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By M. M., Fine

In a laboratory study of grinding and classification' of silica sand, a satisfactory means of producing the medium-fine specification sand desired by producers of flint-glass containers was developed. The best procedure consisted of ball-mill grinding and double classification, which gave a properly sized sand containing less iron than the feed.

Jan 1, 1950

By Robert H. Richards

The object of this paper is to enlarge the field of settling velocities treated by me in my former papers, Close Sizing Before Jigging, and Sorting Before Sizing.' There seemed need of work both on coarser and on finer sizes. Messrs. A. Sidney Warren and M. L. Nagel undertook the investigation for the coarser sizes, from 12.85 mm. down to 2.05 mm. diameter. Their work, because of the closer spacing and because of the increased number of observations and consequent stronger averages, called for a revision of the former work. Messrs. G. A. Barnaby and Ralph Hayden undertook this part of the work, from 2.49 mm. down to 0.28 mm., which is near the limit of sifting. Their work covers the ground much more minutely and comprehensively than the former papers. There remained to be covered the portion of the field too fine for investigation with the sieves. This part, covering the range of grains from 0.48 to 0.03 mm., was undertaken by Mr. E. S. Bardwell. For it he used the elutriation method. 11. The First, or Coarsest, Section of the Field. The first desideratum in this investigation was a series of sieves for sizing the sands preparatory to making the tests. It became necessary, therefore, to decide on a sieve-scale for this purpose. A sieve-scale is a series of sieves in which the dimensions of the holes of the successive members form a series increasing by a definite ratio. There are three natural sieve-scales: 1, progressing by doubling the width of the hole for each suc-

Jan 1, 1908

By Edwin H. McKee

Eruption of rhyolitic ash-flow tuffs in the area of the McDermitt (Cordero) caldera began about 17.4 million yr (m.y.) ago and continued for about 1.5 m.y. During this period of silicic eruptions, a circular area about 30 km in diameter collapsed to form a caldera that subsequently filled with sedimentary and volcanic rocks. A total of more than 200 km30f silicic rocks was erupted from the volcano. The final phase of igneous activity, about 15.0 m.y. ago, included resurgent doming and intrusion in the south-central part of the caldera. Three to 4 m.y. later (-1 2 m.y. ago), hydrothermal solutions using the northern part of the caldera ring fractures as conduits deposited silica, cinnabar, pyrite, alunite, and other minerals in tuffaceous lake beds and volcanic rocks accumulated within the caldera. The ore-forming solutions may have been a residuum from the silicic magma, or connate water, or ground water heated by the still-hot resurgent magma in the central part of the caldera. The source of the mercury and other elements has not been identified.

Jan 1, 1977

By Willard P. Ward

SOME TIME in the year 1874 or 1875, I conceived the idea that spiegeleisen might be made -in a blast furnace from ores that were not carbonates, and which did not contain both manganese and iron in the same ore. Up to this time, such ores had formed the basis of all the spiegel that had been produced; and all the ferromanganese that was on the market before 1875 was made in crucibles, and cost about 00 per ton, for 80 per cent. Mn. I consulted the great steel metallurgist of the day, Alexander Holley, who listened attentively to what I had to say, and told me he did not think my plan was practical, so I abandoned it for the time being. But I was so stubborn that I could not get the notion out of my head. It seemed to me that a good metallurgist should be able to work the thing out in some way. I had already had some experience in smelting refractory lead ores in Utah, and was young and not lacking in self confidence, so after waiting a bit, I got Anton Eilers, the best all-around metallurgist I knew, and J. H. Bramwell, the best iron blast-furnace man I knew, both intimate friends of -mine, to come to my place in Bartow County, Georgia, and look over things. They remained for several days, and made all the examination they thought necessary; and they also advised me to give up the project, and either to keep the furnace running on car-wheel iron or to blow it out. After my talk with Holley, I improved my plant in several ways. I closed the top of the furnace, put in a hot-blast stove, a steam boiler and a Weimer blowing-engine which gave me blast enough, at a pressure high enough for all the requirements of, the furnace, and which I could bring up to a temperature of 600° to 700° F.

Jan 1, 1921

By W. R. Ingalls

Jan 1, 1922

By W. R. Ingalls

Jan 1, 1922

By Francis A. Thomson

DO the curricula of our mineral technology schools prepare their graduates to meet properly the full range of their responsibilities in after life? An unequivocal "no" could be returned to this question, because training and experience in professional work are quite as important as adequate college preparation. Furthermore, a had curriculum with a splendid corps of men doing the teaching and a competent body of students doing the learning will produce a better result than an ideal curriculum in the hands of unqualified teachers and poorly prepared students.

Jan 1, 1937

By J. J. Jakosky

A REVIEW of the progress in applied geophysics during the recent depression years reveals marked advances over the methods employed several years ago. Of late, geophysical work has been curtailed to a Con-siderable extent in the fields of oil and base-metal exploration, its especial domains a few years ago. Greater attention has been directed toward the use of geophysical technique in other engineering problems. Constantly maintained research programs have developed new instruments and per-fected better field, laboratory and interpretation techniques based on experience and skill acquired from years of application in the older geophysical field. During the past two years, geophysical methods have been employed in problems that required information on thickness of fill materials and subsurface bedrock contours. Considerable success has been attained, with subsequent drilling checking the predicted depths within one to five per cent. In general, these problems were similar as far as the fundamen-tal physical and geological conditions were concerned, but they have varied widely in specific detail and in engineering aspects. Character-istic of the different problems are: (1) yardage and bedrock profile in gold-placer mining; (2) water supply, involving underground drainage and storage conditions; (3) bedrock contours in dam-site and other structural investigations; (4) gravel and fill yardage, and other structural features along rights of way and in rock and gravel quarrying. Of particular interest, perhaps, to mining men are the problems of gold placer deposits and water supply. Geophysical work on gold placers is of especial interest because of the present expanded activity in all phases of gold mining. The development of a suitable water supply at an economical cost is often of prime importance in insuring a successful mining venture. Particularly is this true in the arid Southwest. How-ever, the use of geophysical work in water supply is not confined to the needs of mining development.

Jan 1, 1933

By Samuel S. Wyer

THE following abbreviations have been used in, the text: Cassier's, Cassier's Magazine. Eng. Lond., The Engineer (London). Eng. Mag., Engineering Magazine. Eng. and Min. Jour., Engineering and Mining Journal. Eng. News, Engineering News. Eng. Rec., Engineering Record. Engng., Engineering. Engr., The Engineer (Chicago). J. I. and S. I., Journal of the Iron and Steel Institute. Jour. F. I., Journal of the Franklin Institute. Jour. Assn. Eng. Soc., Journal of the Association of Engineering Societies. Mar. Eng., Marine Engineering. . Mem, Soc. Ing. Civ., France, Memoires de la Society des Ingenieurs Civils, France. Prac. Eng., Practical Engineer. Proc. Digs. Soc. of W. Pa., Proceedings of the Engineers' Society of Western Pennsylvania. Proc. I. C. E., Proceedings of the Institute of Civil Engineers. Proc. I. 1M. E., Proceedings Institution of Mechanical Engineers. Trans. A. I. M. E., Transactions of the American Institute Mining Engineers. Sci. Am., Scientific American. Sci. Am. Sup., Scientific American Supplement. Zcitschr. d. V. D. Ing., Zeitschrift des Vereines Dentscher Ingcnieure.

Mar 1, 1905

By Arthur F. Johnson

Plant sites for the light metal industry must be located where ample low cost power is available. In the first half of the century hydroelectric development was the only source of this power-now the best sites have been exploited and those remaining do not promise enough water to permit year-round capacity power plant operation. In searching for economic plant sites engineers have concentrated on locations with vast water power potential. Olin Mathieson Chemical Corp. has been studying the economics of developing water power to make aluminum. However natural gas, lignite, and even atomic energy have also been considered as possible power sources for aluminum production. Economic studies have given consideration not merely to investment and production costs, but to total costs of delivering fabricated products to the market center of the U. S. When delivered costs are considered and when full account is taken of the newest techniques of mining bituminous coal and utilizing it to make electric power, one arrives at the inescapable conclusion that coal has emerged as the economic answer to American aluminum production.

Jan 4, 1955

By W. T. Cardwell

Physically absurd, triple-valued saturations appear in the straight-forward solution of the Buckley-Leverell equations for the displacement of oil by water or gas. From an engineering viewpoint, the triple value causen no difficulty. It is well known how it may be compensnted in order to obtain physically meaningful, numerical results. From a scientific viewpoint, the question still arises: What did the triple value mean? This paper explains how and why the triple value arose in non-capillary Buckley-Leverett theory. The discussion should serve as a background for the understanding and use of the modern method of characteristics in di.~pkzc(>ment theory. INTRODUCTION Displacement theory was introduced to petroleum technologists in 1 941 by Buckley and Leverett.' Their first equation, which they wrote down without derivation, was equivalent to the following: ?s/?t= - qr/F ?f/?r (1) where S = saturation of displacing fluid (a fraction) r = time q,. = total volumetric velocity of both the displacing phase and the phase being displaced (usually, but not necessarily, assumed to be a constant) F = porosity (a fraction) f - fraction of the total volumetric velocity that is the volumetric velocity of the displacing phase (assumed to he a function of S only x = distance. Buckley and Leverett called Eq. I "a material balance equation". Actually it is derived from both a continuity equation, or material balance equation, and Darcy's law. Buckley and Leverett jumped from their Eq. 1 immediately to their Eq. 2, which was the equivalent of the following: (?x/?t)x = qr/F df/ds = qr/F f'(s) (2) The jump from Eq. 1 to Eq. 2 involves apparently simple mathematics, but in that apparently simple mathematics lies a subtle point that is part of the key to the meaning of the triple value to be discussed here. Eq. 2 may be readily interpreted as saying that a point of constant saturation (on a saturation-vs-dis-tance curve) moves with a constant velocity that is proportional to the total volumetric rate, inversely proportional to the porosity, and is otherwise a function of the saturation itself. So that if one knows the derivativc with respect to saturation of the fractional flow function, f(S), for each saturation, one knows the velocity of each point of the moving saturation-vs-distance curve. The function f(S) can he determined experimentally and its derivative f'(S) can be calculated. It turns out that the experimentally derived f'(S) is not a monotonic function of S, but instead it has a definite maximum and declines away at both high and low saturations. This in turn means, in accordance with Eq. 2, that on a moving saturation-vs-distance curve, ccrtain intermediate saturations will travel faster than the saturations either higher or lower. The result is indicated in Fig. 1. In Fig. 1, the abscissas represent distances along a column of porous medium, which column is assumed to be uniform in cross-section perpendicular to the ab-scissal direction. The ordinates represent fractions of pore space occupied by the displacing phase, which may be either water or gas. It is assumed that the saturation is uniform over all planes perpendicular to the abscissal direction. The saturation is a function only of time and one space variable. Time variation of the saturation is represented by change in shape of a curve such as curve AGJ, which represents the initial saturation-vs-

By Donald F. Hammer, Donald W. Peterson

The Magma mine at Superior, Arizona, has produced over 13 million tons of ore yielding 1.5 billion pounds of copper. It is a mesathermal deposit, and, although the bulk of the ore has come from the Magma vein, most of the recent production has come from replacement deposits in limestone. The mine lies in a Precambrian and Paleozoic sequence of rocks that includes schist, diabase, quartzite, shale, and limestone; nearby, these rocks are intruded by igneous bodies of Mesozoic age that were probably the source of the ore-bearing fluids. Locally, these rocks are overlain by Cenozoic volcanic rocks and conglomerate. Layered rocks at the mine dip eastward about 30°. The area is extensively faulted, and surface faults are grouped into an earlier east-trending set and a later northtrending set. An additional set of diagonal faults that trends northwest and northeast is recognized underground. The east-trending Magma vein-fault, with its splits and branches, is the principal mineralized structure of the district. The bulk of the ore occurs in large ore shoots that plunge steeply westward and are sporadically connected by irregular ore shoots dipping gently eastward. The main ore controls apparently are selective zones of permeability related to the transverse faults. A bed of crystalline limestone near the base of the Martin Limestone (Devonian) is the host for the replacement ore bodies-discontinuous tabular pods dipping eastward parallel to the bedding. Selective permeability is again the apparent ore control, caused both by local hydrothermal solution of limestone and by deformation along faults. The principal copper minerals in the vein are chalcopyrite, bornite, enargite, tennantite, chalcocite, and digenite; these minerals vary in abundance according to a distinct zoning pattern. The upper part of the mine yielded considerable zinc as sphalerite, and the oxidized zone was rich in silver. The chief gangue minerals are pyrite, quartz, and hematite. In the limestone replacement bodies, chalcopyrite and bornite are the chief ore minerals.

Jan 1, 1968

Connecticut Geological and Natural History Survey, P O Box 1106, New Haven, Conn W. E Britton, Superintendent. A complete list of Bulletins available will be sent upon request. Address all inquiries for publications to: George S Godard, State Librarian, Hartford, Conn Fifty-one Bulletins have been issued, 15 of which are of particular interest, dealing with the geology of the state, and are available as follows; 4, The clays and clay industries of Connecticut, by G. F Loughlin (1905), 35 cents; 8, Bibliography of Connecticut geology, by H E Gregory (1907), 20 cents, 13, The lithology of Connecticut, by J Barrell and G. F Loughlin (1910), 45 cents, 18, Triassic fishes of Connecticut, by C. R Eastman (1911), 30 cents, 23, Central Connecticut in the geologic past, by J. Barrell (1915), 20 cents, 24, Triassic life of the Connecticut Valley, by R Lull (1915), 70 cents, 29, The Quaternary geology of the New Haven region, Connecticut, by F. Ward (1920), 60 cents, 30, Drainage modifications, and glaciation in the Danbury region, Connecticut, by Ruth S. Harvey (1920), 55 cents, 33, Geology of the Stonington region, Connecticut, by L H. Martin (1925), 60 cents, 40, The geology of the Shepaug Aqueduct Tunnel, Litchfield County, Connecticut, by W M. Agar (1927), 50 cents; 41, Guide to the geology of Middletown, Connecticut, and Vicinity, by W. N Rice and W. G Foye (1927), $1, 44, Report on the water resources of Connecticut, by R. H Suttee (1928), $1, 46, The physical history of the Connecticut shoreline, by H S Sharp (1929), 75 cents; 47, The glacial geology of Connecticut, by R F. Flint (1929), $2, 51, Minerals of Connecticut, by J F Schairer (1932), 75 cents Bulletin 51 explains the physical and chemical properties of minerals, their classification, and describes more than 100 common minerals found in Connecticut. A bibliography is included The Survey gratuitously distributes all its Bulletins to state residents, scientific institutions, etc. Prices quoted are to private citizens of other states

Jan 1, 1933

J. J. MCLELLAN, Webb City, Mo.-The Media mill, at the time it was built, was the largest mill that had been designed in the Joplin district. It was put up in a hurry, to take advantage of the high prices for zinc ore in 1915, by the owners of an adjacent plant, which had been very profitable. They owned a compound Corliss engine, and to take advantage of a single-unit drive it was necessary to build the mill in the form chosen, which involved making the hopper feed directly through the breakers and rolls, the undersize from the screen passing at once to the jigs, the oversize going through the rolls and returning to the original trommels. The mill was built in fairly good proportion; crushing was done by jaw breakers, Webb City pattern,' and three sets of 42-in. (106.7-cm.) Cornish rolls for reducing the oversize. The jigs were larger than the usual practice. The roughers were two six-cell jigs, with 42 by 48-in. cells. The cleaner jig was the largest ever constructed in the district up to that time, having seven 36 by 48-in. cells, for treating the rougher jigs. There was also a chat rougher. "Smittem," as used in our district, is the partly concentrated product from the rougher, which is finished on the cleaner jigs. "Chats" are the middlings proper, that is, they are the grains of chert with included particles of sulphide; the very low-grade smittem is sometimes included among the chats. When drawing chats from a jig, we also draw about ten times greater quantity of barren chert in order to insure complete recovery of mineral. This mixture of middlings and tailings is taken to a set of 30-in. rolls, the crushed product then going to a chat rougher, a comparatively small jig, with 26 by 36-in. cells. The principal departure of the Media mill from the usual practice was to build a hopper sufficiently high to give gravity feed to the jigs, without using elevators. The sludge plant, for table treatment of sand and slime, also contained several innovations in the manner of distributing the feed. The tables were arranged in two rows and the feed ran around the outside in a launder having two or three cone classifiers

Jan 1, 1918

By George J. Young

(San Francisco meeting, October, 1911.) THE nature of slimes handled in the treatment of gold- and silver-ores has been discussed in technical literature to a considerable extent. The subject of slime-filtration from the practical worker's stand-point has also received much comment, and scattered through the literature of the subject are descriptions of many slime-filtration installations. Articles of this nature serve a valuable purpose and assist materially in the design of new and the improvement of old plants. The subject of the physics of slime-filtration has been touched upon to only a slight extent. The underlying principles are worthy of more intensive study and experimentation than they have received, and the main purpose of this paper is to present the results of such study and experimental work as will serve to make clear in part at least many of the principles which control the filtration of slime. Nature of Slime. Much has bean written concerning an accurate definition of the term ? slime," but no comprehensive definition seems to be generally accepted. The reason for this is clear. A slime consists of at least three different substances, each, when separated, possessing distinctly different physical and to a certain extent chemical properties. These substances are extremely fine sand, a colloidal material which may be and generally is in a coagulated condition, and a colloidal material which is in a non-coagulated condition. Suspending a slime in a relatively large volume of water by shaking and allowing sedimentation to take place, results in the fine sand settling out with comparative rapidity, followed by the coagulated material, which settles much more slowly and finally a certain portion remains

Nov 1, 1911

By R. HAYDEN, H. B. HALLOWELL, H. O. Hofman

THE object of refining copper in the reverberatory furnace is to obtain a metal which will have the highest attainable degree of malleability, ductility and electric conductivity, and present at the same time a level surface when it solidifies in the mold after casting. These desirable physical properties are governed by the character of the impurities and the forms in which they are present, by the amount of cuprous oxide retained by the copper, by the quantity of gas held in solid solution, by the casting-temperature, and by the thickness of the casting. The effects of impurities, of cuprous oxide and of gases upon the mechanical properties of copper have been studied by Hampe in his classical paper "Contributions to the Metallurgy of Copper." The most recent research into the effect of metals upon the electrical conductivity of copper is that of Addicks.2 The influence of cuprous oxide upon the electrical conductivity has been investigated by Walker' and Addicks.4 The absorption of gases has received' attention by Hampe,5 Stahl 6 and Heyn.7 The effects of casting-temperature have been noted by Stahl.8

Mar 1, 1907

Institute of Metals Division Iron and Steel Division Extractive Metallurgy Division Council A W Thornton (ISD), Chairman, R W Shearman, Secretary, C S Barrett (IMD), J C Kinnear, Jr (EMD), John Chipman (ISD), J S Smart, Jr (IMD), A W Schlechten (EMD), M E Volin (MED), D S Eppelsheimer (MIED) Journal of Metals Editorial Advisory Committee J S Smart, Jr, Chairman, W A Dean, J J Golden,T D Jones, Evan Just, J C Kinnear, Jr, M Tenenbaum Pacific Northwest Regional Conference E R Marble, General Chairman, Marshall Huntting, Assistant General Chairman, W C Douglass, Mining Chairman, H C Hughes, Mining Chairman for British Columbia, W C Douglass, Mining Chair¬man for United States, Paul Billingsley, Geology Chairman, W D Nesbeitt, Miner¬als Beneficiation Chairman, H D Kelley, Industrial Minerals Chairman, J G Johnston, Metals Chairman, Lloyd Banning, Iron and Steel Chairman, W G Rouillard, Extractive Metallurgy Chairman, E C Roberts, Physical Metallurgy Chairman, D A Pifer, Mineral Industry Education Chairman, Frederick Brien, General Arrangements Chairman Metals Branch Membership Committee C M Squarcy, Chairman, R C Cole, Harold Mar¬golin, M E Nickel, S K Scovil Bylaws Committee A W Thornton, Chairman, W R Hibbard, Jr, J S Smart, Jr (IMD), John Chipman, T S Washburn (ISD), T D Jones, J D Sullivan (EMD)

Jan 1, 1956

The Cuajone and Toquepala copper projects are located in the extreme southern area of Peru. Since 1960, Southern Peru Copper Company has operated the Toquepala open -pit mine, flotation mill, 110 smelter, townsites, power plants, and railroad. Toquepala and 10, the smelter and port location, are connected by a 110-mile-long (176 lun) railroad. Much of Toquepala's infrastructure has been used for the Cuajone project. Cuajone, at an elevation of 11,400 ft (3475 m), required five standard-guage railroad tunnels with a combined length of 17 miles (27.2 km) to connect with Toquepala so concentrates could be shipped to the no smelter. The total cost of Cuajone is estimated at $726 million for a designed annual capacity of 180,000 tons of copper, equivalent to about $4,000 per ton of installed production capacity. This relatively low cost per ton, by today's standards, has been made possible through the use of the 110-to Toquepala railroad, the ability to expand the 110 copper smelter, and other favorable factors. To mine the 468 million tons of copper sulfide or e at a grade of 1.0% copper, approximately 24 1 million tons of waste were stripped- before mining of ore to supply the new Botiflaca 45, 000 ton per day concentrator. The mining rate must exceed 300,000 tons of waste plus ore per day to maintain the 45, 0 00 tpd sulfide ore milling rate which was to be reached at the end of 1976. Waste stripping is done with 15 cu yd electric shovels and 120 -ton trucks. Ore mining is done with 8 and 9 yd shovels. A railroad connects the pit with the 60 in. by 89 in. Allis-Chalmers gyratory crusher. Side-dump railroad cars of 50.cu yd capacity dump onto a 0 16 ft 9 in. long (5. 1 m) grizzly inclined at 40º with 7 to 8 in. (178 to 203 rnrn) bar spacings. The grizzly is divided into two 22 ft 4 in. (6.8 m) wide sections and two side -dump railroad cars discharge simultaneously into the 150-ton capacity dump pocket. A Barco rock manipulator is used for breaking or removing oversize from the dump pocket. The bin receiving the grizzly undersize has a capacity of 5,000 tons, and the pocket beneath the crusher holds 900 tons. Each is equipped with an 84 in. apron feeder, which feeds a 60 in. (1.52 m) conveyor belt to the 150,000 ton coarse ore stockpile, where the ore is distributed by a 72 in. (1. 83 m) tripper conveyor. The 45, 000 live tons in the coarse ore stockpile are reclaimed by twelve 48 in. (1. 22 m) apron feeders. Maintenance on the crusher eccentric is made easy by an eccentric

Jan 1, 1978

By E. S. Machlin

An extension of the thermodynamic theory has been made for the case of irreversible growth processes occurring by the motion of an interface. The theory is applicable to such diverse phenomena as diffusion, growth in recrystallization, continuous grain growth, growth of carbides, etc., growth of eutectoid products, growth in solidification, recovery, "slipless" flow, etc. THE publication of a recent book1 has served to focus attention on a very powerful means of treating certain irreversible processes. This method which has been formally described as the thermodynamic theory of irreversible processes is applicable to processes which involve an approach to equilibrium and for which the deviations from equilibrium are small. The irreversible processes can be classified into three groups: chemical reactions, transport processes (diffusion, heat and electrical flows), and relaxation phenomena involving a degradation of internal energy to more stable states. The limits of applicability of the theory can be precisely defined1,2 for each type of irreversible process. For example, in a chemical reaction at constant temperature and pressure, the Gibbs free energy released per mol in the process should be less than the thermal energy, RT. Another type of irreversible process, which sometimes involves a combination of the first two of the above-mentioned groups, is treated in this paper. This process is one characterized by the motion of an interface separating two regions having different values of free energy and may be briefly described as a growth process. Prigogine2 and Herring3 have treated special cases of this type of process. Previous conscious applications of the theory in metallurgy have been limited to the field of diffusion, one of the transport processes. Darken,4 Bardeen,5 Prigogine2 and others have made significant contributions in this respect. Some other applications of the theory are described in this paper. The Theory The thermodynamic theory of irreversible processes is based on the work of Onsager,6 DeDonder,7 Prigogine2 and others. A resume of the theory has been given by Prigogine2 and DeGroot.1 A brief description of the theory follows, although for a complete understanding the reader is urged to read the references. It is first assumed that the change in entropy, even for a system removed from equilibrium, is given by dS = [dU + pdV - Si µi, dn, - Sk Pk dxk]T-1 Using this expression, the irreversible entropy production in the system is calculated by subtracting the contribution to the change in entropy of the system by transfer of heat, work, or matter from the surroundings. Thus, for example, the irreversible entropy production of a system at constant temperature and pressure is given by dtS = — — dG (DeDonder7) Now it has been shown by Prigogine,2 DeDonder,7 and DeGroot1 that the rate of irreversible entropy production diS/dt, when calculated in the manner suggested, can be written as a sum of products of conjugate forces XK and fluxes Jk, i.e., d,s/ = Sk Jk Xk [I-1] dt The assumption is next made that a linear relation exists between a given flux and the forces, obtained from Eq. I-1, i.e., Ji = Sk Lik Xk (i = 1, 2, . . . n) [I-2] Generally, there is a degree of freedom in choice of the fluxes and forces. However, for all the choices consistent with Eq. I-1 the Onsager8 relations, based on the principle of microscopic reversibility, namely, Lik = Lki, are valid. The coefficients Lik, depending upon the choice of the conjugate fluxes and forces, may be more or less dependent upon the parameters defining the state of the system. In general, the proper choice of fluxes and forces utilizing Eq. I-1, makes the coefficients Lik independent of time. Also, because many of the three classes of irreversible phenomena have already been treated,1,2 a proper choice can be made by analogy. In any case, the validity of Eq. 1-2, from whatever choice made using Eq. I-1, must be tested by experimentation. The theory, thus, comprises the following steps: 1—The irreversible entropy production is calculated to yield Eq. I-1. 2—The terms in Eq. I-1 are grouped

Jan 1, 1954

By George Simkovich

It was hypothesized that solid-state point defects should alter the flotation properties of solids. Tests conducted on pure AgCl and AgCl doped with CdC12 show that atomic point defects exhibit an important role in the floatability of AgC1. Tests conducted on PbS doped with Ag2s or Bi2S3, also show that the defect structures resulting from these dope additions, i.e., a combination of electronic and atomic point defects, contribute significantly to the flotation of PbS. IT has been established that flotation occurs only when a finite contact angle exists between a solid and a gaseous bubble.' This angle, measured through the liquid phase, is expressed by the equation where the are inter facial free energies and the subscripts S, G, and L represent solid, gas, and liquid phases, respectively. As is seen in Eq. [I] three interface free energies, sG, sl, and GL, enter into the contact angle equation. Therefore, any variation in these energies which sufficiently varies the contact angle will, in turn, vary flotation processes. Changes made in any of the phases concerned, i.e., gas, liquid, or solid phase, are reflected through the changes occurring in two of the surface energy terms. Thus, a change in the liquid composition would be noted in sL and GL, and it is this phase, the liquid, which is most frequently altered in flotation studies., Changes in the solid phase must be reflected through the changes occurring in the sG and sL terms. In particular, it is hypothesized that changes in the surface concentrations of point defects in the solid-phase will alter the sG and sL terms which, in turn, will be reflected by flotation results. As an illustration of this hypothesis one may consider the defect structure and the flotation of AgC1. The bulk defect structure of AgCl is essentially one involving equal number of cation vacancies and interstitial cations.3 Upon adding CdC1, to AgC1, a greater number of silver ion vacancies are created in the bulk of the crystal.4 On the surface of the crystal the smaller binding forces and the free space accomodations may also allow for the creation of "surface interstitial anions", which will be designated as ad-anions. Thus, the point defect structure of the surface of AgCl doped with CdCl, will consist of cation vacancies and/or adanions. If the molecular forces responsible for the surface energies, ?SG and ?sL, are significantly altered by the presence of these surface point defects, then differences in flotation results will be noted as the concentration of these defects is varied. The defects present in AgCl are predominantly atomic in nature. In the case of PbS both electronic and atomic defects are present.5 This compound conducts electrically by either electrons or electron holes depending upon whether excess lead or excess sulfur is present. Upon disolving BiS3 in stoichio-metric PbS, one increases the concentration of cation vacancies and the number of electron carriers in the bulk of the crystal.5" At the surface, the possibility of ad-anions must also be considered. Conversely, upon dissolving AgS in stoichiometric PbS one increases the concentration of interstitial cations and the number of electronhole carriers in the bulk of the crystal.5,6' At the surface the interstitial cations will be designated as ad-cations. Thus, the point defect structure of the surface of a PbS crystal doped with Bi2S3 will consist of a number of cation vacancies and/or ad-anions and an excess of electrons. Conversely the point defects on the surface of a PbS crystal doped with Ag2S will consist of a number of ad-cations and an excess of electron holes. Again, as in the case of AgC1, should the molecular forces responsible for the magnitude of the interface free energies, ?sG and ?sL, be significantly altered by the presence of these surface defects then significant differences in flotation results will be noted as the concentration of these defects is varied. EXPERIMENTAL To test this hypothesis flotation tests were conducted on pure and doped AgCl and on PbS doped with either Bi2S3 or Ag2S. Preparation of the AgCl samples was performed as follows: AgCl and weighed amounts of CdC1, were melted in a porcelain crucible. The melt was then forced through a capillary tube and the particles emitted solidified in air as they fell about 1.5 meters. Spherical particles, -0.50 + 0.25 mm, were separated from the remaining solidified material

Jan 1, 1963