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By W. Philippoff

ALTHOUGH Gaudin1 and more recently Sutherland2 have calculated the probability of collision of a falling mineral particle with a rising bubble, there is no published information concerning the details of the mechanism of attachment of a collector-coated particle to a bubble. During the past year the writer has developed a theory for the mechanism of attachment, which has been substantiated experimentally.' Funds for the investigation and for some of the equipment used have been supplied by the Mines Experiment Station of the University of Minnesota. Motion picture studies of the phenomena involved in the collision between mineral particles and bubbles, such as those of Spedden and Hannan,3 show that the contact can be completed within 0.3 millisec. Formulas developed for rigid bodies have hitherto been used' for the calculation of the motion of bubble and particle, but it is obvious that a bubble cannot be regarded as a rigid body. On the contrary, Spedden and Hannan's pictures show a great degree of deformation during the collision. The time of attachment was calculated as the time the particle drifted past the bubble. Time of Collision The theory presented in this paper enables calculation of the time of collision; using the concept that the bubble, or more generally, a liquid-air interface, acts as an elastic body. The elasticity, defined as the restoring force on a mechanical deformation, is caused by, the surface tension and is the result of the principle of the minimum of free surface energy. It is well known that an elasticity together with a mass determines a frequency of vibration. The vibrations of jets and drops caused by the elasticity of the interface are known to comply exactly with the classical theory of capillarity.5 However, the vibrations of isolated bubbles, as distinct from foams, have not been investigated previously. The following equation, presented elsewhere,' has been deduced for these frequencies: [3fB = 9.20•'./V•Vn- (n-1) • (n+2) /8[1]] in which fB is the frequency of a harmonic of the bubble in cycles per second, V the volume of the bubble in cc, n a number determining the order of the harmonic, and n = 2 the basic vibration. The first (basic) harmonic describes a change of the spherical bubble to an ellipsoidal bubble. The higher harmonics are more complicated, for the circumference of the bubble is divided approximately into as many parts' as the order of the harmonic. As an example, Spedden and Hannan's published motion picture of, a vibrating bubble corresponds to the sixth harmonic. Eq 1 shows that only the first and third harmonics are simple multiples (1 and 3), all the others being irrational fractions of the basic frequency. This means that the shape of the vibration can change with time and is in general unsymmetric in respect to the time axis. Such conditions prevail when there is a distributed elasticity or mass, as in the case of vibrating membranes or rods. The constant 9.20 is valid for water at room temperature, but a general solution involving the physical constants of the liquid has not been found. The case of the floating particle is much easier to treat I than that of the bubble. It can be assumed that the elasticity is caused exclusively by the interface and that the mass is concentrated in the particle together with some adhering water. The following expression for the frequency of a system, of one degree of freedom can be applied: [1E/m[2] fP = 27] Here f, is the frequency of the particle vibration in cycles per second, E the elasticity in dynes per cm, and m the mass in grams. The classical theory of impact phenomena gives the time of collision during the striking of a spring (in this case the surface of the bubble) by a mass, as: [t~ = 2/f = 7r\/m/E[3]] It is now possible to develop an expression for the elasticity of a floating cylindrical particle. The force equilibrium of a cylinder floating end on at the air-liquid interface is given by the well-known equation (Poisson' 1831) [aP = 4 D2.pL•g•h +7rD•y sin a[4]] which accounts for the buoyancy and the action of the surface tension where P is the force acting on the particle in dynes (weight-buoyancy), D the diameter of the cylinder in cm, pL the density of the liquid in grams per cc, g the acceleration of gravity = 981 cm per sec2, h the depression of the cylinder below the surface of-the liquid in cm, y the surface tension in dynes per cm and a the supporting angle' or the one required to insure equilibrium, a being smaller than the contact angle ?. Although demonstrated by Poisson, it has not

Jan 1, 1952

By Ronald D. Hill, Janet L. Auerbach

It is estimated that the mining industry generates over 2.1 petrograms per year of solid waste. These wastes are overburden, waste rock, low grade ore, concentrate (tailing), sludges from treatment facilities and wastes from support facilities. Concentrate wastes present the greatest environmental problem. Three recent federal laws impact the disposal of waste from mining: Resource Conservation and Recovery Act of 1976 (RCRA), Surface Mining Control and Reclamation Act of 1977, and Uranium Mill Tailings Radiation Control Act of 1978. RCRA specified a special study on mining waste which was to include an analysis of: (1) sources and volumes of waste produced, (2) present disposal practices, (3) potential dangers to health and the environment, (4) alternate disposal methods, (5) cost of disposal, and (6) potential for use of waste.

Jan 1, 1980

By E-Tu Zen Sun

Yunnan, a mountainous province in southwestern China, began to assume its place as an important producer of copper toward the end of the Ming dynasty (latter part of the 16th century), and since then has continued, with minor interruptions, to occupy a leading position as one of the few areas in China where relatively significant amounts of this metal can be produced. Among the copper deposits of this province, those of the following three localities have stood out as being the most significant. 1. Tung-ch'uan, in northeastern Yunnan. Here the ores are primarily bornite and chalcocite, with copper content ranging from 2% to 15% the most noteworthy T'ang-tan mine producing ores averaging 12% copper. Estimated total reserve of pure copper in this area is approximately 1,000,000 metric tons.

Jan 7, 1964

By R. Chanchani

Single and mixed mineral flotation behavior and the mechanisms for the loss of selectivity in 1:1 and 95:5 apatite: dolomite mineral mixtures are presented. Loss of selectivity in mixed mineral systems is attributed to depletion of oleate ions available for adsorption by bulk precipitation with calcium and magnesium ions dissolved from dolomite. Flotation after two-stage conditioning was found to be a potential technique to separate dolomite from apatite. This method involves conditioning at pH 10 followed by reconditioning at a lower pH. The results indicate that selective flotation of dolomite, a minor mineral in south Florida phosphate deposits, could be obtained by reconditioning at pH below 4.5. Higher selectivity was observed for mixed minerals as compared to that of single minerals.

Jan 1, 1986

1. A passenger rickshaw in China. 2. A Pekin cart carrying coal, on dirt roads; the cost works out to 15 or 20 c. per ton-mile. 3. Coolie with wheelbarrow. This one has a small load, but barrow men carry ordinarily 250 lb., occasionally 400 if with a helper. He goes about 18 miles a day and the cost is about 25c. gold per ton-mile, though it varies widely. 4. Coolie delivering coal balls in Pekin. He carries about 65 lb. On some roads with a different arrangement a coolie carries 133 lb., making about one ton-kilometer per day. 5. Truck used by the Government Fuel Yard at Washington. Carries 71/2 tons in an hour as far as a barrow man carries 1/4 ton in a day.

Jan 8, 1928

By T. C. Desollar

THE group of iron-ore mines known as the Red Ore Mines, owned and operated by the Woodward Iron Co., is on Red Mountain approximately ten miles southwest of Birmingham, Ala. At the, present time No. 1 and No. 3 mines are active, No. 2 mines having been abandoned in 1928. Ore from this group of mines was first mined in 1882, and originally came from open cuts along the outcrop, but, when the "soft ore" (weathered hematite) was mined out and the harder ore was encountered, it became necessary to develop the orebody by means of slopes driven in the ore formation. The three mines to date have produced more than 22,000,000 tons, and the two operating mines now have a capacity of over 1,000,000 tons per year.

Jan 1, 1933

By H. J. Beattie, G. C. Gould

J. B. Seabrook' recently published properties of a low-alloy Ni-A1 age-hardening steel known commercially as "Nitralloy-N". He mentioned three possible mechanisms of age hardening, viz. order-disorder in the matrix, order -disorder in a precipitate, and a precipitate that goes in and out of solution reversibly without losing coherency. The following results indicate that the last - mentioned of these mechanisms is the cause of age hardening in Nitralloy-N. The reversibility of the age hardening with a sub-critical solution temperature was demonstrated strikingly by Seabrook, whose results are reproduced in Fig. 1. Aging for 22 hr at 975°F (525°C) can reharden the fully-tempered martensite to its original as-quenched hardness of R, 45. A Nitralloy steel was obtained from Seabrook' with the following analysis:

Jan 1, 1962

By George G. Griswold

The Parkes process of lead refining is based on the fact that when zinc isemixed with molten lead bullion, it forms an alloy with the silver and gold. This alloy freezes at a higher temperature and is of a lower specific gravity than the lead. With proper regulation of the temperature, the alloy solidifies and floats on top of the lead bath, from which it is removed and the silver, gold, and zinc recovered. The alloy should contain the maximum amount of silver (Ag2Zn,). The usual practice is to make two additions of the zinc. The first addition gives an alloy, or zinc crust, the zinc of which is saturated and is treated for the recovery of its zinc and silver; the crust from the second addition contains an excess of zinc and is used for the first addition on the following kettle. The crust produced depends on a number of items: purity of bullion, temperature, care with which kettle work is performed, addition of zinc, pressure used in expelling lead from crust, etc. It is desirable to make the concentration of silver in the zinc crust as high as possible; otherwise an undue amount of byproducts is produced, which greatly increases the cost of refining. It was formerly considered good practice to make a concentration of 20 :1. That is to say, if the lead bullion assayed 150 oz. dorê per ton, the assay of the retort bullion recovered from the zinc crust should be 3000 oz. per ton. As a matter of fact, the concentration should never, except on bullion assaying over 300 oz., be so low, and with low-grade bullion it should be 50:1. In one lead refinery where, ordinarily, the work was good, on a bullion averaging about 200 oz. per ton, a concentration of 24:1 was common; but how it was obtained was known only to the foremen. Changes occurred, and under new foremen the kettle work fell off badly; the problem then was to bring about this greater concentration. As is customary, the refincry had a "schedule" for its 60-ton kettles, which gave the number of pounds of zinc required for all possible assays, on both the first and the second zincing. Using this schedule, high temperatures

Jan 1, 1924

By Raymond Mancha

TO determine the optimum inside dimension of an airshaft, it is necessary to strike the proper balance between the cost of power for air friction and turbulence losses within the airshaft, on the one hand, and the cost of sinking the airshaft, on the other. An airshaft larger than necessary is extravagant because the increased amortization rate exceeds the reduction in power cost. Conversely, an airshaft smaller than is needed wastes more power than can be justified by the corresponding reduction in amortization rate. The airshaft power is a function of the air volume Q cu. ft. per min. and the air-pressure drop p in. water gauge across the airshaft. † The airshaft pressure drop is calculated by the formula: R X l X O X Q2 P= 5-2 X A3 wherein R is the air-friction coefficient for the portion of the airshaft 1 ft. deep, 0 ft. in perimeter and A sq. ft. in area, when passing an air volume of Q cu. ft. per minute. The airpower w kw. dissipated within the airshaft is computed by the formula: w= 0.746Q X P 6345 With a combined over-all unit efficiency of the fan and drive of E per cent, the air-shaft power requirements become W = 100w There are 8760 hours per year, so with energy at I cent per kilowatt-hour the annual cost per kilowatt for continuous operation is $87.60; therefore, with energy at C¢ per kw-hr. the annual airshaft power cost MI dollars per year becomes: M1 = 87.60W X C which, expressed by the component parts, becomes: M1 V 5.2X4' / XQ Z 0.746 X 100 X 87.60 X C V 60 X E ) The amortization rate a dollars per year per dollar invested includes both depreciation and interest on the investment. These in turn involve the expected useful life of the airshaft and available molletary interest rate. For the purpose of this discussion the cost of airshaft sinking is assumed to comprise a fixed move-in charge Y dollars, which covers the cost of transporting, erecting and removing the shaft-sinking equipment and is independent of the air-shaft size. Also, it is assumed that the cost of shaft lining, if any, is fixed at $X per cu. yd. of lining material and that excava-

Jan 1, 1947

By Raymond Mancha

TO determine the optimum inside dimension of an airshaft, it is necessary to strike the proper balance between the cost of power for air friction and turbulence losses within the airshaft, on the one hand, and the cost of sinking the airshaft, on the other. An airshaft larger than necessary is extravagant because the increased amortization rate exceeds the reduction in power cost. Conversely, an airshaft smaller than is needed wastes more power than can be justified by the corresponding reduction in amortization rate. The airshaft power is a function of the air volume Q cu. ft. per min. and the air-pressure drop p in. water gauge across the airshaft. † The airshaft pressure drop is calculated by the formula: R X l X O X Q2 P= 5-2 X A3 wherein R is the air-friction coefficient for the portion of the airshaft 1 ft. deep, 0 ft. in perimeter and A sq. ft. in area, when passing an air volume of Q cu. ft. per minute. The airpower w kw. dissipated within the airshaft is computed by the formula: w= 0.746Q X P 6345 With a combined over-all unit efficiency of the fan and drive of E per cent, the air-shaft power requirements become W = 100w There are 8760 hours per year, so with energy at I cent per kilowatt-hour the annual cost per kilowatt for continuous operation is $87.60; therefore, with energy at C¢ per kw-hr. the annual airshaft power cost MI dollars per year becomes: M1 = 87.60W X C which, expressed by the component parts, becomes: M1 V 5.2X4' / XQ Z 0.746 X 100 X 87.60 X C V 60 X E ) The amortization rate a dollars per year per dollar invested includes both depreciation and interest on the investment. These in turn involve the expected useful life of the airshaft and available molletary interest rate. For the purpose of this discussion the cost of airshaft sinking is assumed to comprise a fixed move-in charge Y dollars, which covers the cost of transporting, erecting and removing the shaft-sinking equipment and is independent of the air-shaft size. Also, it is assumed that the cost of shaft lining, if any, is fixed at $X per cu. yd. of lining material and that excava-

Jan 1, 1947

By Robert D. Thomson

LISTED among strategic and critical minerals for stockpiling, mica is an important raw material in electronic and electrical equipment industries. Each year large quantities are consumed in the manufacture of television and radio tubes, radar sets, generators, transformers, electric toasters, and irons. Crude mica, which comes from the mine in crystals or in rough books of various shapes and sizes, is known as run-of-mine or book mica. Structural imperfections, impurities, rough edges, and defective laminae are removed by cobbing, rifting, and trimming to produce a marketable block mica or film mica.' After the rough books have been hand-cobbed to remove adhering rock, dirt, and crushed or defective mica they are rifted, or split. In the U.S. a straight-bladed knife is generally used for rifting. Products of this operation are classed broadly as untrimmed sheet mica and scrap. Sheet mica is any relatively flat piece sufficiently free from physical defects to be cut or stamped into specified shapes for industrial use. Sheet mica is classed as block, film, and splittings. Block mica is not less than 0.007 in. thick with a minimum usable area of 1 sq in. Film mica is split from the better qualities of block mica to groups of specified thickness ranging from 0.0012 to 0.004 in. Splittings are sheets with maximum thickness of 0.0012 in. and minimum usable area of 3/4 sq in. As virtually no mica splittings are produced in the U.S., they will not be discussed in this report. Small, low quality block is subdivided as punch and washer. Punch mica is thumb-trimmed material large enough to yield a circular disk of at least 11/2 in. diam for stained quality mica and 1 1/4 to 2 in. for clear quality. Poorer lots, often referred to as washer mica, are also included in the general term punch mica. Trimming, the next step in processing sheet mica, removes broken and ragged edges, loose scales, and other major imperfections. Trimming may be done with a knife, sickle, shears, or fingers. In the U.S. it is usually done with a 3-in. linoleum knife to obtain a bevel-edged cut. If ragged edges are broken off with the thumb and fingers, the mica is called thumb-trimmed. Full-trimmed is rifted mica trimmed on all sides with all cracks, reeves, and

Jan 1, 1957

By F. J. Martin, W. G. Hubler

The Beattie mine is at about the center of Duparquet township in the Province of Quebec, Canada. It is 22 miles northwest of the town of Noranda. The elevation is approximately 1200 ft. above sea level. This locality, long considered a favorable one from the geological point of view, has been prospected for over 20 years, but no discoveries of economic importance were made until the present orebody was found by John Beattie in 1930. The specific gravity of the ore is 2.77. The gold occurs in intimate association with the sulfides, pyrite and arsenopyrite, which in turn are very finely disseminated in a silicified porphyry. The bulk of the gold is associated with the pyrite, only a small proportion being with the arsenopyrite. There are small amounts of magnetite, ilmenite and chalcopyrite present in the ore. There is also some hematite in the ore that is mined from near the surface in the open pit. Metallurgical Problems and Methods or Attack 1. The ore is extremely hard and resistant to grinding. 2. The sulfide minerals are finely disseminated in the gangue. 3. The gold, in turn, is so intimately associated with the sulfides that grinding to even 5 microns will not release all of the values for cyanidation. 4. It is necessary to make a high ratio of concentration in order to obtain a product sufficiently high in gold to meet high shipping and treatment charges. Hardness of the Ore.—Owing to the extreme resistance of the ore to grinding, it was recognized that grinding costs would be high. Microscopic tests showed that grinding to 95 per cent minus 325 mesh would be necessary to liberate a sufficient amount of the values in order to obtain a tailing assaying 0.02 oz. gold per ton, which is considered to have the economical minimum gold content that can be obtained. It is not feasible to grind this hard low-grade ore (0.18 to 0.20 oz.) to 95 per cent minus 325 mesh, so it was necessary to overcome the problem in another way. The following method was decided upon: (1) Fine crushing to minus 1/4 in.; (2) relatively coarse primary grinding; flotation of low-grade concentrates in the primary and rougher circuits and discarding the

Jan 1, 1935

The Institute maintains a dual relationship with students: (1) an individual relationship with a Student Associate; and (2) a relationship with local organizations of students, known as Affiliated Student Societies or Student Chapters. 1. The conditions of Student Associateship are set forth in Section 9, Article I, of the Bylaws of the Institute (see page 62 and following pages). During 1934, sundry amendments were made for the purpose of improving the student relationship. Postgraduate students are now eligible; and associateship can be maintained, with the payment of the regular dues of $2 per year, for 18 months following graduation in June. With his regular dues, each Student Associate is entitled to receive during the year his choice of MINING AND METALLURGY, METALS TECHNOLOGY, MINING TECHNOLOGY, PETROLEUM TECHNOLOGY, or two "classes" of Technical

Jan 1, 1944

By J. A. Bowknocker

NATURAL GAS was secured in the Trenton limestone near Findlay, Hancock County, in 1884, and oil in the following year. Drilling was rapid so that the production increased by leaps and bounds; in 1896, it exceeded 25,250,000 bbl., the maximum for the field. Since that time, the yield has decreased steadily and in 1921 was only 1,447,243 bbl. The territory extends as an arc of a circle from near the western end of Lake Erie southwest into Indiana, which it enters in Adams and Jay Counties. Sixteen counties are listed in Ohio but five of them combined had a new production of only 264 bbl. and they might well be omitted. Progress in the Trenton limestone field of northwest Ohio in 1923 is shown in Table 1.

Jan 3, 1924

The Institute maintains a dual relationship with students: (1) an individual relationship with a Student Associate; and (2) a relationship with local organizations of students, known as Affiliated Student Societies or Student Chapters. 1. The conditions of Student Associateship are set forth in Section 9, Article I, of the Bylaws of the Institute (see page 62 and following pages). During 1934, sundry amendments were made for the purpose of improving the student relationship. Postgraduate students are now eligible; and associateship can be maintained, with the payment of the regular dues of $2 per year, for 18 months following graduation in June. With his regular dues, each Student Associate is entitled to receive during the year his choice of MINING AND METALLURGY, METALS TECHNOLOGY, MINING TECHNOLOGY, PETROLEUM TECHNOLOGY, or two "classes" of Technical

Jan 1, 1942

(This list. includes only those who have entered military service within the past month, or whose entry has only recently become known to us; it also includes a few names of those whose titles or assignments have been changed within the month. A complete list will he found in the Year Book mailed with this Bulletin. Another Honor Roll is maintained in the reception room of the Institute.) ALDEN, HERBERT W., Lieutenant-Colonel, Ordnance Dept. ALDER, ALFRED; Engineers' Reserve Corps. ALFORD, NEWELL G., Sergeant, Bureau of War Risk Insurance, Headquarters 84th Division. AMBLER, HARRY A., Lieutenant, 30th Infantry. ANDERSON, GEORGE K., JR., Sec. C, 1st Co.; 3d Officers' Training Camp. AYER, -FRANK A., 1st Lieutenant, 43d Squadron, 3d Prov. Regiment, Aviation Camp.

Jan 3, 1918

Edward K. Landis, Philadelphia, Pa.: In studying Mr. Thackray's paper it seemed that a critical comparison of the results from different methods therein reported would he of interest. For this purpose Table I. was constructed by grouping all determinations made by the same method, and the probable errors were calculated. In this table all chemists titrating with permanganate (A1, E, F, G and 0 of Mr. Thackray's paper) are classed under "Emmerton;" those titrating with nitric acid (C, J, S and Y) under " Handy; " those re Probable error of result: a, ±0.0008996; b, ±0.000694; c, ±0.00107; d, ±0.00115; e, ±0.000674; f, ±0.000473; g, ±0.003675; h, ±20.0007959; i,0.000.5098; k, ±0.0008303. Probable error of single determination: a, ±0.001989; b, ±0.001547; c, ±0.00214; d, ±0.0023;e, ±0.00116;f, ±0.000818;g, ±0.0019;h, ±0.00224; i, 40.00143; k, ±0.00234. The formula for calculating the probable error is 0.6745, where N (N— 1)' S is the sum of the squares of the differences from the mean and N is the number of determinations.

Jan 1, 1897

By R. C. Mahon

Operators concerned with the destruction of their piping by acid mine waters will be interested in the method by which this problem was solved at the Cardiff mine of the Homer group. Rubber lined, or acid resisting metal pipes were found too expensive. Casting concrete lining in pipe would have required a minimum thickness of one inch, thus excessively reducing the pipe's diameter, as well as taking twenty four hours per length of pipe. The Naylor Pipe Co. of Chicago, having experimented with centrifugal lining of pipe with concrete, provided information which eventually solved the problem. An experimental plant was constructed as shown, and the following procedure developed : (1) Kerosene is used to remove the interior oil coating of new pipe. Closed with blank flanges, the pipe is revolved for eight minutes at varying speeds. Stopping and starting the motor achieves a good washing action. The kerosene is then drained off, and similar washing action with caustic soda removes any excess. Swabbing in done with burlap fastened to a 1/2-in. pipe. (2) The aggregate, made of one. part quick-setting cement and two

Jan 1, 1949

By E. Mille, R. Geffken

The Mg-Si and Mg-Ge phase diagrams were rede-levtnined by thermal analysis, and the existence of a single congruent melting compound in each system was confirmed. The melting points of the two compounds Mg2Ge and ,Wg2Si were found to be 1117.4° and 1085.0°C respectively. The euteclics for the Mg-Ge system occur at 635.6°C (1.15 at. pcl Ge) and 696. 7°C (64.3 at. pct Ge); for the Mg-Si system the eutectics are at 6376°C (1.16 at. pct Si) and 945.6°C (53.0 al. pcl Si). The phase diagrams and known thermodynamic data were used to calculate activity values for both systems. The activities calculated for the Mg-Ge system agreed very well with those previously published. Partial molar enthalpy values for the Mg-Si systetn were calculated from the phase diagram for the composition region where no experimental values have been reported. THE phase diagram for any system is an important source of thermodynamic data. Steiner, Miller, and Komarek1 have derived equations which permit calculation of the activity in binary systems with an inter-metallic compound! if the liquidus and enthalpy data are known. The thermodynamic properties of the Mg-Ge and Mg-Si systems have recently been determined in this by by an isopiestic method, and it was considered that it would be interesting to compare these directly determined values with those computed from the phase diagram. The basic features of the Mg-Ge and Mg-Si systems are essentially similar. The one intermediate compound present in each system. Mg2X, crystallizes in the antifluorite structure and melts congruently. Raynor4 has accurately determined the temperature and composition of the magnesium-rich eutectic in both the Mg-Ge and Mg-Si systems. Klemm and West-linning5 investigated the entire Mg-Ge liquidus, employing sintered alumina crucibles; the purity of the magnesium and germanium starting materials was not reported. The melt was not stirred, and the temperature was automatically recorded to an accuracy of ±3°C. The authors reported large weight changes due to magnesium evaporation between 50 and 67 at. pct Mg. The Mg-Si system has been studied by a number of investigators, and the results have been compiled by Hansen and Anderko.6 Significant discrepancies exist between the two principle investigations of voge17 and Wohler and Schliephake.8 Two different grades of silicon were used by Vogel, one of 99.2 pct purity and the other quite impure, containing 6 pct Fe and 1.7 pct Al. The magnesium purity was not specified. The melts were contained in graphite crucibles with porcelain thermocouple protection tubes under an atmosphere of hydrogen. Samples weighing 10 g were rapidly heated to 50° to 100°C above the liquidus: held, and then rapidly cooled without stirring. Accuracy was ±1 at. pct which is equivalent to a maximum error in temperature of ±18°C. Wohler and Schliephake used 97.9 pct Mg and 99.48 pct Si. The graphite crucibles contained a stirrer and the 15-g samples were melted under an atmosphere of streaming hydrogen. The samples were chemically analyzed after each run. Because of the scarcity of the data, the impurity of the starting materials, and the resultant uncertainty and inconsistency in the published liquidus values, it was decided to undertake a reevaluation of the Mg-Ge and Mg-Si phase diagrams by thermal analysis. EXPERIMENTAL PROCEDURE Alloys were prepared from 99.99+ pct Mg (Dominion Magnesium Ltd.) with impurities in ppm: 20 Al, 30 Zn, 10 Si, <1 Ni, <1 Cu. <10 Fe; 99.999 pct Ge (United Mineral and Chemical Corp.), and 99.999 pct Si (Wacker Chemie Corp.). All graphite parts were machined from high-density (1.89 g per cu cm) G-grade graphite obtained from Basic Carbon Corp. with a total ash content of 0.04 pct. Boron nitride parts were machined from rods of National-grade H.B.N. boron nitride. All graphite and boron nitride pieces were baked out under running vacuum at 1100°C for 24 hr before us Cylindrical graphite crucibles (1; in. OD, 23/4 in. long, l3/8 in. ID) were tightly closed with threaded graphite covers which had 21/4-in.-long thermocouple wells and 1/4-in.-diam off-center holes for stirrers. The cover and thermocouple well were machined from a single piece of graphite. A stirrer was made from a flat cylindrical graphite plate perforated with five 3/16-in.-diam holes and a 1/2-in.-diam central hole, and was held parallel to the crucible bottom by a 1/4-in.-diam. 4-in.-long graphite rod which screwed into the plate and extended up through a tightly fitting hole in the crucible cover. An iron core enclosed in a glass capsule was attached to the stirrer with an 18-in.-long molybdenum wire, so that the stirrer could be magnetically raised and lowered from outside the system. One crucible and stirrer with essentially the same dimensions given above was made entirely of boron nitride. Chunks of magnesium were premelted, cast into 11/2-in.-diam. rods, and then cut into lengths varying from a to 1 in. A 5/16-in. hole was drilled through the center of each piece to accommodate the thermocouple well and the individual pieces were then cleaned and rinsed with acetone. The total weight of an alloy was 50 to 70 g in the Mg-Ge system and 40 to 60 g in the Mg-Si system. The pure components were weighed to an accuracy

Jan 1, 1969

By M. A. Dayananda, R. E. Grace

Vapor-solid diffusion couples were employed in a study of ternary diffusion in the single-phase copper-rich corner of the Cu-Zn-Mn system Interdiffusion coefficients were measured at three different compositions corresponding to the intersections of diffusion paths determined at 850°C. Intrinsic diffusion coefficients were determined at two compositions by the Philibert-Guy method. New relations between the various intrinsic diffusion coefficients are also presented. MOST of the investigations of ternary diffusion have been made with "sandwich" couples formed by welding together two homogeneous solid solutions with or without markers placed at the interface. With such couples Kirkaldy and his coworkers1,2 have determined interdiffusion coefficients which describe ternary diffusion in the substitutional alloy systems, Cu-Mn-A1 and Zn-Cu-Al. Guy and Leroy3 have reported intrinsic diffusion coefficients for Co-Ni-Cr alloys as a function of composition using the analysis of Philibert and Guy.4 The use of semi-infinite diffusion couples, for example, vapor-solid couples, where the diffusing species are supplied from a vapor source in contact with a diffusion disk, has so far been confined to studies of binary diffusion. Balluffi et a1.5,6 have successfully determined the interdiffusion as well as the intrinsic diffusion coefficients in several binary metallic systems employing vapor-solid couples with markers initially placed at the vapor-solid interface. They have also discussed the general advantages and limitations of such couples. Vapor-solid diffusion couples can successfully be employed in ternary diffusion studies. The importance of such couples in ternary diffusion lies in the fact that inert markers lie close to the vapor-solid interface, and the composition of the marker plane is virtually known before experimentation begins. Another minor advantage is that the method of Philibert and Guy4 may be used with three alloys instead of four. Lastly, the diffusion paths need not be S-shaped, as pointed out by Meijering7 for "sandwich" couples. The Cu-Zn-Mn system is convenient for ternary diffusion studies because of the large single-phase field in the copper-rich corner. The vapor pressure of zinc above such alloys is known, and X-ray measurements indicate that the molar volume is nearly constant over a wide range of compositions.8,9 It is the purpose of this paper a) to extend the analysis of Balluffi and seigle5 to permit an evaluation of interdiffusion coefficients in ternary vapor-solid couples, b) to use the method of Philibert and Guy to determine intrinsic diffusion coefficients with such couples, and c) to present experimental data on both interdiffusion and intrinsic diffusion coefficients for the Cu-Zn-Mn system at 850°C. INTERDIFFUSION IN TERNARY VAPOR-SOLID COUPLES The analysis of Balluffi and seigle5 is extended in this section to a vapor-solid couple where two solutes diffuse from a vapor source into a ternary solid solution. To take into account the expansion of the diffusion disk caused by the absorption of mass from the vapor phase, the total fluxes are expressed on the basis of a coordinate system that moves with the velocity of the vapor-solid interface; thus. where D3ij are the intrinsic diffusion coefficients,4 v(x, t) is the local Kirkendall velocity of mass flow, and F(t) is the negative velocity of the vapor-solid interface (x = 0). Both these velocities are based on a fixed coordinate system far removed from the diffusion zone. Using the continuity relations and Darken&apos;s method1&apos; for a ternary system in which components 1 and 2 diffuse from the vapor phase into a solid of negligible vapor pressure, one obtains

Jan 1, 1965