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By C. S. Yust, C. S. Morgan

ThIS note reports the observation of masses of dislocation etch pits around the weld necks of small single-crystal particles of calcium fluoride sintered to a cleaved face of a larger CaFz crystal. Crystal particles in the -50 +I00 mesh size range were placed on freshly cleaved CaFz surfaces and heated at 1250°C for 30 min in a tantalum container in an argon atmosphere. The sintered specimens were then etched at room temperature for 40 to 50 min in a 2 pct sulfamic acid solution which is a selective etch for dislocations in caF2.' Figs. 1 through 3 show the masses of dislocation etch pits observed around weld necks after etching. In some cases, particles were gone after removal of the specimens from the furnace although weld necks were readily visible. In other instances, no etch pits formed around a weld neck. A possible cause of concentrations of dislocations on the crystal surface is mechanical deformation of the base crystal when particles are dropped on it. If such a deformation does occur, it would be much smaller than that caused by the light punching of a crystal with a sharp instrument which results in large concentrations of etch pits. However, crystals deformed by punching with the sharp instrument and annealed at the conditions of these experiments (1250°C for 30 min) before etching showed no concentrations of dislocation etch pits. It is obvious that dislocations from the much smaller deformations, possibly created when particles are placed on the surface, would also anneal out. Etching of large crystals which had particles placed on them in the usual manner but which were not heated showed no dislocation concentrations such as shown in Fig. 1. The magnitude of dislocation etch-pit concentrations did not vary with extensive variation of the cooling rate. The appearance of many of the etch-pit clusters is typical of a well-annealed condition, indicating that the dislocation concentrations formed before the specimen temperature was lowered. Therefore, it is evident that thermal stresses in the neck area did not create the deformation indicated by the presence of the dislocations. The possibility exists that the etch-pit concentrations at places where particles had been removed may be the result of deformation accompanying the fracture of the sintered bond. That this is not so was demonstrated by breaking off particles around which no etch pits occurred. Re-etching never resulted in the large concentrations observed at sintering sites. The stress available to effect material movement during sintering of two particles will depend on the geometry at the contact point but can easily exceed the macroscopic yield stress in CaFz systems. It appears that the plastic deformation observed results from sintering or simply from the weight of the small particles. It has been previously argued that plastic flow makes an important contribution to the initial densification of oxides having the fluorite crystal structure.2p3 If plastic deformation occurs, it would begin as soon as the temperature is sufficiently high

Jan 1, 1967

In the Philippines, where distances are spoken of in terms off fight time, the Sipalay copper mines are two flight hours southeast of Manila on the island of Negros. After landing at the airport in Bacolod, it is then 170 km (106 milers) by surface transportation to Marinduque Mining and Industrial Corp.'s expanding copper operation. While copper deposits were discovered in the area in 1936-and one mine, the Binulig, began operations soon after-it wasn't until 1956 that stripping at Sipalay and construction of a 4000-t/d (4400-stpd) mill began. The mill went into operation in May 1957, and the first shipment of copper concentrate was made three months later.

Jan 8, 1978

By B. D. Harden

FOR over fifty years the Spanish mine, 21 miles northeast of Nevada City, in Nevada County, California, has been one of the Bradley properties. Between 1883 and 1889 it was operated by the late Frederick W. Bradley and P. R. Bradley. The ore averaged only about $1 a ton at that time but the mine was credited with a production of about $900,000 in that period. The property was then closed down until 1922, when the Bradley interests reopened it and continued development for the next nine years, when a 50-ton mill was built. This began operation in April, 1931. This was a selective flotation plant, with the tailing treated on Wilfley tables, and operated on ore from the No. 4 and No. 16 tunnel stopes. This ran from $3 to $6 in gold, 2 to 3 oz. of silver, copper 0.6 per cent, lead 1.5,

Jan 1, 1935

By G. I. Madden, L. H. Van Vlack

WhEN basic refractories which contain peri-clase, MgO, are used in steel furnaces, they are altered by iron oxide to form magnesiowiistite, (Mg,Fe)O, and an iron-rich magnesioferrite, (Mg,Fe)Fe2O4. Silica, which is usually present, produces a silicate liquid that surrounds the solid phases. The individual crystalline grains of the above two solid phases grow at elevated temperatures. Previous papersL" showed that, if either periclase or magnesiowiistite is present as the only solid phase, its grain size increases in proportion to temperature and in proportion to the square root of time; the growth rate is reduced slightly if the amount of silicate liquid is increased. Similar results have been observed for iron-rich magnesioferrite.3 To determine the effect of the presence of two solid phases on the rate of grain growth, micro-structural studies have been made on samples containing both magnesiowustite and magnesioferrite. The experimental procedure was the same as that followed in the previous studies of this type.'12 Briefly, this included determination of compositions from the available phase relationships4 that would produce the two phases of interest at the firing temperature and using reagent-grade raw materials to prepare mixtures of these compositions. The mixtures were pressed into pellet-size samples and then fired at the desired time and temperature. The samples were water-quenched to preserve the microstructure present at the firing temperature. Standard reflected-light metallographic techniques were used for sample examination and sample analysis. Grain sizes were determined by measuring the mean diameter of a number of randomly selected grains in a two-dimensional microsection. A large cross section of the sample was covered to prevent biased data resulting from such effects as localized differences in the radius of curvature of the crystal grains. Examination indicates that grain growth is restricted when more than one solid phase is present. This is illustrated in Fig. 1 for: (a) magnesiowustite plus a silicate liquid; (b) magnesioferrite plus a silicate liquid; and (c) magnesiowiistite and magnesioferrite plus a silicate liquid. Fig. 2 plots the

Jan 1, 1964

By Dr. O’Neil Thomas J., Donald W. Gentry

There are mines that make us happy, There are mines that make us blue, There are mines that steal away the tear-drops As the sunbeams steal away the dew. There are mines that have lost the ore chute faulted, When the ore's forever lost to view, But the mines that fill my heart with sunshine, Are the mines that I sold to you. -Anonymous INTRODUCTION The preceding chapters have discussed, in various degrees of detail, the primary considerations necessary to perform a cash flow analysis of a mining-related investment opportunity. Although the previous discussions regarding the manipulations, calculations, and interrelationships of the various components of the pro forma income statement were illustrated in the text, many individuals are un- familiar with the format and appearance of a final spread sheet for the evaluation of a mining property. As a result, it seems appropriate to conclude this book with an abbreviated case study of an actual mine property (currently in production) showing the cash flow analysis and some back-up data. Obviously all of the supporting data and calculations for the case study presented cannot be provided; however, reference is made to the major assumptions utilized and to the appropriate procedures employed in the calculations, as described elsewhere in the text. The problem associated with using any case study for illustrative purposes is that one tends to be overwhelmed by detail. For instance, specific costs, prices, expenditure timings, and other variable values may be challenged because they either do not conform to one's expectations or are not consistent with specific operating experiences. When this occurs the instructional value of the problem becomes obscured. The purpose of most case studies, and particularly the one presented in this chapter, is to expose the student to the methodology, procedure, and format associated with performing a cash flow analysis of a mining property. It is not to laboriously wade through the specific details associated with operating and capital cost development, mine plans, or equipment schedules. It should be noted, how- ever, that the values represented in this case study result from specific mine plans, operating procedures, equipment spreads, manpower requirements, and other en-

Jan 1, 1984

By John Hays Hammond

Discussion of the paper of John Hays Hammond, presented at the Chattanooga meeting, October, 1908, and published in Bi.-Monthly Bulletin., No. 24, November, 1908, pp. 1171 to 117S. PROF. HENRY Louis, Newcastle-upon-Tyne, En j. (communication to the Secretary'`) :-I welcome Mr. Hammond's paper as an. attempt to give definiteness to the best modern professional practice. Such a codification of our professional ethics is urgently needed, seeing how widely the views of mining engineers differ on some of the point-,. raised, for example, I have no hesitation it) performing a class of work, as to which Mr. Hammond seems to entertain some doubts, and, on the other hand, I strongly condemn a practice which he appears to recommend. I have not the least hesitation in making reports for vendors of mining properties, and am constantly doing so; . the best justification for this practice may be found in the fact that such reports have been repeatedly accepted by buyers as giving a correct representation of the facts of the case, which is all that should be demanded from any report. On the other hand, Mr. Hammond advocates that mitring engineers should take payment for their reports tin shares of a company to be floated upon the basis of such reports. I hold that this is ethically wrong, as even the most honest of men is liable to be unconsciously biased under these conditions. Indeed, I go much further, and maintain that a mining engineer who re¬ports or advises upon mining properties should never hold any-mining shares at all, or be himself interested in any mine,' and this has been my consistent practice for many years. A man who holds shares in a mine, and is called upon to report upon a neighboring property or a similar mine, can never be wholly unbiased, and even if lie could be, he would always lay himself open to the suspicion that he was giving a favorable report so as to-enhance the value of the property in which he himself is interested, or an unfavorable report so as to stifle competi-

Jun 1, 1909

By MERLE HOWARD GUISE

WHEN I was a boy I walked into Fairbanks in 1905. I was but a soft chechako, and arrived with blisters covering my feet, as a result of "mushing" the 400-mile trail on foot. Because of them, the display windows of the trading posts were first to catch my eye-dog and horse collars, harness and sled parts! And because of my enthusiasm for things adventurous, I looked long upon the prospectors' gold pans, shovels, rifles, camp equipment, and what not. Today those windows are filled with motor car accessories, tires and repair parts; yes, even thermos bottles and vacuum cleaners! There were many chance meetings with little parties of prospectors in my youth, and it always set my blood to tingling. Sometimes it was a 70-year-old sun-baked son of the Arizona desert, wrangling his stubborn, faithful jenny away from some outfitting store, at others a shovel-ended poling b0at in northern Canada, \vith the partners and the dogs towing upstream along the bank, or an old sourdough, with tug-rope around neck and hand on the spruce sapling gee-pole, mushing along behind his two or three old, plodding malamutes, dragging a little Yukon sled piled high with rusty sheet-iron stove, pick and shovel, cross-cut saw and axe, rifle, bales of dog salmon, and other paraphernalia. These meetings envisioned the panning of old creek beds and draws in the search for as yet undiscovered pay-channels; they meant the toughest kind of work sinking a hole to bedrock in some far-away valley of promise; they suggested wood fires to thaw the frozen muck and gravel and crude windlass and hand-made tub to hoist the water and the mud; but loudest of all they spoke of Adventure.

Jan 1, 1929

Mr. Tays (communication to the Secretary): Mr. Wynne's criticism of my paper* brings forward a few points which are really important, and might properly have been considered in the original paper. By calling attention to them he has rendered me a service. It is quite true, as Mr. Wynne says, that, in the tests reported by me, the Bryan mill was always working at a relative disadvantage, and my comparison of the work of this mill with that of the stamp-battery should be interpreted, therefore, so much the more favorably to the mill. Of course, wire screens can be used to advantage on the Bryan mill, if they are not of smaller size than 30-mesh; but

Jan 1, 1902

Jan 1, 1938

Jan 1, 1938

By AIME

TITANIUM-RICH ilmenite deposits, situated in the Allard Lake area in Quebec some 400 miles down the St. Lawrence River from Quebec City and 28 miles north of Havre St. Pierre on the north shore of the Gulf of St. Lawrence, are undergoing an intensive development program by the joint efforts of the Kennecott Copper Corp. and The New Jersey Zinc Co. Easily accessible ore, amounting to about 125 million long tons and carrying from thirty to forty per cent titanium oxide, has been delimited. Plans are being made for construction of an electric smelter at Sorel, on the south bank of the St. Lawrence midway beween Montreal and Three Rivers, which will produce 650 long tons of high-grade titanium slag and 500 long tons of iron per day from 1500 long tons of ore. Occurrence of ilmenite ore in this area has been known since J. A. Retty reported his geological work in the lower Romaine River area for the Quebec Bureau of Mines in 1941. In this report Dr. Retty mentions the presence of anorthosite rocks, some of which were rich in ilmenite. Claims were staked by several interests but the small showings and complex metallurgy were too formidable for any organization not adequately equipped with capital, metallurgical knowhow, and market outlets. However, Kennecott became interested and through a newly formed Canadian subsidiary, Kennco Explorations Ltd., options were taken up under the direction of A. H. Robertson. An area of 300 square miles was traversed in the summers of 1945 and 1946. During 1946 and 1947 geophysical and diamond-drill prospecting disclosed a num-

Jan 1, 1948

By T. H. Alden

T. H. Alden (General Electric Research Laboratory)—This paper as well as earlier ones of Dr. Wood represent an important contribution to the experimental description of fatigue fracture. The mechanism of fracture proposed by the authors, however, is not established by this data nor supported by other data existing in the literature. Although taper section metallography provides a rather detailed picture of fatigue crack geometry, photographs so obtained must be interpreted with care. The narrow bands revealed by etching, frequently associated with surface notches, are labeled by the authors "fissures". Measurement shows, taking into account the 20 to 1 taper magnification, that the depth of these structures is at most 2 to 3 times the width. This distinction is important in the conception of a mechanism of crack formation. It is difficult, for example, to imagine a deep, narrow fissure arising from a "ratchet slip" model. A surface notch, on the other hand, may form easily by this mechanism. The notches observed in the present work are the subsurface evidence of the surface slip bands or striations in which fatigue cracks are known to originate.4-6 It is clear that an understanding of the structure of these slip bands is of key importance in understanding the mechanism of fracture. The evidence presented shows that these regions etch preferentially, possibly because they contain a high density of lattice defects, or as the authors state equivalently, because they are "abnormally distorted." However, it is not possible to conclude that the distortion consists of a high density of vacant lattice sites. The fact of a high total shear strain in itself does not assure a predominance of point defects as opposed to other defects, for example, dislocations. Other evidence in the literature which suggests unusual densities of point defects formed by fatigue7-' refers not to the striations or fissures, but to the material between fissures (the "matrix"). If a choice must be made, the preferential etching would seem to be evidence for a high dislocation density, since dislocations are known to encourage chemical attack in copper;g no such effect is known for the case of point defects. A third alternative is that the slip bands are actually cracked, but that near its tip the crack is too narrow to be detected by the authors' metal-lographic technique. In this case the rapid etching can be readily understood in terms of the increased chemical activity of surface atoms. Unless a vacancy mechanism is operative, the motion of dislocations to-and-fro on single slip planes will not lead to crack growth. Point defect or dislocation loop generation are the principal non-reversible effects predicted by this model. In any case, the nonuniform roughening of the surface in a slip band6 requires a flexibility of dislocation motion which is not a part of the to-and-fro fine slip idea. The same is probably true of crack growth by a shear mechanism. Either some dislocations must change their slip planes near the end of the band and return on different planes,'0 or dislocations of opposite sign annihilate." The mechanism by which these processes occur in copper at room temperature or below is that of cross slip. Thus cross slip appears to be essential to fatigue crack growth.6'10"12 The fact that a tensile stress opens the slip bands into broad cracks does not indicate the structure of the bands or the mechanism by which cracks form. The charactersitic concentration of slip into bands during fatigue shows a low resistance to shear strain in these regions. (This fact in itself may be inconsistent with a high concentration of vacancies.) The authors contend also that continuing shear produces an additional mechanical weakening so that the bands fracture easily (are pulled apart) under the influence of the superimposed tensile stress. It is equally possible that the only weakness is a weakness in shear, that the crack propagates by a shear mechanism, and that subsequently the tensile stress pulls the crack apart. Even the direct observation of bands opened by a tensile stress would not be conclusive since, as argued above, they may be fine cracks. The same argument applies to internal cracks, their existence in the presence of a tensile stress not indicating the mechanism of formation. Internal cracks originating in regions of heavy shear have also been seen following tensile deformation of OFHC copper,13 so that this mode of fracture is not unique to combined tensile and fatigue straining. The authors point out in their companion report14 that 90 pct of the cracks formed during pure tor-sional strain were within 8 deg of the normal to the specimen axis. If the tensile stress were an important factor in crack propagation, it is surprising that the cracks cluster about the plane in which the normal stress vanishes. Similarly, a study of zinc single crystals showed that for various orientations the life correlated well with the resolved shear stress on the basal plane,'= and was not dependent on the normal stress across this plane. W. A. Wood and H. M. Bendler (Authors' reply) -Dr. Alden's discussion emphasizes the essential point in the relation of slip band structure to

Jan 1, 1963

By Gregory L. Gullord

In September, 1975, production was begun at the new milling facility of ASARCO Incorporated, the Young Mill. The mill is located adjacent to the Young Mine 35 km (22 miles) east of Knoxville, Tennessee. The Young Mill replaced the obsolete Mascot Mill which had been operating since 1913. The basic flow sheet of Mascot was retained for the construction of the Young Mill, with a 20% increase in capacity included in the design. The Young Mill is capable of processing 7710 - t/d (8500 stpd) of crude ore from three underground mines (Young, Immel and Coy) yielding 300 - t/d (330 stpd) of 63% zinc concentrate. The Young Mill is unique in that 92.5% of the ore milled is recovered as saleable products, including zinc concentrate, construction aggregate, sand and agricultural limestone. Processing at the Young Mill is divided into five basic stages: two-stage crushing, heavy media separation, grinding-flotation, concentrate filtering and drying, and limestone by-products recovery. The ore bodies are located in the Knox formation, which consists of primary dolomite, secondary dolomite and limestone with silicas in the form of chert and jasperoid. The zinc mineralization occurs as an exceptionally pure sphalerite. The ore contains an occasional abundance of pyrite and traces of fluorite and barite. TWO STAGE CRUSHING Ore enters the crushing section from two points. The Young Mine ore is hoisted into a 816 ton (900 st) bin which feeds a 1.52m (60 in) conveyor via a 1.52 m (60 in) vibrating feeder. The Immel ore is trucked 10 km (6 miles) by an independent contractor and weighed on automatic recording truck scales at the entrance to the property.

Jan 1, 1977

By H. David Swain

On Bougainville Island in Papua New Guinea, Bougainville Copper Ltd. (BCL) has successfully applied electronic data processing (EDP) techniques to pit operations and mine planning. Though the EDP program is not complete, BCL has realized significant improvements in short and long range mine planning, and equipment and manpower utilization. About 80% of BCL's 4000 employees are Papua New Guinea nationals, and most have little education or training. The operational characteristics of the computer equipment, however, have been quickly adapted by users with low educational standards.

Jan 3, 1979

By William M. Newton, John E. Sherborne

The value of the electric log as a means of interpreting underground structures has been increasingly demonstrated by its almost universal present-day use. It becomes important, therefore, to be able to evaluate the factors that affect the values obtained. By far the greatest number of electric logs are measured today in boreholes filled with rotary mud, the properties of which may exert an important influence on the electric log. In an effort to establish what the order of magnitude of such effects might be, a series of investigations was made in the laboratory and the field. Apparatus suitable for either field or laboratory use was designed and a procedure established for determining the factors that affect the resistivity of drilling muds over a wide variation in mud condition. Five muds representative of the types of clay-base muds employed in California were tested and the following observations were made: 1. The effect of raising the temperature from 8o° to i8o°F. is to decrease the resistivit~ of the mud or filtrate approximately 50 per cent. 2. The resistivity of the mud in most cases closely approximates that of its filtrate. 3. The change in the resistivities of muds caused by the addition of chemical is not the same function of the amount of chemical added for each mud. 4. The effect produced by increased sodium chloride content is to reduce markedly the resistivity of the mud and its filtrate. 5. Weighting materials, such as baroid and limestone, tend to increase the resistivity of drilling mud. 6. Cement and counteracting reagents reduce mud resistivity. The results of the investigation indicate that the mud resistivity is materially affected by the addition of electrolytes whether these are added for the purpose of conditioning the mud or enter the mud when salt beds or highly saline structures are penetrated. It should be observed, however, that the magnitude of the effect produced upon the electric log by changes in mud resistivity is also dependent upon the relative salinity of the water en. countered in the formation being logged. The laboratory data are supplemented by field data, which indicate that both the self-potential and resistivity curves are influenced by mud resistivity.

Jan 1, 1946

By John E. Sherborne, William M. Newton

The value of the electric log as a means of interpreting underground structures has been increasingly demonstrated by its almost universal present-day use. It becomes important, therefore, to be able to evaluate the factors that affect the values obtained. By far the greatest number of electric logs are measured today in boreholes filled with rotary mud, the properties of which may exert an important influence on the electric log. In an effort to establish what the order of magnitude of such effects might be, a series of investigations was made in the laboratory and the field. Apparatus suitable for either field or laboratory use was designed and a procedure established for determining the factors that affect the resistivity of drilling muds over a wide variation in mud condition. Five muds representative of the types of clay-base muds employed in California were tested and the following observations were made: 1. The effect of raising the temperature from 8o° to i8o°F. is to decrease the resistivit~ of the mud or filtrate approximately 50 per cent. 2. The resistivity of the mud in most cases closely approximates that of its filtrate. 3. The change in the resistivities of muds caused by the addition of chemical is not the same function of the amount of chemical added for each mud. 4. The effect produced by increased sodium chloride content is to reduce markedly the resistivity of the mud and its filtrate. 5. Weighting materials, such as baroid and limestone, tend to increase the resistivity of drilling mud. 6. Cement and counteracting reagents reduce mud resistivity. The results of the investigation indicate that the mud resistivity is materially affected by the addition of electrolytes whether these are added for the purpose of conditioning the mud or enter the mud when salt beds or highly saline structures are penetrated. It should be observed, however, that the magnitude of the effect produced upon the electric log by changes in mud resistivity is also dependent upon the relative salinity of the water en. countered in the formation being logged. The laboratory data are supplemented by field data, which indicate that both the self-potential and resistivity curves are influenced by mud resistivity.

Jan 1, 1946

By J. H. Henderson, T. E. Morrisson

An irvestigation has been made of the production of oil through horizontal fractures of high capacity and large radius placed at the base of producing formations. The specific aitns of the study were to (I) determine by model studies the reservoir performance when gravity drainage is the only producing mechanism, and (2) develop a method of predicting such perfortnance from commonly measured reservoir proper-ties. Although the theoretical approach tailed to develop a rigorous analytic sorution to the transient problem, it (lid lead to a practical method of predicting performance. Predictions (Ire in good agreement with rates and recoveries observed in scaled-model experinzents. Capillary effects and the influence of relative permzenbil-ity are taken into account. The experimental program was mainly concerned with the influenre of fracture radius, fracture capacily and capillary hold-up on the total recovery and the rate of recovery. Much of the experimental work was done on a triangular model which represented one-eighth of a square well pattern, so constritcted that horizontal fractures of varying radii and flow capacity could be studied. An electrolytic model was used to relate the initial production rates to fracture radius, formation thickness and the drainage radius of the well pattern. The conclusions reached as a resrtlt of the work are as follows. I. The production of oil under gravity force alone into a well-propped horizontal fracture, whose radius is of the order of hundreds of feet, is a recovery method which combines high recoveries with very acceptable production rates. 2. The mechanism is effective in "dead oil" reservoirs as well as in reservoirs which possess the energy of solution gas. 3. A method of predicting performance has been developed which gives good agreement with experimental behavior in cases of practicnl interest. Even for very thick beds and large fracture radii, where actual conditions do not conform to the assumptions made, the method gives order of magnitude predictions which would not otherwise be possible. INTRODUCTION Gravity drainage of oil from a formation which has continuous ver- tical permeability over a reasonable depth interval is a surprisingly effective method of recovery. However, for a conventional well the production rates which result from gravity drainage are so low that the economics are seldom attractive. The same formation may produce rapidly and profitably by gravity alone through a high capacity, extensive (i.e., > 100-ft radius) horizontal fracture placed near the bottom of the pay section. Fig. 1 shows a schematic diagram of the plan. Energy in the reservoir gas is not a necessary condition for this recovery process. With a sufficiently large fracture, attractive production rates will result from gravity flow alone, and the producing GOR need only be the solution GOR. It is, of course, necessary to keep the fluid level in

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

By D. L. McDanels, J. W. Weeton, R. W. Jech

An investigation was conducted to determine the stress-strain behavior and tensile properties of metallic composites and to relate them to the properties of the base materials. Tungsten fibers in a copper matrix were chosen as the model sys-tem to investigate these properties. Room-temp-atzcre tensile and dynamic -modulus tests were used To meet the demand for improved structural materials, considerable effort is being directed toward the creation of composite materials. One such material under investigation is the fiber-reinforced composite, in which a ductile, relatively weak matrix is reinforced with high-strength fibers. Some work has been done on the reinforcement of metallic matrices with metallic fibers1"5 as well as with ceramic-whisker reinforcement. Summaries of much of this work have been published by Mach-lin7 and Baske~.' Work done at the Lewis Research Center of NASA-" has involved the making and testing of composites composed of a fiber, tungsten, and a matrix, copper, which were insoluble in each other. An equation was presented that showed the relation between the ultimate tensile strength of the composites and the strengths and relative volume percents of the components. This relation was verified experimentally for composites containing fibers extending the full length of the specimen as well as for composites reinforced with short-length or discontinuous fibers. Since the publication of the preliminary results,9'10 additional data have been obtained. This paper presents these data as well as analyses of the stress-strain behavior and the mechanics of deformation of uni-axially oriented, fiber-reinforced metallic composites, in which both components are mutually insoluble. EXPERIMENTAL PROCEDURE Composites were made with high-purity copper as the matrix and 3-, 5-, and 7-mil-diam tungsten wire as the reinforcing fiber. Some specimens were made in which the reinforcing fiber extended completely through the full length of the composite test section. The fibers were placed in ceramic to determine these properties. The composites were reinforced with either continuous or discontinuos tungsten fibers. The tensile properties and stress-strain behavior of composites reinforced with either type of reinforcement were similar, and in both cases the full strength of the fiber was utilized. tubes to insure axial orientation and infiltrated with copper at 2200°F for 1 hr. Composites were also made with short-length (3/8 in. long) 5-mil-diam tungsten fibers as discontinuous reinforcement and infiltrated under the same conditions. The reinforcing fibers in both cases were longitudinally oriented in the direction parallel to the tensile axis. Room-temperature tensile tests were conducted on the composites, stress-strain curves were obtained, and ultimate tensile strength and elongation were measured. Dynamic modulus of elasticity, based upon the resonant frequency induced in the flexural mode of vibration, was also determined for the composites and the components. A more detailed discussion of the experimental procedure employed in this investigation may be found in Ref. 11. RESULTS Room-temperature tensile tests were conducted on 3-, 5-, and 7-mil-diam tungsten wires which had been annealed for 1 hr at 2200°F and show the tensile strength of the wires to be 331,000, 327,000, and 290,000 psi, respectively. Since all the composites were infiltrated under these conditions, the strengths were considered to represent the strength of the fibers in the composites throughout this study. The average tensile strength of the annealed copper used as the matrix in this investigation was 27,800 psi. Results of room-temperature tensile tests on composites reinforced with 3-, 5-, or 7-mil-diam tungsten fibers are plotted as functions of composition in Fig. 1. These data represent previously reported datag,l0 as well as data more recently obtained. The line shown on each curve represents a prediction of tensile strength as a function of composition; the calculation of this line was explained in Refs. 9 and 10. A similar plot is presented in Fig. l(d) for composites reinforced with short-length, discontinuous 5-mil-diam tungsten fibers. Again, both the previously reported and the recent data are presented, and the line shown is identical to that shown for

Jan 1, 1965

By W. O. Philbrook, R. S. Kaplan

Rates of oxidation were studied for levitation-melted samples of Fe-C, Fe-Si, Fe-C-Si, Fe-C-P, Fe-C-Mn, and Fe-C-S alloys oxidized by mixtures of either 5 or 10 pct O2, in helium at several temperatures in the range 1850o to 2050°C. The concentrations of the oxidized elements decreased linearly with time. Mass transport in the gas phase was found to be the rate-controlling step. Ilowever, a mulliple -film model was necessary to account for the flux of iron and manganese vapor counter to the oxygen flow. THE advent of the basic oxygen and spray-refining processes of steelmaking has generated considerable interest in the kinetics of reactions between oxygen-bearing gases and liquid iron alloys. The object of this research was the determination of the role of mass transport in the gas and metal phases and of surface chemical reactions in the overall oxidation process. Of the reactions for elimination of elements dissolved in liquid iron, the oxidation of carbon has been investigated most extensively. Studies by Fuji and Ura,1 Fuji,' and Gunji et a1.,3 done with pilot-scale basic oxygen furnaces, indicated that mass transport of gaseous oxygen was rate controlling when the metal carbon content was greater than 0.15 to 0.30 pct. When the carbon content was less than this critical amount, diffusion of carbon dissolved in the iron was thought to be rate limiting. L. A. Baker et a1.4,5 levitated samples of iron-carbon alloys and oxidized them in CO-CO2, CO-C02-He, and O2-He atmospheres at 1660°C. These investigators found that the metal carbon concentration decreased linearly with time and their samples exploded when the carbon content fell below about 0.8 pct. They concluded that the rate-limiting step was the transfer of oxidant to the gas-metal interface. A model based on this rate-limiting step predicted decarburization rates within a factor of two of those experimentally observed. The explosion of the samples was attributed to a shift in rate-controlling step from gas-phase mass transport to transport of carbon dissolved in the metal. L. A. Baker and R. G. ward6 and R. Baker7 used freely falling droplets to investigate oxidation kinetics. In both papers, the authors speculated that flame fronts may have been partially responsible for the lack of better agreement between experiment and theory. Swisher and Turkdogan8 oxidized liquid iron having an initial carbon content of 0.97 pct with CO-CO2 and CO-C02-Ar mixtures at 1580°C. They concluded that a surface reaction was the rate controlling step. Iron-silicon alloys have been oxidized by R. Baker7 and Filipov and Martynov.9 R. Baker 7 also studied iron-carbon-silicon alloys falling as liquid droplets through oxygen. He found that the rate of both carbon and silicon oxidation varied inversely with the drop radius. When the initial silicon concentration was greater than 6 pct, the samples cooled during their fall. Manganese oxidation has been studied by R. Baker,7 and by Filipov and Martynov.9 ward10 investigated the loss of manganese from liquid iron under vacuum. He found that mass transport of manganese vapor was rate limiting in argon atmospheres of 0.02 torr to 700 torr pressure. Iron-sulfur alloys were desulfurized with H2-He and H2-Ar mixtures by Peters et al.11 A model based on the transport of H2S from the gas-metal interface into the bulk gas gave fair agreement between the predictions of the model and the experimental results. EXPERIMENTAL TECHNIQUE Essentially, the technique consisted of using helium-oxygen gas mixtures to oxidize levitated samples of liquid binary and ternary iron-base alloys. The fused silica reaction tube is shown in Fig. 1. The coil design is similar to that of L. A. Baker et al.4'5 A Tef-lon-sheathed, ferritic stainless steel lifter (B) and an alumina pedestal (C) were used to support the sample in the coil prior to levitation and for the recovery of the sample. Samples were inserted into

Jan 1, 1970