Search Documents

By M. E. Wadsworth, R. D. Groves, B. W. Madsen

Experimental results obtained from large-scale (7 ton), long-term (500 days) leaching of low-tenor copper sulfide ores were interpreted by a geometric model involving the movement of a reaction zone through the ore fragments. The postulated leaching mechanism involved mixed kinetics and included diffusion of the reacting species through the host rock and a chemical reaction at the surface of the mineral particles. Ore properties which were considered were Ore particle size and shape, grade of ore, and mineral content. Excellent agreement between the mixed kinetic model and the laboratory leaching results was obtained when -1/2-in. ore particles were not included in the leach. Also, a satisfactory prediction of copper recovery from +1/2-in. ore with a different particle size distribution was made; however, it was necessary to modify the shape factor in the model. Prediction of copper recovery from an ore sample which included the -1/2-in. fine fraction and leaching for 460 days was 56.5%, and the recovery from leaching was 47.0%. The presence of fines caused solution channeling and a deficiency of oxygen which inhibited the leaching rate. Also, compaction of fines around coarser particles interfered with circulation around the ore particles, and bulk solution transport probably was a rate controlling factor.

Jan 1, 1976

By Edwin Shorey

IN THE southwestern Wisconsin zinc district, lying in Lafayette, Grant, and Iowa Counties, and the adjoining territory in northwestern Illinois, the orebodies are generally small, and are mined out in a few years. Many of the mines are developed with an expectation of five years or less of actual production. For this reason, as well as for considerations of economy, certain features in the development practice, which have been worked out with a view toward keeping the ratio of time required for, development to that occupied by actual production as small as possible, are of interest. ORGANIZATION The organization of a crew for, this work is as follows: Inasmuch as speed in sinking is desirable, the shaft crew comprises three shifts working 8 hr. each. In the smaller shafts, running up to 6 by 12 ft. (1.8 by 3.6 in.) in size, two men are employed on a shift; in larger shafts an additional man is usually employed. A mine foreman, or ground boss, has general control of the work of the three shifts. He is usually with the crew on the first and the early part of the second shifts, and plans the work to be done for the third shift when it comes on. His schedule, of course, is flexible and when pump changes, or other special conditions warrant, he, arranges his working time to suit the occasion. The surface crew for a sinking operation is made up of two hoistermen, each working 12-hr. shifts. Since the various operations in the shaft must be conducted in succession,. and not in combination, one with the other, separate attendance for hoisting and general plant is unnecessary. Drilling is done when no hoisting is necessary and vice versa. The hoisterman trams out and dumps the excavated material which the crew in the shaft is mucking, as a part of his regular hoisting work.

Jan 8, 1920

By A. F. Witt, A. M. Gaudin, A. K. Biswas

Finite contact angles in the rutile-water-organic liquid system are traceable to contamination or are due to addition of a surface-active agent. Finite contact angles are invariably accompanied by hysteresis.1-7 Besides surfactant concentration and pH, the nature of the organic liquid is found to be a factor influencing the magnitude of contact angle hysteresis. In a recent paper the authors have reviewed principles and applications of measurement methods for contact angles and their hysteresis.22 In this paper, these methods are applied to a system consisting of rutile, an organic liquid (benzene, decane, or dode-cane) and water. Surfactant (dodecylamine hydro-chloride) was used at various concentrations and various pH values. MATERIALS A synthetic rutile crystal supplied by the Linde Co. was used. It is a cylinder 1/2 in. diam, with faces cut perpendicular to the c-axis. The crystal is stated to be alumina-free and to be 99.9% pure. Rutile is a high surface energy solid, its calculated average field strength being 2.7 x 105 e.s.u.,9 its dielectric constant10 is 114. The zero point of charge of rutile was measured11 and found to be at pH 6.0. The atomic distances and bond angles of the tetragonal crystal of rutile have been precisely determined.l2 The organic liquids were specially purified. Reagent grade benzene was repeatedly shaken with concentrated sulfuric acid to remove thiophene, then neutralized with sodium hydroxide solution, rinsed with distilled water, dried overnight over anhydrous calcium chloride and filtered. The refractive index of this chemically purified benzene was 1.4977 (at 25°C) - very close to that of pure benzene (n25 1.4979).13 Both n-decane and n-dodecane were washed with aqueous sodium hydroxide, concentrated sulfuric acid (repeatedly, until the acid layer was colorless) and again with alkali, to free the organic hydrocarbon from fatty acids and unsaturated hydrocarbons. The organic phases were subsequently washed with distilled water and dried over anhydrous sodium sulfate. The filtered hydrocarbons were then distilled under vacuum (9-10 mm pressure). Decane, thus purified, showed traces of unsaturated and of carboxylic compounds. On gas chromatographic analysis the purified n-dodecane showed the presence of two impurities. However, the relative retention times of these components did not change substantially when measured on a polar or a nonpolar column. This indicates that the compounds were probably in the same polarity class, i.e. the components were nonpolar like dodecane. Conductivity water has always been one of the liquids. Conductivity of the water used was 10-6 ohm-' cm". Dodecyl ammonium chloride was prepared from pure amine (supplied by Armour and Co., Chicago), by Li in the MIT Mineral Engineering Laboratory.14 The critical micelle concentration at 25°C is known, 0.0138 mol per liter15 or 3.06 gpl. All our experiments have been done at concentrations lower than the critical micelle concentration. The glass vessels, glass drop holder and the rutile crystal were all cleaned with hot chromic acid followed by distilled water, concentrated hydrochloric acid, and again distilled water, and conductivity water. During the experiments, a nitrogen atmosphere was maintained. For this purpose, commercially purified nitrogen was further purified by passing it over hot copper wire at 450°C, then through columns of acidic chromous chloride solution, concentrated alkali solution and distilled water. APPARATUS AND METHODS Hysteresis was produced by the "captive drop" or constant volume drop method as well as by the "expanding-contracting drop" or variable volume drop method. The image of the drop while it is expanding, contracting or moving is projected on a screen and photographed. The developed film is projected through an enlarger and the contact angles measured with a protractor.

Jan 1, 1964

By Arthur Knapp

The petroleum industry is confronted with the problem of conservalion. This is not a simple problem in view of a wide difference of opinion among authorities as to whether conservation is necessary and the specific direction that it should take. Many writers accuse the petroleum industry of wasting the natural resources of the country. Others link the consuming public with the industry in this waste. Let us define our terms; agree, if possible, on where and when waste occurs in connection with either the recovery or use of petroleum and select such plans for conservation as appear most practical. A plan for conserv3tion which appears to be logical today may not meet the problem tomorrow. The conservation of petroleum is closely linked with the advancement of marly arts and sciences and as these advance, the plan of conservation has to change. The need for conservation does not necessarily rest upon the elimination of waste. There is not necessarily a fixed connection between waste and conservation. Conservation may be necessary or desirable although there is no waste. Definitions Waste: Useless or unnecessary expenditure. Conservation: The preservation of the natural resources for economical use. Both definitions contain adjectives the interpretation of which is extremely difficult. It is the determination of what expenditures are "unnecessary" or what uses are "economical" that will require study and agreement. If one lets his automobile engine run in cold weather in order to keep it hot, it is difficult to measure that necessity. If an automobile is driven two blocks, when the driver is physically capable of walking, what is the measure of necessity. This question is in the realm of one of the oldest of sociological problems, "What is a luxury?"—a problem which has not been solved. The history of society indicates that the measure of a man's wealth has been the measure of necessity. What he can afford to buy without stinting himself in some other direction, is not a luxury to him and, if it fulfills his desires, may be considered his necessity.

Jan 1, 1927

By W. E. Keck

THE flotative properties of the principal minerals in Michigan's potential iron ores have been investigated to develop methods of bene-ficiation for the ores. One of these minerals, magnetite, is of considerable importance as a source of iron. Study of its flotation was similar to that of hematite1, another iron mineral in these potential ores. The present research consisted essentially of: (1) a survey of the literature on mag-netite flotation, (2) the preparation of pure magnetite, (3) the develop-ment of laboratory procedure and (4) flotation experimentation. Literature an Magnetite Flotation.-For the purpose of this discussion, the results of previous work on the flotation of magnetite can be sum-marized as follows. The mineral has been floated with pine oil2, and it has also been separated from synthetic mixtures with silicates by the use of the same reagent2. Magnetite and apatite in iron-ore slimes have been separated by flotation of apatite with sodium palmitate3. These data were utilized in the present investigation. Preparation of Magnetite.-The pure mineral was prepared from the magnetic-separator concentrate of an iron ore (obtained from the Wither-bee Sherman Corporation, Port Henry, N. Y.). This concentrate was slowly comminuted with laboratory rolls and pulverizer to pass 65 mesh and was then tabled several times. Tabling yielded a relatively coarse magnetite concentrate, tailing and slimes. The two latter materials were rejected insofar as the present work is concerned, and treatment of the magnetite (table concentrate) was continued by separating it into -65 + 200 and -200-mesh sizes. Separation of the sizes was made by first dry screening and then wet screening. The -200-mesh material was rejected to eliminate possible introduction of error into flotation

Jan 1, 1937

By Robert L. Haffner

When mining operations of The Eagle-Picher Co. began in the Illinois-Wisconsin zinc mining field in 1949, all underground loading of broken ore and waste was by caterpillar-tracked machines. Beginning in 1956 rubber-tired end-loaders were brought in; ultimately they completely supplanted the tracked units. End-loaders proved to have the mobility needed for the mining conditions and additional merit in auxiliary capacities. Eagle-Picher operates five mines in this area; two are entered by shafts and three by inclined adits. Several ore zones, some of which are attenuated over a considerable distance, are worked from the same entry. Consequently underground haulage roads connecting or following these orebodies have attained great length. In addition, working places are often widely separated because of the character of the mining operations which include pillar recovery and extending haulage connections into old workings. At one mine, the haulage distance is 5000 ft on either side of the shaft, at another the maximum one-way distance is 8400 ft, and at another the present road system of 6800 ft is expected to reach 10,000 to 12,000 ft.

Jan 6, 1962

By Arthur F. Taggart

In 1900, Elmore found that if an acidulated pulp was stirred up with an oil which was relatively insoluble in and lighter than water, and the mixture was allowed to stratify, much of the sulfide would be found hanging to the lower surface of the floating body of oil and could be skimmed off or overflowed with it. The action of the flotation agent here is twofold, first to select the sulfide from the gangue—what today is called collection—and second, to buoy the collected sulfide away from the gangue. The action in collecting is illustrated by Fig. 1: which contrasts the behavior of drops of oil brought, under water, to the surfaces of gangue and sulfide particles, respectively. The oil displaces water from the surface of the sulfide; the water displaces oil from the gangue surface. If, instead of considering the solid particles the fixed parts of the system of oil, water and solids. we consider the oil and water fixed and the solids presented to the surface of contact, the condition will be as shown in Fig. 2; the sulfide tends to be drawn into the interface and the gangue to be excluded. The sulfide particles are held in the oil-water surface by the tension of this surface. The buoyant effect is supplied by the oil droplets in bringing the sulfides to the water surface, but not in holding them there. Gas as Buoyant Medium of Flotation In 1906 Sulman. Picard and Ballot discovered a practical and substantially fool-proof method of doing what Everson, in 1886, and Fro-nlcnt. DeBavay Bessel and Elmore had been doing in the intervening years, viz.: using gas in place of oil as the buoyant medium for flotation, but retaining oil as the agent. To all of these inventors "oil," with no qualification as to its kind and no true understanding of its function, was the important thing. Hut they placed on the oil an additional burden viz.: froth-making, and it soon became apparent that not all oils were suitable for the dual purpose. As a matter of fact, it is probable that each of these inventors knew only one suitable oil at the time he wrote his patent, but used the generic term in the patent with the usual idea

Jan 1, 1928

By J. S. Brown, A. G. Guy

With the exception of the work of Tammann and Hartmann,1 no published information has been found on the structural changes produced in eutectic structures as the result of heating following plastic deformation. In part this lack of information may be due to the fact that many eutectic structures contain an intermetallic compound as a prominent phase, and as a consequence have been considered to be unworkable. For example, Tammann and Hartmann were able to obtain useful data only on those alloys that they could greatly reduce in thickness by cold rolling. This restriction placed on the investigation of alloys containing intermetallic compounds has been largely removed by the work of Savitskii2 which showed that large deformations of such alloys can be produced by relatively slow compression at temperatures near the melting range. It was possible, therefore, to carry out the present work on a range of binary eutectics including one composed of two intermetallic compounds. The essential results obtained on the alloy systems studied are illustrated by the Pb-Mg eutectic containing 33.2 pct Mg, Fig 1. The cast structure, Fig la, was obtained by melting together magnesium of 99.8 pct purity and chemically pure test lead, casting into a heated, small steel mold, and furnace cooling in the mold from about the eutectic temperature. The fairly coarse eutectic structure thus obtained was too brittle to work at room temperature without cracking. Fig 16 shows the worked structure obtained by compressing a 1/2-in. cube 70 pct in about 15 sec at 550°F and then water quenching. The pronounced changes in the distribution of the two phases produced by heating the worked alloy at 850°F for 1 hr are shown in Fig lc. Recrystallization of both phases appears to have taken place, and the mechanical properties of the cast alloy must have been significantly changed by the working and heat treatment. Similar results were obtained with the Mg-59.5 pet Bi, Mg-36.4 pet Sn, Mg-65.4 pet Cu, and Bi-40 pet Cd eutectics, only the last of which could be worked at room temperature. Tammann and Hartmann reported a thickening and shortening of the needles of the eutectics which they heated about 10°C below the melting range for 1 hr after drastic cold rolling. They found the following eutectics, given the indicated amounts of reduc- tion, to have a granular structure after heat treatment: Sn-9 pet Zn (98 pet); Cd-82.5 pet Pb (60 pet); and Bi-43.5 pet Pb (90 pet). On the other hand the alloy Al-11.7 pet Si (60 pet) showed no change after heating. Tammann and Hartmann observed a distinct shrinking of the needles in unworked eutectics subjected to heat-treatment. In the present work inappreciable change in the eutectic structure was found on heating undeformed alloys. In summary, it appears that eutectic structures can be recrystallized into a "spheroidized" condition by heating near the eutectic temperature after severe deformation. If the eutectic contains one or more brittle phases the necessary deformation can be accomplished by pressing at high temperatures. It is reasonable to expect that this tendency towards equiaxed grains from the plate- or needle-like eutectic structure should be general since the energy relations and mode of growth in recrystallization are so different from those that hold for eutectic crystallization. References 1. G. Tammann and H. Hartmann: Ztsch. Melallkunde (1937) 29, 141-144. 2. E. M. Savitskii: Doklady Akad. Nauk S.S.S.R. (1940) 62, 349-351. Abstr. in Melal Prog. (July, 1949) 56, 126, 128.

Jan 1, 1950

By E. B. Hunt

Paraffin deposition has been studied in the laboratory under conditions simulating deposition in well tubing. A theoretical analysis has been made of the cooling of the oil and the precipitation of paraffin from the oil as it flows up the well tubing and through surface flowlines. It is proposed that paraffin deposits are initiated by the precipitation of paraffin directly on or adjacent to the pipe wall and grow by diffusion of paraffin from solution to the deposit. This mechanism is consistent with laboratory and field observations, and has proved useful in the design and interpretation of laboratory paraffin-deposition tests. Tests have been made of the effect of plastic pipe coatings and chemical additives on paraffin deposition. INTRODUCTION Paraffin deposits which form in well tubing and surface flowlines interfere with production and must be removed. Over the years much progress has been made in developing and improving methods of removing these deposits after they form. Much less progress has been made in developing methods of preventing or inhibiting the formation of paraffin deposits. This is due, it is believed, to the lack of knowledge of the mechanism of paraffin deposition, the absence of satisfactory laboratory testing methods and the difficulties in evaluating the results of field tests of preventive treatments. The present investigation was undertaken to elucidate the mechanism of paraffin deposition and to develop suitable laboratory tests for studying the inhibition of paraffin deposition in well tubing and surface flowlines. Current theories on the mechanism of paraffin deposition have been evolved from field observations, from laboratory studies of various factors which might be involved in paraffin deposition, and from laboratory paraffin-deposition tests.1-9 Paraffin deposits have been formed in the laboratory by immersing a cold finger into a hot wax-oil solution and by flowing hot wax-oil solutions through cooled pipe or over cooled plates. These laboratory conditions differ in important features from field conditions, and the observed deposition behavior is not entirely field-like." Thus, there is reason to question the field applicability of the results of these tests. The present investigation was undertaken to determine how to perform and interpret laboratory paraffin-deposition tests to obtain information on the inhibition of deposition in the field. The paraffin problem in the broadest sense encompasses the formation of any predominantly organic deposit in well tubing, surface flowlines and other equipment in contact with crude oil or gas. The present investigation was limited to paraffin deposition involving the precipitation of paraffin wax from solution by cooling and its concentration in a deposit on a cooled surface. This probably excludes its applicability to those problems arising from asphaltic-base crudes, but not those arising from paraffin-or mixed-base crudes. This also excludes its applicability to emulsion and congealing oil problems which are often included as part of the paraffin problem. The phenomenon of cooling appears to be the controlling factor in paraffin deposition involving the precipitation of paraffin wax and its concentration in the deposit. Deposits of this type are usually found in the field only where cooling occurs. Early in this laboratory investigation, it was not found possible to form deposits under constant temperature conditions from a wax-oil slurry, either by steady flow through pipe or by gas-lift up a pipe. Thus, the investigation was limited to situations involving cooling. THEORY The relationships involved in establishing the temperature profiles in an oil stream as it flows up well tubing with a linear (geothermal) pipe-wall temperature distribution or through surface flowlines with essentially constant pipe-wall temperature are presented in the Appendix. The relationship between radial distance in the pipe and the rate of cooling of the oil is then combined with a relationship between cloud point and rate of cooling to develop the pattern of formation of a wax cloud in the oil. The following discussion of paraffin deposition under various laboratory and field conditions is based upon this development which is presented in the Appendix. PARAFFIN DEPOSITION IN SURFACE FLOWLINES The average temperature of the oil coming out of a well is somewhat higher than the ground temperature. Thus, the oil continues to cool on its trip through the surface flowline, and wax deposition can occur. The temperature distributions calculated from Eq. A-4 are given in Fig. 1. As can be seen, almost all the cooling occurs in the first 500 ft from the wellhead. In addition, the radial temperature gradient near the wall decreases rapidly with distance and becomes very small after a few hundred feet. Thus, growth of a paraffin deposit would be expected to decrease rapidly with distance from the wellhead and become negligible after a few hundred feet, since growth is dependent on concentration gradient. Wax precipitation and diffusion of wax to the already

By L. D. Godshall

A great deal has been written of late regarding the loss of silver in assaying; very discordant results have been published by different writers, and much uncertainty exists concerning even approximate losses in a careful determination of silver, as represented by a fire-assay. In the present paper it has been the aim of the writer to determine as accurately as possible the losses sustained by silver, under certain specified conditions, during the process of cupellation. Such losses are well known to be due to absorption by the cupel and volatilization. The conditions, however, which govern these losses are not believed by the writer to be so well understood. The most important of these are : 1. The effect of variable quantities of silver used. 2. The temperature of cupellation. 3. The character and quantity of impurities in the lead button. 4. The weight of the lead button. 5. The nature of the cupel. The following experiments were made for the purpose of demonstrating, as nearly as possible, the total loss of silver in cupellation under the most favorable conditions to be obtained in commercial assaying. Chemically pure silver and pure lead were taken. The latter was obtained from test-lead, first melted into a bar, from which pieces of the desired weight were cut and accurately weighed. The experiments recorded in this paper were planned by the writer, but executed throughout by Mr. J. N. Walker, whose ability as an accurate, careful and painstaking assayer is too well known and recognized throughout the West to require any further endorsement from me.

Jan 1, 1897

By James H. Hance

Discussion of the paper of JAMES H. HANCE, presented at the New York meeting, .February, 1916, and printed in Bulletin No. 110, February, 1916, pp. 299 to 326. FREDERIC P. DEWEY, Washington, D. C. (communication to the Secretary*).-I wish to congratulate Professor Hance and to thank him for his extremely valuable addition to the fund of data upon this subject. It presents clearly conclusive and incontrovertible proof of the unreliability of drill samples of this class of metal for determining the value of such bullion. I am afraid, however, that his hope that some one in the mint service might continue such an investigation upon a more elaborate and exhaustive scale is, for the present at least, doomed to disappointment. As a practical matter, the mint service is not now particularly interested in segregation in crude bullion. So much trouble and friction arose, -both in the original purchase and in the transfer from one institution to another, in handling segregated bullion, that it became necessary to adopt drastic measures and now it is seldom attempted to determine the value of such bullion in the service. When bullion known or even suspected of being segregated is presented for purchase, it is at once strongly refined in the pot and the disturbing elements so far removed that concordant assays may certainly be obtained from the dip samples and a reasonably fair agreement obtained from drill samples. The mint service prefers that the owner should refine his bullion himself, but if he does not we will do it at his expense and return the slag to him when desired. Much work has been done in the mint service trying to arrive at the value of deposits of segregated bullion without strong refining. It was no unusual thing for such deposits to be melted three times at the purchasing office and to have 30 to 40 assays on the metal made before buying it. Yet when shipped to a mint it was found necessary to melt two or three times more and to make 15 to 25 assays before the mint would accept the bar, and there were considerable differences between the valuations of the two offices. In what was undoubtedly the worst case ever investigated, the purchasing office melted the deposit, 953 oz., three times, with a loss of 105.5 oz., and made 46 assays; the mint melted three times, with a loss of 6.6 oz., and made 28 assays. The mint allowed the purchasing office 1.178 oz. of fine gold more than the purchasing office claimed, while an extensive investigation of the mint samples by the Bureau, in which over 100 independent assays were made in various service laboratories, indicated that the metal carried 0.7 to 0.9 oz. more of fine gold than the mint allowed. Preliminary assays on the original metal

Jan 5, 1916

By A. E. Bellis

THE CHAIRMAN (ALBERT SAUVEUR, Cambridge, Mass.).-Any information likely to throw light on the constitution and proper treatment of high-speed steel in order to obtain maximum results, should surely he welcomed. All users of high-speed steel, I believe, will agree with the authors that, in order to obtain satisfactory results, it is not sufficient to heat all brands of high-speed steel to one and the same temperature; apparently very slight differences of chemical composition seem to call for marked differences in temperature. I think that all of us agree that a properly treated piece of high-speed steel should have a fine austenitic or polyhedral structure and that an appreciable quantity of free carbide may be present in the case of very high tungsten steels. What we seem to lack is a satisfactory method, quick and reliable, of ascertaining when the proper structure has been obtained. I think Mr. Bellis' paper is a step in the right direction. To the untrained eye, however, it is not an easy matter to select from some of his photomicrographs the one representing the best structure; for instance, in the case of steel A, we wonder why temperatures of 2,250 and 2,300 do not yield the same results, seeing that both structures are apparently alike, and the same might apply to some of the other samples. I have no doubt, however, that the experienced observer is capable of detecting structural differences that are not made plain here and by which he is able to select the proper quenching temperature. COLIN G. FINK, East Orange, N. J.-On page 68 the authors say that the use of a barium chloride bath to eliminate this difficulty has the disadvantage that the surface of the tool becomes decarbonized." I would like to ask whether they actually found that the surface was decarbonized, or whether they base this conclusion on softening alone? A. E. BELLIS, Springfield, Mass.-No, we have never demonstrated that it was a decarbonization, it is just the softening of the steel. The addition of ferrocyanide to the ferrochloride bath has been suggested. I think that is not altogether satisfactory, because the ferrocyanide bath changes composition very rapidly at these high temperatures, and it would be just a question of luck whether or not it had too much or too little ferrocyanide in the bath giving equilibrium with the carbon content.

Jan 4, 1917

By ZJ. H. Brophy, A. L. Prill, H. W. Hayden

The effect of Group VIII transition-element additions on the sintering of tungsten powders is shown to be dependent on the phase relationships of the particular tungsten-Group VIII metal alloy system. The acceleration of sintering with nickel additions is diminished by alloying nickel with copper which is known to diminish both the tungsten solubility in nickel and the solid-vapor surface energy. In work previously published on the effects of additions of Ni, Pd, Pt, Rh, Ru, and Ir, which form solid solutions or intermediate phases of wide composition width with tungsten, sintering behavior is independent of element concentration beyond that concentration necessary to form a continuous layer on the surface of the tungsten powders employed. The sintering behavior of tungsten with additions of iron or cobalt, which form intermetallic compounds with tungsten, is highly dependent on addition-element concentration. Additions in excess of amounts necessary to form continuous layers lead to successively decreased sintering rates. The effects of certain Group VIII transition metals on the sintering rates of tungsten at temperatures below those at which a liquid phase would be predicted have recently been investigated by the present authors1-4 It was found that small additions of palladium, nickel, rhodium, platinum, and ruthenium accelerate the rate of tungsten sintering. Additions of iridium decelerated the rate of densification compared to that of pure tungsten in the same temperature range. In all cases the rate of densification changed with increasing amounts of these additions, up to those compositions at which a continuous layer was formed on the surfaces of the tungsten-powder particles. The rate of densification was then independent of further increases of the compositions of any of these addition elements. These observations were consistent with a sintering model in which the addition element formed an interface with tungsten in which tungsten dif-fusivity was either greater or less than its grain boundary self-diffusivity. Kinetic analysis of this model indicated that linear shrinkage should vary according to the relation:

Jan 1, 1964

By E. V. Daveler

THE milling plant of the Alaska-Gastineau Mining Co. is located at the town of Thane, Alaska, on Gastineau Channel, 4 mi. south of Juneau and directly across the channel from the Ready Bullion mine of the Treadwell mines on Douglas Island. Previous to the organization of the Alaska-Gastineau Mining Co., in 1912, the milling was done at the stamp mill of the Alaska Perseverance Co. located at the mine in Silver Bow Basin. But the contemplated increase in production made it necessary to locate the mill on Gastineau Channel, as not enough water was available at the mine during the winter months, nor was there room for taking care of the large tonnage of tailings that would ultimately be discarded from the mill. CHARACTER OF ORE The gold and silver values occur in quartz lenses associated with pyrrhotite, galena, arsenical pyrites, and zinc blende. These lenses occur in large bodies of slate, schist, and metagabbro, which also carry some valuable metallic contents. With the essential low cost of mining, it was necessary to mine large bodies of low-grade material containing the high-grade streaks. Of the minerals, pyrrhotite, the magnetic sulfide of iron, is predominant, and galena is the next sulfide present in quantity. The gold occurs free and coarse and associated with the iron sulfide in its finer state. The silver occurs with the lead or is alloyed with the gold. A chemical analysis of the ore shows Silver 0.10 oz. Magnesia 0.4 per cent. Silica 59.7 per cent. Sulfur 1.2 per cent. Iron 5.2 per cent. Lead 0.1 per cent. Alumina 21.4 per cent. Zinc 0.2 per cent. Lime 5.0 per cent.

Jan 1, 1920

By Charles A. Ashburner

VERY little is known of the economical value of the cod-bells of the State of Texas. The first authentic statement in regard to their occurrence is that contained in the reports of the United States Exploratians for the Pacific Railroad, near the 32d parallel of latitude, published in 1863-55. Professor William P. Biake reports, "that a number of seams of bituininorls coal, varying in thickness from two to four feet, have been opened along the Brazos River, in Young County, about one hundred and fifty miles west of Fort Worth." Dr: Shurunrd also states, " that the claracteristic fossil fornis of the Carbeiferaas Era have been found with this coal, and considers the age of the formation established. Foesils obtained from the carboniteroas limestone remove all doubt of the age of these deposits."† In the spring of 1879, I was called upon by some Eastern capitalisets to make an examination of the Brazos coal-field, in order to obtain the thickness, extent., and value of the coal which could be mined and be'made merchantable fir stearn, heating, and metallurgical purposes. The demand for coal in this section of the country is great, and a fuel which in our Eastern markets might be considered of inferior quality, would here find a ready sale. It must be remernbered that the market value of a coal does not depen'd upon its absoltite purity, but upon its actual value in heat units which it is capable of prodwing. A poor coal which can be cheaply milled near the consuper, is infinitely more remunerative to a mining company than a superior coal whose cost to the consumer is greatly increased by high mining charges and railroad freights. The value of the Texan coals does not depend upon their purity but upon their low first cost and nearness to a market. A glance at a geological map of the United States, will show that the Brazos coal-field is the extreme southwestern extension of what may be called the Missourian, Fourth or Western, bituminous coal

Jan 1, 1881

By Walter R. Hibbard, Harold Margolin

DURING preliminary tests on the aging of a Cu-plus 5 pct Ag alloy,' a specimen which had been overaged 24 hr at 550°C was annealed in a nitrogen-hydrogen atmosphere first for 2 hr and then for an additional 28 hr at 600°C. After each anneal the specimen was cooled to room temperature in about ½ hr and X-ray photograms were made. The first film, Fig. la, revealed two sets of copper-base lines, one intense and corresponding to the parameter at 550°C, the other fainter and shifted away from the beam, corresponding to the larger parameter at 600°C (see arrows). The 30-hr film, Fig. lb, revealed the same two sets of copper-base lines with a reversal of intensity. In neither case do the copper lines form a broad band which would be indicative of a range of compositions. This phenomenon is thus a "discontinuous" type of solution. A similar phenomenon was observed in a Ag-rich Cu-Ag alloy.' Finlay and Hibbard9 have suggested that directional rather than random solution of precipitate occurs in some alloys. Conceivably, for Cu-Ag alloys, the matrix-transition-precipitate precipitation sequence is reversible for the re-solution of the precipitate caused by rapidly raising the annealing temperature of an overaged specimen. A copper-base transition structure supersaturated with solute might be formed around the precipitate as it dissolves, thus obviating the necessity for a gradually changing solute composition of the matrix. The solute atoms then might be transferred rapidly and locally from the transition to the matrix phase in the proper amount and at the proper location to obtain directly the new ex- panded solid solution. The theory implies a minimum of diEusion of solute in the matrix (i.e., no significant range of matrix composition) and possibly suggests that the composition of the transition structure will vary with the conditions of re-solution. A transition copper phase found in aged Cu-Ag alloys1 might fulfill this function. Evidence regarding this suggestion could be obtained in Cu-Ag alloys by overaging a specimen until no trace of the expanded copper lattice is present and then subjecting the specimen to a retrogression treatment. Re-appearance of the transition copper phase would confirm the theory. Additional details could be secured by varying both aging and retrogression temperatures. References 'H. Margolin and W. R. Hibbard, Jr.: Effect of Ternary Additions on the Age Hardening of a Copper-Silver Alloy. Trans. AIME (1951) 191, p. 174; Journal of Metals (Feb. 1951) TP 3002E. 2 W. Ageew, M. Hansen, and G. Sachs: Decomposition and Changes in Properties of Super-saturated Silver-Copper Alloys. Ztsch. Physik (1930) 66, p. 350. 3W. L. Finlay and W. R. Hibbard, Jr.: Some Effects of Applied Stresses on Precipitation Phenomena. Trans. AIME (1949) 180, p. 255; Metals Technology (Sept.

Jan 1, 1952

By Arthur B. Foote

Ore production from the property of the Miami Copper Co. began early in 1911. Until 1925 this ore came from the so-called high-grade orebodies, which contained a little over 2 per cent. copper. This ore was mined by the following methods: 1. Top slicing after mining the peaks by square setting, which produced 4,524,347 tons, including ore from square setting. 2. Shrinkage stoping with sublevel caving of the pillars, which produced 2,230,577 tons. 3. Undercut caving with hand tramming, which produced 15,427,672 tons. Estimating December tonnage, the total ore mined to the end of 1929 will amount to slightly more than 43,000,000 tons. The first method was described by E. G. Deane' and the second by D. B. Scott,' and the third, together with a general description of the mine, by J. H. Hensley, Jr.' The geology of the district has been worked out by Dr. F. L. Ransome.2 The author acknowledges also the assistance of R. W. Hughes, assistant mine superintendent, E. V. Graybeal, chief mine engineer, A. J. McDermid and S. R. Burdick, engineers of Miami Copper Co., Miami, Arizona. Factors Influencing Selection of Mining Methods The mining method described herein was selected primarily with a low mining cost in view and was developed to avoid as far as possible dilution of the already very low-grade ore. In 1924, with the exhaustion of the high-grade orebodies in sight, it was decided to develop the low-grade orebody, which at that time contained 36,000,000 tons of ore assaying 1.06 per cent. copper, and had an area of 50 acres with an average thickness of 206 ft. overlain by an average thickness of 320 ft. of barren capping.

Jan 1, 1930

By Oscar T. Marzke

Four alloys that precipitate the alpha phase from the beta of the copper-zinc system were heat-treated in various ways to develop as many forms of the segregate as possible. It was found that the precipitate may have the form either of plates or of needles. Plates usually result when precipitation occurs at low temperatures and needles when precipitation takes place at high temperatures. The needles tend to align themselves along certain planes in the matrix and to coalesce into plnte-like structures. The two phases were found to be related so that a (111) plane and [Oil] direction of the precipitate are parallel to a 10111 plane and 11111 direction of the matrix. DISCUSSION (E. A. Anderson presiding) D. W. Smith, Pittsburgh, Pa. (Written discussion).—Tllis report by Dr. Marzke covers completely all possible heat treatinents over a considerable range of compositiol~s in which a1pha precipitates from beta brass, and may be said to complete the Inctallographic part of this problern The lining up of ncedles of segregate to form plates, espeeially as shown in Fig. 5, appears to he regular, although the author's frequency plot in Fig. 11 makes it appear rather irregular. Has the author attempted anY correlation between some of the major dircetions and the oricntntaion of the parent grain as determined by X-ray analysis? Also, in Figs. 4, 5 and 6 the cross-sections of the needles appear to be straightsided and regular. Have these directions been correlated with the matrix latttice? Dr. Mnrzkr 's method of interpretation of the orientation rclationships between the alpha. and beta phases is a bit uncertain and seems to wed more explanation. If this relationship, as staited is such that :L (1111 plane and a [I 10] direction of that plane in the precipitate is parallel to a. {110} p1ane and a [111] direction of that, plane in the matrix, there mill be a maximum of 24 possible orientations of the alpha phase within a. single grain of the beta phasc. This relationship is expressed strercographical1y in Fig. 13, ill which the locations of a11 of the alpha {111} poles for the 24 orientations of alpha me given. Fig. 12 chccks fairly closely with this thcoretical plot,. with a few exeeptions which may be due to the inaceuracy inherent in the method used by the anthor in determining the orientations of the segregates. The method might have been refined somewhat had corrections been made for the displacement of the slip p1ancs upon deformation.

Jan 1, 1933

By Z. Moser, W. Ptak

The experiments were carried out by the method of measuring the electromotive force of concentration cells having zinc as a reference electrode, the second electrode being the liquid alloy Zn-Sn-Cd-Pb. The electrolyte consisted of liquid chlorides and had zinc ions. The measurements were made for seventy -five alloys of different mole fractions within the temperature range of 714° to 877°K. The experimental results enabled the calculation of the activity of zinc in tested solutions. The activities of zinc were calculated by means of Krupkowski's formulas.3 In addition, the formulas for coefficients of activity of zinc, tin, cadmium. and lead as the function of composition and temperature were given. Activity of zinc was compared with the values obtained from experimental results, and good agreement has been observed. On this basis it can be stated that the theoretical formulas are suitable for determining the thermodynamic properties of liquid quaternary metal solutions. IN the metallurgical processes being carried out at present multicomponent liquid metal solutions take part. For the thermodynamic analysis of these processes it is necessary to know the thermodynamic properties of these solutions. Therefore, many experimental and theoretical papers deal with this problem. The theoretical papers are generally based on the assumption that the structure of liquid metals is similar to their structure in the solid state. In this manner the model of liquid solution, consequently described by means of statistical thermodynamics, has been accepted. This method is being lately developed, especially for solid solutions. Statistical thermodynamics was applied among others by Guggenheim 1 for describing the thermodynamic properties. Unfortunately, the formulas of statistical thermodynamics are often not suitable for the interpretation of experimental results. Attention should be drawn to the relations obtained by means of formulas of phenomenological thermodynamics which always have constants derived with the aid of experimental methods. In the case of the multi-component solutions which contain some additions of impurities besides the basic metal, wagner2 introduced interaction parameters. Equations for the relationship between the activity coefficients and composition were also given by Krupkowski." he application of these formulas requires a good knowledge of the thermodynamic properties of the corresponding binary systems. In these formulas, as in Wagner's, there appear constants which should be determined from ex- perimental data. Nowadays, different experimental methods are applied for evaluating the thermodynamic functions of solutions, for instance: vapor pressure measurements, calorimetric methods, and the measurements of electromotive force of concentration cells. In the present paper this last method for evaluating the thermodynamic properties of four-component systems, Zn-Sn-Cd-Pb, was applied. For instance in the case of Zn-Sn solutions Alabyshev and Landratov, 4 Fiorani and Valenti, 5 and ptak6 performed the investigations. The Zn-Pb system was worked out by Kleppa 7 and Cd-Pb and Cd-Sn by Elliot and chipman.' This method was also applied for determining the activity of zinc in ternary solutions. 1) EXPERIMENTAL METHOD The experimental arrangement with detailed description is given in Fig. 1. It consists of resistance furnaces, one serving for melting samples and the other containing the flat-bottomed, measuring quartz tube with the liquid electrolyte. Liquid metals and alloys are in glass supremax tubes, which have an opening in their lower part above the metal level. This opening allows the filling of the tubes by the electrolyte. In these tubes tungsten wires are placed which by means of suitable conductors are connected with a potentiometer. It is assumed that tungsten dissolves Fig. 1—Schematic diagram of the experimental arrangement for the investigation of the thermodynamic properties of liquid metal solutions: 1, resistance furnaces; 2, autotransfor-mers; 3, galvanometers; 4, regulator of temperature; 5, gas purifier with concentrated H2SOP; 6, U-tube with P2O5; 7, thermostats; 8, steel block for thermostating; 9, supremax tubes for alloys; 10, tungsten electrodes; 11, inlet and outlet of argon; 12, measuring quartz tube; 13, tube for melting samples; 14, tube for thermocouple; 15, cover of quartz tube; 16, rubber seal; 17, bottom cover; 18, outlet of electrodes to potentiometer; 19, outlet of thermocouples to potentiometer; 20, upper view of the quartz tube cover; 21, orifices for cover screws; 22, orifice for argon inlet; 23, orifice for thermocouple; 24, orifices for tubes containing liquid metals; 25, inlet for water-cooling system.

Jan 1, 1969

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