ternary systems" without any suggested changes. Voce10 suspected the existence of another phase from his study of the cast alloys in the copper-manganese¬silicon system, but evidently hesitated to extrapolate this to the binary diagram, particularly in view of the too ingenious explanation that was advanced" to account for the pools of constituent clearly visible in castings; namely, that they were secondary alpha of twinned orientation deposited from beta. Von Schwarz,12 in 1932, called attention to the fact that this micro-constituent in copper-silicon alloy castings was anisotropic under polar-ized light and asserted that a new phase, not cubic, should be placed in the diagram adjacent to alpha. Sautner,13 on the basis of investigations with the polarizing microscope and with X-rays, introduced this phase into the diagram at about 6 per cent Si. The relevant part of his dia-gram is shown in Fig. 2. Sautner called the new phase beta, renaming the old beta phase zeta. To avoid confusion, in redrawing Fig. 2 the phases have been renamed in accordance with the terminology adopted in the present paper, in which the new phase is called kappa and the other phases retain the designation given them by Arrhenius and Westgren.4

Jan 1, 1939

By Ole Singstad

THE legislatures of New York and New Jersey, determined in 1919 that a vehicular tunnel should be built under the Hudson River. On July 1, 1919, an engineering staff was organized with the late Clifford M. Holland as chief engineer, and this staff was given a number of problems to solve, such as location, size, type of tunnel, method of construction, method of ventilation and cost. After a period of preliminary investigations and studies it was decided to build the tunnel at Canal St., New York, connecting 12th St., Jersey City. This is the center of the heaviest traffic across the Hudson River. It was also decided to build two tunnels-one for west-bound traffic and one for east-bound traffic-the tunnels to be of cast iron, built up of segments and bolted together, each tunnel to have a roadway 20 ft. wide and a clear heat room of 13 ft., 6 in. This is to provide for two lines of vehicles in each direction. The tunnels have an exterior diameter of 29 ft., 6 in. The interior lining is of concrete, the sidewalls tiled with a vitreous white tile and the roadways paved with granite block. The entrances and exits at both ends are separated by two blocks so as to reduce traffic congestion. BASIS OF VENTILATION It was recognized very early that one of the most important problems confronting the engineers was a proper ventilation system. It was estimated that each tunnel as planned would have a traffic capacity of 1900 vehicles per hr. The tunnels are 8500 ft. long between portals, and it was considered that the ventilation should be based on all of these vehicles being operated by gasoline engines. That presented a problem in ventilation unlike any other either in magnitude or character.

Jan 8, 1926

By Edmund Kirby

THE results to come from the application of cheap oxygen to industry in general will be so great that it is not possible to enumerate them beforehand and still less to estimate them. We naturally think first of the fuel to be saved; yet this is only a minor item. The main results will be changes in methods of manufacture or of operation. The speed of operation will be greatly increased, with consequent savings in labor and fixed charges, and also, in most cases, in the cost of fuel. High temperature will be brought within the reach of every manufacturer, whereas it is now available only to those operating expensive electric furnaces located within reach of large water power. New speeds and new temperatures mean improvements and processes not thought of at present. Incidentally the changes in methods will probably change the location of important world industries, the tendency being to concentrate at the fuel centers. The whole subject is so new that most of the data which an engineer requires for definite estimates do not exist. All that is possible now is to obtain a general view of the subject with rough and fragmentary estimates for some of the industries with which we are specially concerned. Most of the figures presented deal with fuel saving merely because there are available no data from which to estimate the effect on speed of operation. When working out the practical problems involved in substituting oxygen for air, in most cases the change will be made step by step; by trying out air enriched with increasing percentages of oxygen. Such partial applications of oxygen will be temporary expedients during the transition and there will be no stopping place short of the complete substitution of air by oxygen. This final stage is therefore the one discussed in this paper.1

Jan 11, 1924

By C. S. Finney, John Mitchell

On December 31, 1959, there existed in the United States 15,993 slot-type coke ovens capable of producing 81,447,700 net tons of coke. These ovens were concentrated in 74 coke plants in 21 different states. As of the same date, there were 7448 beehive ovens in existence at 45 plants in the states of Pennsylvania, Virginia, West Virginia, and Kentucky. Total annual capacity of the existing beehive ovens was 4,368,800 net tons, but only 5148 ovens with a capacity of 3,131,600 tons were in operating condition. It is interesting to compare the average dimensions of slot-type ovens built during recent years with the 30 ft x 5 ½ ft x 16 ½ in. ovens erected at Syracuse, N. Y. in 1892. A composite oven built according to the average dimensions of all those erected between 1954 and 1958, for instance, would be 39 ft long. 12 ft high, and 18 in. in width. The coal capacity would be 16 tons as against the 4.4 tons which could be charged to the Syracuse ovens. Of the 15.993 slot- type ovens in existence at the end of 1959, by far the greater number were built by the Koppers Co. whose total of 11,280 ovens included 7891 Koppers- Becker and 3389 Koppers ovens. Of the remainder, there were 3260 Wilputte, 1350 Semet-Solvay, 63 Otto, and 40 Simon Carves ovens. By-product coke oven plants are usually classified either as furnace or merchant plants. According to the definitions used by the US Bureau of Mines, the former are "those that are owned by or financially affiliated with iron and steel companies whose main business is producing coke for use in their own blast furnaces. All other coke plants are classified as merchant. They include those that manufacture metallurgical, industrial, and residential heating grades of coke for sale on the open market; coke plants associated with chemical companies or gas utilities; and those affiliated with local iron works, where only a small part (less than 50 pct of their output) is used in affiliated blast furnaces." The annual coke capacity of the merchant plants during 1959 was 10,393,000 tons. However, the by-product oven of today is essentially an appurtenance of the iron and steel industry, rather more than 87 pct of total by- product coking capacity being concentrated at furnace plants. This was not always so. There was a time when the merchant plants played a much greater part in meeting the US demand for coke and gas. High noon for the merchant plants was reached during the early 1930's. By 1932 there were as many by- product oven installations being operated by the merchant sector of the industry as by the coke divisions of the iron and steel industry (44 of each), and in the same year the merchant plants produced 46.5 pct of all by-product coke made in the country. Since that time their contribution has drastically declined. In 1940 merchant plants were responsible for only 23.2 pct of total US production, and by 1950 their number had decreased to 30 plants which turned out 18.5 pct of the total by-product coke made. At the end of 1959 only 20 of the 74 existing by-product oven installations were merchant plants. They ac- counted for 12.5 pct of the year's production, or 6,849,786 net tons. This percentage has remained fairly constant since 1954. There are several reasons for the decline of the merchant coking industry. For example. On the grounds of economy, quality control, continuity of supply, and so on, the iron and steel industry usually prefers to control its own mines and carbonize its own coal at or near to the blast furnace rather than rely on independent operators for metallurgical coke. As the steel companies have enlarged their own coking facilities, so has the need for coke obtained from other sources declined. Furthermore, not only has the steel industry increased in self-sufficiency by building mare coke ovens during recent years, but it has also progressively improved the fuel efficiency of its blast furnaces. During the years 1947-49 the average coke consumption per ton of pig iron was 1892.8 lb. During 1958 the corresponding figure was 1613.4 lb. There are many individual furnaces where still better results are being obtained, and further reductions in the average may be expected. Perhaps the greatest threat to the merchant coking plant has been the fantastic increase in the use of natural gas and petroleum products for purposes which manufactured gas once served. So deadly has the com- petition from natural gas and oil been that it has almost eliminated by-product oven installations owned by public utilities. In the peak years of the early 1930's there were 23 such public utility plants. In 1960 only two were left. One of these, owned by the Citizens Gas and Coke Utility, was at Indianapolis, Ind.; the other was the plant operated by the Philadelphia Electric Co. at Chester, Pa. The non-utility merchant plants have also been sorely hit. With gas sales revenues reduced, domestic

Jan 1, 1961

By H. W. Miller, V. H. Wilhem

Although the year 1933 was a period of uncertainty, considerable new development was initiated, with a high percentage of favorable results, for owing to financial conditions only projects of merit were proposed and developed. Unfavorable marketing conditions caused severe financial losses to refinery and sales departments of nearly all companies during the first half of the year. In anticipation of stabilized Government control, earnings were generally favorable during the third quarter but failure of the Government to take legal action against violators of the proration orders, and lack of agreement on a definite plan of curtailment, resulted in considerable overproduction and demoralization of the market structure during most of the final quarter. However, toward the close of the year Government action against violators of the Oil Code had a tendency to decrease overproduction materially and give the market a firmer tone. As a whole, the price structure of crude oil was maintained at a high level during the year; in fact, at a much higher level than the price of refinery products warranted. At no time during the year was production within 10,000 bbl. daily of the state allotment, overproduction of crude reaching a peak of 70,000 bbl. on Sept. 7, average daily average for the year being about 27,000 barrels. Numerous plans for equitable curtailment were prepared and tested during the year, none of which fully solved the many and intricate problems faced by operators who were in most cases willing to curtail if they could feel that cooperation was being practiced by their neighbors. Outstanding events in California oildom during the period under discussion may be classified under the following headings: 1. New discoveries. (a) New development in proven areas. (b) Deeper zones in settled pools. 2. Unproductive wildcat operations. 3. Whipstocking practice and procedure. 4. Progress of unit and orderly plans of development.

Jan 1, 1934

RESEMBLING in some respects the enterprise at R Chuquicamata is that of the New Cornelia Copper Co. at Ajo, Arizona. Controlled from its inception by the Calumet & Arizona Mining Co., New Cornelia became a unit of the Phelps Dodge Corporation when the latter absorbed the Calumet & Arizona company in 1931. Both Ajo and Chuquicamata are situated in low mountains in extremely arid desert country. Both ore deposits consisted-the past tense is used advisedly because the oxidized ore has nearly all been mined at Ajo-of a horizon of leachable oxidized ores overlying sulphide or concentrating ore. The principal technical problem in each case was the development of a method for treating the oxidized ore. In both instances the capping of waste rock was comparatively thin and power-shovel mining in open cuts was the obvious method of exploitation. Nature had smiled on neither place in the matter of climate. Though Ajo does not have the persistent winds for which Chuquicamata is notorious, the comforts of living are largely artificial. And it is only fair to emphasize that at each place the mining companies have achieved remarkable success in providing these comforts. Of course, in point of size New Cornelia must be content with the inferior role. From May, 1917, when production was started, to the middle of June, 1930, the company leached 16,368,000 tons of oxidized ore, thereby virtually exhausting the ores of this class. Up to the same date, about 15,000,000 tons of sulphide ore had been mined, and a rough estimate gives 170,000,000 tons remaining in reserve. The total tonnage does not loom very large in comparison with Chuquicamata's billion tons; but it is exceeded by similar figures for only four of the Porphyry group.

Jan 1, 1933

By David Reger

Introduction THE exhaustion of oil and gas in the United States is proceeding at a rapid pace. This is especially true in fields where the light oils that furnish the most fuel for internal-combustion engines are found, leading to a late estimate by Arnold that the petroleum resources are 36 per cent. exhausted.1 The further remark by Dr. David T. Day at the New York meeting of the Institute, in February, 1916, that the operators of the country are now scarcely able to supply the ever-increasing demand for gasoline, leads the writer to believe that a determined effort will soon be made to secure deeper producing horizons in those regions that now furnish high-grade oil, and in which pump stations and pipe lines offer convenient means for the economical handling of new production. A study of Arnold's table shows further that the States that produce paraffin oil exclusively are 45 per cent. exhausted, this figure being much higher than the average of paraffin and asphalt States altogether. The most extensive of all the paraffin-oil-producing areas is the Appalachian Field, extending with the Appalachian Geo-Syncline from western New York southwestward through western Pennsylvania, western West Virginia, Ohio, Kentucky, and Tennessee, where oil of high gravity is always secured. Of these States, Pennsylvania and West Virginia rank highest in. the quality of their product. In West Virginia, the oil sands dip to a lower level than in any other locality in the Appalachian Geo-Syncline, the Pittsburgh Coal of the Pennsylvanian being only 50 ft. above sea level along the Nineveh Syncline at Wileyville, Wetzel County.2 The very significant fact that the sands of the Mississippian and Upper Devonian Measures furnished the richest oil pools of the State along this

Jan 9, 1916

By Leon Y. Sadler, E. K. Landis

Froth flotation has been described by several authors" as being analogous to a first-order rate process. Although a few investigators"," have found orders other than one fit their data best, the rate is described most often by the first-order equation, [ ] where r is rate of disappearance of floatable mineral by flotation, C(t) is concentration of floatable mineral in the cell, t is time, and k is first-order flotation rate constant. One of the difficulties in using this rate equation to develop a mathematical description of an actual flotation process is the determination of a suitable value of the constant k. The value of k, which reflects the floatability of the floatable mineral, is dependent on the hydrodynamic conditions in the cell, type and concentration of flotation reagents used, pulp density, and pH, method of froth removal, aeration rate, particle characteristics, and many other factors. Therefore, it is reasonable to expect that each particle of floatable material has a distinct value of k and that a unique distribution of k values exists for given feed and cell conditions. This has been observed and discussed by several investigators, and mathematical descriptions of the batch cell and steady-state continuous cell with distributed flotation rate constant have been developed." The mathematical description in the form of a transfer function of the continuous or flow cell under unsteady-state conditions with a distributed flotation rate constant has not been presented in the literature. The purpose of this note is to make such a presentation. The basic features of the perfectly mixed continuous

Jan 1, 1974

By JOHN R. SUMAN

TONIGHT I want to speak of the current problems and the postwar difficulties facing American industry. American industry has done an outstanding job in adjusting its operations to wartime necessity. The national income for 1942 was nearly $120,000,090,000 and of this outlay approximately $55,000,000,000 went for war material. The enormity of the expenditures for war material is indicated by the fact that the expenditures for war purposes alone were greater than the annual gross national income in the period 1931-34. This tremendous production job in turning out a record output of war products was accomplished by industry in spite of a large number of restraining and hampering influences, and I want to mention several of the more important problems.

Jan 1, 1943

Doctor David Yang has presented an important new flotation development in the area of fine particle flotation technology; at the same time Dr. Yang presents an explanation for the effectiveness of this improved new fine flotation system in terms of an optimum dispersion state. The same statement is made for the case of carrier flotation (ultraflotation), in the removal of anatase from kaolinite by addition of calcite (selective flocculation of the anatase - calcite system and dispersion of kaolinite). Dr. Yang's data and statements raise some important questions, and I will adress myself to the more fundamental aspects of this new flotation system. The addition of sodium silicate, well known as a good depressant-dispersant agent for siliceous gangue minerals, is proved to be greatly enhanced by the incorporation of polyvalent metal salts into sodium silicate prior to flotation, producing in this manner a condition, as described by Dr. Yang, of optimum dispersion, which in the case of fine-grained oxidized taconite can be described as selective flocculation (coagulation) of hematite and almost complete dispersion of siliceous gangue components. Dr. Yang recognizes that the main mechanism, while not completely understood at this time, seems to operate by modifying the surface characteristics of the gangue slime particles so as to prevent collector from bonding there to, and making the particles strongly hydrophilic so they will become fully dispersed and consequently will not float during froth flotation. At the same time it appears that the conditioning reagent also modified the surface characteristics of the floated minerals (hematite and spodumene in this case) so that they will aggregate and tend to more readily adsorb the collector, resulting in an improved flotation kinetics and selectivity.

Jan 1, 1979

By R. E. Ogilvie, J. I. Goldstein

The a and y solubility limits in the Fe-Ni phase diagram have been redetermined at temperatures above 500°C. Both a diffusion-couple and a quench and anneal technique were used. The solubility limits were measured with an electron-probe micro-analyzer. The nickel concentration at the phase boundary is increased below 700°C and the a solid-solubility range is much larger than had been previously measured. The solubility limits are also extrapolated to 300°C. It is suggested that the solubility of nickel in a FeNi reaches a maximum in the temperature interval 400o to 500°C. THE equilibrium diagram has been of great use in the field of meteoritics, where the phase relations between kamacite (a) and taenite (?) in metallic meteorites can be described by means of the Fe-Ni diagram. The study of metallic meteorites by electron-probe microanalysis has cast some doubt on the accuracy of the presently available Fe-Ni diagrams.1, 2 Recent thermodynamic studies of the Fe-Ni system also suggest that the diagram may be in error.3 For these reasons the high-temperature (800o to 500°C) part of the diagram was redetermined. INTRODUCTION The currently accepted Fe-Ni diagram is that of Owen and Liu.4 Above 910°C, there is a region of complete solid solubility, ? (fee). Below 910°C, the a (bee) phase is stable in pure iron. The effect of increasing amounts of nickel is to stabilize the y phase. The phases that form when Fe-Ni alloys are heated or cooled bear little relation to the equilibrium diagram. If an alloy is cooled from the y state and held at a temperature within the a + y field, no evidence has been found for the occurrence of the y - a transformation.5 If the alloy is cooled to low enough temperatures the y phase breaks down into a supersaturated bee phase called a2. In fact, in alloys over 27 pet Ni the y phase is retained at room temperature.6 The a, phase has the same composition as the original y. The temperature at which a2 forms, the M, temperature, has been determined experimentally.' A state of equilibrium can be approached by cooling below M, to form a2 and then reheating the alloy into the two-phase region of the diagram. The y phase will then begin to precipitate out of the a2 phase and grow. The growth of the phase, however, is quite slow. Using the interdiffusion coefficients -Da of Goldstein et al.,8 it is estimated that it takes about 1 year to grow a 10-µ-wide region of ? at 700°C in a 5 pet Ni alloy. Owen and Liu4 used the technique just described to form the equilibrium phases. The phases present were determined by means of X-ray analysis. The accuracy of their diagram depends on the number of alloys available near the phase boundary at a given temperature. In this study two different techniques were used to determine the a/a + ? and ?/a + ? solubility limits. The inherent accuracy of both techniques was greatly improved over that used by previous investigators because the phase-boundary compositions were measured with an electron-probe microanalyzer. PROCEDURE The two methods used to determine the Fe-Ni diagram are the diffusion couple (D.C.) and the quench-and-anneal (Q.+A.) techniques. In the first method, diffusion couples whose diffusion path goes through a two-phase region of the phase diagram were used. A description of the technique used for making the diffusion couples has been described in a previous paper.' After the diffusion treatment a discontinuity in the resultant concentration vs distance profile was measured. The nickel concentrations in the a and ? phases at the interface of the discontinuity are the solubility limits of the a and ? phases in the phase diagram at the diffusion temperature. If the interface com-

Jan 1, 1965

By D. T. Peters, J. C. Bisseliches, J. W. Spretnak

The pain boundary relaxation phenomenon in high-purity copper, 0FHC copper, and a precipitation-hardenable alloy o-fCu-2 uit pct Co has been studied by internal ,friction and elastic aftereffect techniques. The data were analyzed by assuming the broad distribution of relaxation times observed obeys a lognormal distribution law which enables calculation of the relaxation strength. Grain size had no effect on relaxation strength, although the peak width increased with increasing grain size and decreasing temperature. A double grain boundary peak was produced in high-purity copper by annealing to produce secondary recrystallization. The activation energy measured for 99.999 pct Cu is 37.5 * 3 kcal per mol and 46.5 kcal per mole for OFHC copper. A small peak in the Cu-Co alloy at about 220°C at 1 cps was deduced to be the grain boundary peak. Its height increased and its activation energy decreased with increasing aging time. Except for erratic peak positions the observations were consistent with the theory of pain boundary sliding. BEFORE the mechanism of the grain boundary internal friction peak in metals can be satisfactorily explained, the detailed characteristics of the relaxation process must be documented. Of interest are the effect of grain size on relaxation strength, the high-temperature background, and peak width and position. The effect on the grain boundary peak of a precipitate at grain boundaries and of the change in distribution of the particles with aging time must also be explained by any existing or forthcoming theory. The model which has received the most attention was proposed by KG' and zener2 and proposes that the anelastic strain results from sliding of adjacent crystals at grain boundaries. The sliding is limited by the interlocking of grain corners. It follows, according to this model, that the relaxation strength is independent of and the relaxation time is proportional to the grain size. The proportionality between grain size, D, and relaxation time, t, has been confirmed by K&' and Bisseliches . In this case, the internal-friction peaks of various specimens can be superimposed by plotting Q-' as a function of the parameter vD exp H/RT where v is the frequency and H the activation energy. However, the data of Starr et 01.' and Leak6 fit better to a parameter containing D to an exponent near two. A meaningful relationship is not always deducible from the shift of peak temperature with grain size. KG7 demonstrated that a twofold variation in grain size obtained by varying the amount of cold work followed by identical recrystallization anneals will cause a peak shift that is too large to be accounted for even by an exponent of two. Since the decreased grain boundary area existing with a larger grain size is exactly compensated for by an increased sliding distance, the relaxation strength should not decrease with increasing grain size. The height of the internal-friction peak has generally been observed to be rather insensitive to grain size as long as the average grain diameter does not approach the specimen diameter. Exceptions have been reported by Koster, Bangert, and Lang8 for copper, and by Leak6 for iron. The observations for copper could well have been confused by the presence df 0.3 pct0. The possibility that the peaks may simply be increasing in width with increasing grain size and that the relaxation strength, which is proportional to the area under the peak, may remain constant was not examined. his point has been checked in this investigation using high-purity copper. Atomic mechanisms to account for damping by sliding at grain boundaries have been proposed by KG7 and Mott. KG predicts the activation energy to be identical to that for self-diffusion. Mott's "island" model suggests the activation energy is nL where n is the number of atoms in an island and L is the latent heat of fusion per atom. Other authors have felt that a value equal to the activa-

Jan 1, 1964

By Terkel Rosenqvist

J. Chipman (Massachusetts Institute of Technology, Cambridge, Mass.)—The fact that the experimental work has been applied to copper rather than iron and that the paper is presented to the Iron and Steel Division, I regard as rather significant. It shows the unity of metallurgy and the fallacy of trying to cut it up by metals. This result for the solubility of sulphur in molten copper correlates with Professor Schuhmann's finding that the published data on the other side of the copper-sulphur miscibility gap are also in error. I should like to ask the author to say a little bit more about the sulphur capacity of the slag. T. Rosenqvist (author's reply)-—I hope that Dr. Chipman will find the derivation of the expression for sulphur capacity more clearly explained in the printed version of the paper than in the oral discussion at the meeting. I feel that this quantity, which actually is the ratio of two activities, can be measured more easily than the individual activities. Even if the ratio CaO/CaS is chosen as the standard state, the expression can be used for any slag, even for slags completely free of lime, and it represents a way to put the desulphurizing power of all slag constituents into one bag. Some doubt has been expressed as to whether oxygen ions really exist in calcium oxide and in molten slags. From a thermodynamic view point that question is of minor importance. The term oxygen ion activity, or any activity for that matter, is defined rigorously by the equation: activity = exp p/RT, where p is the change in free energy connected with the transfer of one mol of ions from the standard state into the slag. Whatever happens to the ion in the slag is of no concern to the thermodynamicist. Regardless of whether the ion is "free" in the slag or not, or whether it is present in a very small amount, its activity can always be expressed, and for a thermo- dynamic calculation that is all we need. However, ionic activities will only be of some real value if they are simple functions of the slag composition, or can be measured easily. Concerning the real nature of the oxygen in the slag, my feeling is that the oxygen atom has a rather multiplex nature depending on how strongly it is tied by covalent forces or polarized by the other atoms or ions present. The oxides of iron, cobalt, and nickel differ from calcium oxide and blast furnace slags as to the amount of free electrons that can give rise to electronic conductivity. In slags we know that the conductivity is mostly ionic. The fact that reversible emf's can be obtained with oxygen electrodes in certain salt melts, indicates a significant amount of oxygen ions in these melts. But extended work, e.g. polaragraphic studies and measurements of transference number; are needed to obtain quantitative information about the real structure of the slags. D. E. Babcock (Republic Steel Corp., Youngstown, Ohio)—-With reference to the ion, it might be well to remember Dr. Moses Gomberg. All of his life he had no use for the ionization theory and he contributed greatly to the field of chemistry on the assumption there was no such thing as ions. I do not think we have to worry about whether the oxygen is ionic or not. I think one thing specifically should be brought to your attention and this I think is one of the important contributions of Dr. Rosenqvist. He pointed out what we know as oxygen potentials or what is described as oxygen potentials. I have used this concept for a long period of time and I want to state that if this concept is properly applied, it vitiates much of what we have in the literature, or makes our usual ideas regarding oxidation seem primitive. That one thing is more valuable than almost all the rest of the discussion as a fundamental basis on which to build a reasonable in-

Jan 1, 1952