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By Schneider, W. G.

IT is not my purpose to burden you with many statistics. The charts herewith should be considered merely as indicating the trend. I believe' that is what is really of interest to us. It is difficult, if not impossible to forecast with any assurance future developments, because of possible new mines, competitive materials, curtailment' or increase in the use of the metal in certain markets, and many other factors that have a vital bearing on any industry. Fig. 1 shows United States smeltet output of copper, starting with 1845. It is estimated that in 1928 the smelter output of copper will be about 1,010,000 tons. Between 1895 and 1905 it increased about 200,000 tons, and between 1905 and 1915 about 240,000 tons. Between 1915 and 1925 the increase was about 140,000 tons. This is an average increase over 30 years of about 190,00Q tons per ten-year period. At the present time the indications are that this demand for increased production will continue. As to whether or not we have the supplies or facilities to maintain this increase or a greater one, remains to be seen. Provided it is possible for United States smelters to increase their production, they should be producing at the rate of about 1,210,000 tons or more per year by 1935.

Jan 1, 1928

By Allan B. Tanner

The effects of radon in drillholes on gamma-ray logs have been described by L. S. Hilpert and C. M. Bunker1 Since these effects may cause drastic error in the evaluation of uranium deposits, it is useful to know the conditions under which significant amounts of radon tend to accumulate in drill- holes. In the studies described here, atmospheric conditions were found to dominate in the control of the behavior of radon in drillholes in the vicinity of a uranium orebody. The site of the investigation was in McKinley County, New Mexico, about 12 miles north of Grants. Drillholes of 4 ¼ -in. diam, on 25-ft and 100- ft centers, penetrate ore in dry rock at a depth of about 100 ft. A geologic log of the drillhole of primary interest is shown in Fig. 1. Gamma-ray logs revealed three zones of ore-grade mineralization in the Todilto limestone. A 6-ft zone, the lowest of the three, assayed 0.20 pct U3O8 by chemical analysis. The limestone ores in this area contain disseminated uraninite and some yellow and orange secondary minerals.

Jan 7, 1959

By Lewis T. Wright

(Pittsburg Meeting, March, 1910.) I HAVE long been aware that ferruginous copper furnace slags if fused in the electric arc will yield metallic iron containing copper, and in order to confirm this knowledge, and to obtain further information of the behavior of such slags in the high temperature and reducing conditions of the electric furnace, a number of samples of slag were fused in an experimental electric furnace. The results obtained, given in Table I., show that a very large amount of metallic iron was produced, and that this iron carried with it practically all the copper, gold, and silver, and more than 50 per cent. of the sulphur, of the original slag. The metallic buttons formed in the electric furnace were clean, hard, but not brittle.

Mar 1, 1910

By Anthony William Deller

MAJOR battles in the present war have been fought in American research laboratories. Without the outstanding contributions made by our scientists, engineers, and technologists in mining and metallurgy, many of our achievements in the present war would have been impossible. All recognize the fact that modern research has found the answer to problems which seemed insuperable. For the duration, many of these inventions must be maintained as war secrets. But aside from these, the record of accomplishment in peace and war, especially in the past few decades, known to all, demonstrates what scientific and industrial research can accomplish. It may be regarded as axiomatic that the development of modern industry is based principally upon research devoted to making inventions and discoveries. We have come a long way from the sixteenth century, when Agricola published his classical "De Re Metallica:" With our vastly increased knowledge we are now commercially producing dozens of metals entirely unknown at that time. Further, with our modern methods of research and development, a large number of invaluable alloy compositions have been produced. These include numerous age-hardenable alloys, cupronickels, "Everbrite", "Everdur", "Duralumin", "Elinvar", "Hastelloy", "Inconel", "Invar", "Monel", "Ni-chrome", "Ni-Hard", "Ni-Resist", "Permaloy", "Silcrome", stainless steels and irons and other alloy steels, "Stellite", and zinc die-casting alloys.

Jan 1, 1945

By W. G. Jewitt

YELLOWKNIFE, the most northerly Canadian gold mining district, is once more in the throes of a boom. Touched off by spectacular and well-publicized diamond-drilling results on the property of Giant Yellowknife Gold Mines, Ltd., mining companies and the general public are competing for mining claims and for the shares of companies owning mining claims in the area, with little regard for values. Such a stock-market boom has various unfortunate consequences but undoubtedly one beneficial result is that considerable amounts of money are made available for serious development. The Yellowknife mining area lies on the north shore of Great Slave Lake, in the Northwest Territories, at a latitude of approximately 62°30' north. The topography is a low-relief phase of that usual in the Canadian Laurentian shield. Roughly, one third of the surface is lake-covered, one third muskeg or overburden, and one third is bare

Jan 1, 1944

By R. G. Weavind, R. S. Young, I. Wolf

ONE of the most important fields of investigation at the Diamond Research Laboratory in Johannesburg is concerned with improvements in metallurgical practices for the diamond mining companies, with particular reference to increased recoveries of the smaller industrial stones. Considerable work has been done on the possible application of flotation processes to the diamond industry. From the viewpoint of recovery processes, diamonds in their natural state may be grouped into two classes, the water-repellent diamonds, which adhere to a grease surface, and the water-avid diamonds, which, because of their wettability, will not adhere to a grease surface and must be recovered by means other than the grease tables used for water-repellent diamonds. Experiments in the flotation of small diamonds from both kimberlite and alluvial deposits indicate the following conclusions: Water-repellent diamonds: Satisfactory flotation of —16 mesh diamonds, which are naturally water-repellent, may be accomplished using either Aero-float 25 together with cresylic acid, or Du Pont B23 as frother together with kerosine as auxiliary oily conditioner or froth stiffener. The quantities of reagents required are of the order of 0.15 lb per ton Aerofloat and 0.18 lb per ton cresylic acid. The use of acid circuits is detrimental, and for best results a pH between 7 and 9 should be maintained. R. G. WEAVIND and I. WOLF are with the Diamond Research Laboratory, Johannesburg, South Africa, and R. S. YOUNG, Member AIME, is Director of Research, Diamond Research Laboratory. TN 76B. Manuscript, March 23, 1951. A flotation period of 5 to 10 min is necessary to insure that all floatable diamonds are removed. Diamonds larger than 16 mesh cannot be recovered satisfactorily by flotation. Xanthates do not act as collectors for diamonds, and this is probably associated with their inability to impart a water-repellent surface to this mineral. Water-repellent diamonds smaller than 28 mesh can be floated quite well by the addition of a frother alone, such as pine oil or Du Pont B23. Water-avid diamonds: Partial flotation of the smaller sizes of wettable diamonds can be achieved by preconditioning with fatty acid soaps, cationic amines, and similar reagents, which will impart a water-repellent film to diamonds. Washing to remove excess reagent, followed by flotation, will result in a fair recovery, but the latter is much lower than for water-repellent diamonds. Crushed boart: Recovery of crushed boart from the waste products of industrial uses is best accomplished by first conditioning the diamonds present in the mixture with fatty acids, cationic amines, etc., removing the conditioning agent by washing, and floating in a cell of the pneumatic type. Flotation reagents found to be most suitable are Du Pont B23, and Aerofloat 25 together with cresylic acid. The optimum quantities are 1.2 g Du Pont B23, and 0.55 g Aerofloat plus 1.4 g cresylic acid, per liter of pulp in the cell. A solids-to-water ratio of 1 to 4 is found to be the most suitable, and alkaline circuits are necessary for best results. Diamonds larger than 28 mesh are not recovered satisfactorily by this procedure, but for finer sizes flotation offers an excellent procedure for the reclamation of this strategic industrial material.

Jan 1, 1952

By W. O. Philbrook, R. H. Spitzer, F. S. Manning

A generalized mathematical model has been developed to describe the kinetics of the gaseous, topo-chemical reduction of porous hematite spheres. Gas-solid reduction is permitted at each of three advancing interfaces and is controlled by a complex series-parallel sequence of chemical and transport steps. Despite the fact that transport resistances are significant to the advance of each interface, little deviation from linear advance is predicted for the first 98 pct of reduction. Calculations to predict the movement of magnetite /wustite interface by a solid-state diffusion mechanism have been incorporated into the earlier dense-pellet model.' The porous-pellet model is found to give a better description than the dense-pellet one for McKewan's measurements2 of interface movements in dense polycrystalline hematite reduced in hydrogen-water vapor mixtures. THIS paper reports a continuation of work"3" directed toward the better understanding of gas-solid reactions and the development of mathematical models that may be helpful in the design or control of ore-reduction processes. Laboratory studies of the reduction of single oxide samples in tube furnaces normally employ an abundant excess of pure reducing gas. Reduction may appear to be adequately described by a model assuming gas-solid reaction solely at the iron/wustite interface.''' However, when iron ore is reduced in either a fixed bed or an efficiently operated counter-current column, there are portions of the bed where the partially spent gas is no longer capable of reducing wustite to iron. Nevertheless, the formation of the intermediate reaction products, wustite or magnetite, can and does continue. In order to account for this aspect of the reduction of beds of particles, three semiempirical mathematical models were devised.' One of these was for the limiting case of completely dense particles, and two alternatives were provided for porous particles. For purposes of the analysis, a dense pellet was defined as one in which the wustite and magnetite layers were impervious to the reducing gas when the atmosphere was capable of forming iron. In a porous pellet, the intermediate product layers were assumed to be sufficiently permeable to allow reducing gas to penetrate beyond the iron/wustite interface to form wustite and magnetite by removal of oxygen as a gaseous product rather than by a solid-state redfiction mechanism. Further progress required a better understanding of the reaction of the individual particles with the gas stream. A comprehensive mathematical treatment was developed' to describe the continually changing interplay of transport and reaction steps

Jan 1, 1967

By Saluja, Sunder S.

Man had to learn to break rocks as early as the Stone Age, when they formed his main source of raw material. He started with chipping and over the years has reached a stage where he can employ atomic blasts and break, with one blast, millions of tons of rock. In between these two extremes there have been several stages of development including fire setting, use of the expansion of water on freezing in chipped cracks in cold climates, the use of low or deflagrating explosive black powder in about the 17th century, the use of high explosives with the discovery of nitroglycerine in 1846 by Sobrero, followed by the monumental discoveries of the great Swedish scientist Alfred Nobel in the latter half of the nineteenth century.

Jan 1, 1968

By J. J. Van Nouhuys

THE economics of aerial survey and the technical processes by the aid of which vertical and oblique aerial photographs are turned into line maps showing the most profuse topographical detail such as contours, rivers, roads, plantations, habitations and cultivated lands do not concern us here. They have been ably and exhaustively described in the publi-cations of the British War Office, handbooks on surveying methods and on photogrammetry and in the South African mining, engineering and geological press. Suffice it to mention that for geological interpretation vertical photo-graphs are used on such scales as soon to 1/5,000 to 1/10,000, overlapping each other by 55 to 60 per cent in the direction of flight and some 10 to 20 per cent sideways on to the next sequence or strip. Through this duplication in the overlap the stereoscopic examination becomes possible. The standards by which monochrome aerial photographs are inter-preted can be grouped under the following headings: 1. Continuity.-The continuity of topographic relief not obtainable on the ground owing to the smallness of man relative to that relief. Here lies the greatest value of aerial survey with relation to geology. An immediate alignment can often be made of drainages running in different directions on each side of a hill; saddles and gorges in the mountainsides; abrupt termination of outcrop or indubitable signs of faulting. Most conclusive evidence is thus often obtained about faults which may be perfectly visible at one place on the ground but cannot elsewhere be identified because of decreased throw. Similarly, dikes can often be followed notwithstanding frequent interruption and disappearance under the soil. Scattered outcrop in scrub-covered or bush-covered country can be conveniently located and often correlated, with a large saving of time compared with field work. The same applies to geological contacts. Once these have been established at a few points on the ground, the intervening stretches can be drawn in.

Jan 1, 1937

By H. F. Kendall, J. H. Ffolliott

MANY papers and reports have been devoted to the geology and ore deposits of the Ducktown district, Tennessee, especially the complete report by W. H. Emmons and F. B. Laney, published as Professional Paper 139, by the U. S. Geological Survey. The present paper discusses the work of the geological organization of the Tennessee Copper Co., which is based on the field work of the above paper and the consulting work of W. H. Emmons. The Ducktown basin lies in the southeastern corner of Tennessee and extends a short distance into Georgia and North Carolina. All productive mines are contained in an area of 15 sq. mi. in the center of this basin, which is an undulating plateau at an elevation of 1650 to 1800 ft. above sea level. It is surrounded by the relatively high mountains of the southern Appalachian region. The rocks are of early Cambrian age. Deposition of the ores probably took place during the latter part of the Paleozoic era. The ore deposits are rudely tabular to lens-shaped bodies of massive sulfide, varying from a few feet to over 200 ft. in width. In general they all strike northeast and dip southeast at angles from 45° to 70°. Locally, where affected by folding and faulting, the variations in dip may be even greater. The lodes usually are parallel at distances of from one-half to one mile measured normal to the strike. The deposits are a replacement of a fairly continuous bed or a series of disconnected limestone lenses, highly folded and somewhat faulted, which probably represent the same stratigraphic horizon.

Jan 1, 1933

E. A. H. Tays, San Blas, Sinaloa, Mex. (communication to the Secretary*):—The results obtained by Messrs. Hofman and Hayward in their experiments, proving that a low percentage of copper sulphate with a variable percentage of salt, depending on the ore, gives the best results, confirm practical mill-work which I did in 1895. I have none of my notes, taken at the time, to refer to, so have to rely solely on memory, which precludes the conciseness that is alway desirable. In 1894 I took charge of the plant of the San Rafael Company, near Chinipas, Chihuahua, Mex., which at that time was treating a very refractory ore carrying about $15 in gold and from 20 to 25 oz. of silver per ton, the bullion being about 300 fine in gold. The silver in the ore was in the form of a sulphide. Although carrying an average of 0.75 oz. of gold per ton, free gold could rarely be seen by panning, but upon roasting a sample of the ore the gold became visible at once—a result which was discovered by chance and used to advantage later. In order to utilize the old mill to the best advantage, it was decided to use pan-amalgamation after roasting. The roasting, done in a lime-kiln, was similar to the ordinary " burning " operation. The roasted ore was trammed to the mill-bins and crushed by 10 stamps to pass a 30-mesh screen. The pulp was de-watered and fed to four 1-ton pans. My recollection is that upon starting the mill-work, the charge contained 1.5 lb. of copper sulphate and 5 per cent. of salt per ton. From the start the extraction was unsatisfactory and the loss of quicksilver was very large. Experiments were then carried out on a working scale. First, the quantity of copper sulphate was increased 4 oz. at a time; then it was reduced

Jan 1, 1910

By Bradley Stoughton

A LL over our great country I have been privileged to see, during the last six weeks, the manifestation of a new spirit among engineers. Partly under the inspiration of leaders whose influence has been felt not only nationally, but internationally, - partly through the recognition of the service that engineers have been able to render to the nation during the recent crisis, a new self-consciousness has been acquired by the individuals, and now this self-consciousness seeks expression in opportunities for service and participation in public affairs. The engineer . no longer sees himself a mere reservoir of information to be tapped when some one is in need of cold facts, no. more an administrator of mere material things, but a potential administrator of- public affairs, a citizen and a human being, with the responsibilities, as well as the privileges of citizenship.

Jan 1, 1920

By John A. Gann

THE Iron and Steel Division has shared in the general increased activity of the industry. The fall meeting at Chicago was not only well attended but particularly characterized by the virility and scope of the discussions at the various sessions. The program for the February meeting indicates a similar interest in technological developments. The Blast-Furnace Committee continues to have the hearty support of the industry with discussions of such a nature as to be of real help to the operator as well ass the technologist. The work of the Open-Hearth Committee continues to be outstanding, with ever increasing attendance and ever mounting interest in the meetings. Formation of a conference on the physical chemistry of steelmaking has given those interested in this phase of work an organization allowing the same

Jan 1, 1936

By J. P. BONARDI, William F. Boericke

BOULDER COUNTY, Colorado, ranked during the war years and until the end of 1918 as one of the foremost tungsten-producing districts of the world. In 1919 production fell off drastically, due to heavy importations of foreign ores from China, Burma and South America. So large were the imports that even after the enactment of a protective tariff in 1922 of 45c. per lb. on tungsten metal, equivalent to $7.14 per unit (201b.) of tungstic acid? (WO,), the stocks of metal in this country were extensive enough to supply the demands of industry, and prevent general resumption of mining by domestic producers. Even today there are only two producers in the Boulder district though at one time as many as twenty separate companies were in operation. About the same ratio holds for other tungsten-producing districts in the country, including California and Nevada. Total consumption of tungsten concentrate in terms of 60 per cent WO2 in the United States amounted to approximately 3790 tons in 1928, according to Frank L. Hess.' Of this amount, domestic mines contributed 1290 tons, and the rest, 2500 tons, was imported. Yet in 1917, with tungsten concentrate selling at $20 per unit, the Boulder district alone produced 2707 tons, indicating the effect of enhanced ore price upon production. It is believed by American tungsten miners that, given a sufficiently high tariff, all the demands of industry can be met by domestic production without placing a prohibitive burden on consumers. For instance, in steel manufacturing the percentage of tungsten entering into the manufacture is so small that, ?regardless of cost, it can constitute but a small fraction of the cost of steel to the buyer.

Jan 1, 1929

By S. A. Falconer

D. A. Dahlstrom—Mr. Falconer has done an admirable job of proving the adaptability of the cyclone to the beneficiation of a very difficult size range in the preparation of coal. The addition of the cyclone to other coarser size methods makes it economically feasible for the coal operator to rigorously control his marketed products at a high and uniform quality level down to the 48 and 100-mesh size. Furthermore, it should be pointed out that by utilizing the cyclone as a deslimer or classifier the —3 200-mesh fraction, usually containing large percentages of undesirable material, can also be quickly and cheaply removed from the clean coal. Advantages of such a step are several: (1) Reduction of ash content, especially where clays and slimes are serious. (2) lower moisture content of the final coal. (3) easier mechanical and thermal de-watering of the fine coal due to higher cake and bed permeabilities. The author has indicated that adjustable control means should be installed on the cyclone operating on a heavy-media slurry. This also holds true for the cyclone acting as classifier, deslimer or preliminary dewatering agent and is worthy of special emphasis. Such controls, while not necessarily automatic, must be simple, rapidly adjustable, and require a minimum of attention. Three methods available to the operator are (1) throttling valve on the feed line, (2) back pressure valve on the overflow, and (3) adjustable diameter underflow nozzles. The first two, while fulfilling the specifications, suffer the disadvantage of restricting capacity if severe throttling is necessary. The third method has little effect on capacity and easily maintains an underflow of correct moisture content. Several designs are possible, but two find the widest application. The first was developed by Robert Piros of The Truax-Traer Coal Co. and uses a simple casting containing two holders for underflow nozzles which can be rotated about an axis parallel to the cyclone centerline. These holders retain the underflow nozzle flush with the conical section walls. When a change in nozzle diameter is required, the new size is placed in the spare holder and rotated into place. A second design utilizes a soft rubber cylindrical tube which is compressed or released from three sides, causing the inner diameter of the tube to decrease or increase. This is achieved by using a machine-threaded,

Jan 1, 1951

By S. A. Falconer

D. A. Dahlstrom—Mr. Falconer has done an admirable job of proving the adaptability of the cyclone to the beneficiation of a very difficult size range in the preparation of coal. The addition of the cyclone to other coarser size methods makes it economically feasible for the coal operator to rigorously control his marketed products at a high and uniform quality level down to the 48 and 100-mesh size. Furthermore, it should be pointed out that by utilizing the cyclone as a deslimer or classifier the —3 200-mesh fraction, usually containing large percentages of undesirable material, can also be quickly and cheaply removed from the clean coal. Advantages of such a step are several: (1) Reduction of ash content, especially where clays and slimes are serious. (2) lower moisture content of the final coal. (3) easier mechanical and thermal de-watering of the fine coal due to higher cake and bed permeabilities. The author has indicated that adjustable control means should be installed on the cyclone operating on a heavy-media slurry. This also holds true for the cyclone acting as classifier, deslimer or preliminary dewatering agent and is worthy of special emphasis. Such controls, while not necessarily automatic, must be simple, rapidly adjustable, and require a minimum of attention. Three methods available to the operator are (1) throttling valve on the feed line, (2) back pressure valve on the overflow, and (3) adjustable diameter underflow nozzles. The first two, while fulfilling the specifications, suffer the disadvantage of restricting capacity if severe throttling is necessary. The third method has little effect on capacity and easily maintains an underflow of correct moisture content. Several designs are possible, but two find the widest application. The first was developed by Robert Piros of The Truax-Traer Coal Co. and uses a simple casting containing two holders for underflow nozzles which can be rotated about an axis parallel to the cyclone centerline. These holders retain the underflow nozzle flush with the conical section walls. When a change in nozzle diameter is required, the new size is placed in the spare holder and rotated into place. A second design utilizes a soft rubber cylindrical tube which is compressed or released from three sides, causing the inner diameter of the tube to decrease or increase. This is achieved by using a machine-threaded,

Jan 1, 1951

By James Aston

A PROPER consideration of this subject is not confined to the technical channels of production and metallurgy. It concerns an industry, and should cover economic aspects which are of material importance in any program of development. The discussion may logically be treated under three subdivisions, as follows: (1) manufacture, (2) characteristics related to quality of material; (3) adaptability and exploitation of product. MANUFACTURE OF WROUGHT IRON The manufacture of wrought iron is the most ancient art of the ferrous metal industry. The eighty years or less of existence of processes identi-fied with our modern "Age of Steel" is a relatively brief interval com-pared with the several thousand years associated with the production of wrought iron by man. From the primitive early methods of production, manufacture for many centuries followed the line of direct reduction. There were developments as experience was gained through the years; but man's needs for a strong, ductile, forgeable product were met by reducing the ore to metallic iron in a single-stage operation. Following the development several centuries ago of what has become our modern blast-furnace operation, manufacture of wrought iron was gradually transformed into a two-stage method of first producing cast iron and then refining this to the desired degree of forgeability; the fore-runner in principle of today's scheme of manufacture of steel. The product retained the essential characteristics of highly refined base metal with iron-silicate slag incorporation, which were associated with the material resulting from direct reduction methods. Cort's invention of the puddling process in 1784 is a landmark in wrought-iron manufacture. It consisted essentially in adapting a coal-fired reverberatory furnace to the refining operation; thus lifting the industry out of the slough of

Jan 1, 1935

By Byron E. Eldred

(Pittsburg Meeting. March, 1010.) GENERALLY speaking, the practical study of combustion has been made mainly from the stand-point of the steam engineer. This. narrow view-point has left open a large field for scientific research on the application of combustion in other arts, where the conditions of heat-utilization are widely different from those presented in the steam-generator. The great economic importance of the boiler and the ease of measuring its performance, together with the comparative uniformity of conditions in the steam-generator, is, probably, quite largely responsible for the practical neglect of the study of the use of fuels in other arts save only on the basis of their thermal value. Yet these other arts show quite plainly that a thermal-value basis alone is Dot sufficient. For example, in burning lime, under ordinary conditions of firing, a cord of wood will do as much work as a ton of coal, though the latter affords more than twice the number of heat-units. Similar results are evidenced in burning brick, in the roasting of certain ores, in reheating billets, and in many other arts where heat is to be applied over extended areas to fragmental masses of more or less refractory materials. In these arts much is to be gained by a careful study of the application of the heating-agent in the form of the long flame, and in the production of the heat in contact with, or in direct proximity to, the object to be heated. Of necessity, in boiler-practice, combustion cannot be maintained in actual contact with, or in close proximity to, the object to be heated. Speaking in a general way, heat is imparted from burning bodies to things to be heated in two ways : directly, by radiation, and indirectly, by transfer of the sensible heat of hot gases by convection or contact; by conduction from the hot uses. Both ways are utilized in boiler-practice-directly, by

Jun 1, 1910

By E. W. Davis

THE large iron-ore producers on the Mesabi Range are able to maintain the silica in their shipping products at from 8 to 10 per cent by mixing ores of various grades, some assaying 4 per cent silica and some as high as 18 per cent silica. For each ton of 4 per cent silica ore mined, a ton of 14 per cent silica ore can be mined and mixed with it and the average grade maintained at 9 per cent. This mixing operation has made possible the utilization of large cluantities of ore too lean to be used alone. and herein lies the advantage of the producers who operate a number of mines at the same time. As the grade of the ore from one of the properties falls off, a little high-grade ore from another property can be mixed with it and the average maintained, while if one property alone were being operated all of the ore below grade would be left behind.

Jan 1, 1930

By Barry D. Lichter, Pierre Sommelet

High-temperature heat contents of InSb, GaSb, and AlSb were measured over the temperature range 400" to 1450°K using a diphenyl ether drop calorimeter. Smoothed ualues of the thermal properties, H$ - H:9s, have been derived and are tabulated at even temperature intervals. The heats of fusion of the three compounds were determined as, respectively, 5707 *100, 7780 * 100, and 9800 5 3011 cal per g-atorn at the determined melting points of 797" l°, 985" * , and 1330" * 5°K. The calculated entropies of fusion are, respectively, 7.16 0.12, 7.90 * 0.11, and 7.37 * 0.23 cal per deg per g-atotn. The heat capacities increase substantially on tnelting in contrast to the behauior of structurally related germanium and silicon. Deriations from the Kopp-Neumann rule are negative for solid compounds and positive for the liquid phases. Previously obsevrrd "post melting" in InSb is confirmed. The high-temperature thermal properties of 111-V compounds are presently not well-established, despite the technical importance of these semiconducting cbmpounds. Uncertainties in available heats of fusion and heat contents have seriously hampered thermo-chemical evaluations' and thermodynamic analyses of phase equilibria2"" in these systems. This paper reports results of high-temperature heat content investigations of InSb, GaSb, and AlSb measured in the range 400" to 1450°K employing a diphenyl ether drop calorimeter. Similar measurements for InAs and GaAs will be reported in a following publication.~ EXPERIMENTAL PROCEDURES Samples. High-purity samples of the compounds InSb and GaSb were supplied in the form of crushed crystal fragments by Dr. Carl Thurmond of the Bell Telephone Laboratories and in the form of single crystals by Dr. A. Strauss of the M.I.T. Lincoln Laboratory. Single-crystal samples of semiconductor-grade AlSb were supplied by Dr. W. P. Allred of the Bell and Howell Research Center. Chemical analyses indicated that all compounds were stoichiometric to *0.1 at. pct, which is within the experimental uncertainties of the analyses. Samples were crushed, weighed, and encapsulated in evacuated, thin-walled, fused silica capsules. The capsules were nearly identical in external shape, 2 cm by 2 cm diam, but varied in weight due to differences in wall thickness. One sample of AlSb was contained in a thin-walled, high-purity alumina cup encapsulated in silica and used for heat content determinations of liquid AlSb. The capsule materials showed no visual evidence of reaction with any of the compounds. The sample and capsule weights are given in Table I. Calorimeter. A Bunsen-type calorimeter, similar in design to a previously described instrument6 but employing diphenyl ether (C6H5)'0 as the calorimetric substance, was used for measurements of heat contents above 300.0°K, the melting point of diphenyl ether. Heat input to the calorimeter caused isothermal melting of diphenyl ether, and the resulting increase in volume was measured by displacement of mercury from the calorimeter into a 200 cm horizontal, calibrated capillary, 1.25 * 0.01 mm diam, or into a weighed beaker. The advantages of diphenyl ether over water have been previously pointed out7 and include: i) an increase by a factor of 3.5 in sensitivity as measured by the ratio of the volume change to the enthalpy change on fusion, ii) the smaller required extrapolation from the melting point to the standard temperature of 298.17"K, and iii) the positive volume change on fusion of diphenyl ether in contrast to the contraction which occurs on fusion of ice. Diphenyl ether was purified by fractional crystallization to 99.95 mol pct as determined from the melting point depression with fraction crystallized. During assembly of the calorimeter, the ether was repeatedly outgassed under high vacuum to remove dissolved air. The calorimeter receiving vessel consisted of an 8-in.-long by 1:-in.-diam copper tube with twelve horizontal 3-in.-diam radiator "fins" for dissipating heat to the surrounding mantle of diphenyl ether. Before forming the mantle the chamber surrounding the receiving vessel contained 3300 cu cm of liquid diphenyl ether above 250 cu cm of mercury which was

Jan 1, 1970