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By L. Seigle, R. Resnick

An inert-marker movement experiment indicates that the ratio of the intrinsic diffusion coefficients DC:DTa = 80:l in TaC at 2500°C. Measurements of the diffmion coefficient of carbon in nonstoichiometric TaC at temperatures from 1700° to 2700°C reveal that Dc increases with decreasing carbon content, but much less than expected from the probable change in vacancy concentration with carbon content. A diffusion process involving two simultaneously operating mechanisms is postulated, and shown to be theoretically feasible. The average value of the carbon diffusion coefficient is given by DC = 0.18 exp[(-85,000 ± 3000)/RT] sq cm per sec over the composition range 46 to 49.5 at. pct C. BECAUSE of their high melting points and hardness, the carbides of the IV, V, and VI group transition metals, along with those of uranium, have attracted considerable interest for applications at high temperatures. In these applications the reactivity of the materials is important, and, since rates of diffusion within the compounds influence reactivity, a knowledge of diffusion kinetics and mechanisms is desirable. While many investigations of the mechanical and electrical properties of these compounds have been made, only two fundamental investigations of diffusion in the carbides are known. Chubb, Getz, and Townleyl measured the diffusivity of carbon and uranium in UC, and Gel'd and Liubimov2 measured the diffusivity of carbon and niobium in NbC. This paper describes an investigation of the diffusion of carbon in tantalum monocarbide and, in particular, the influence of carbon deficiency on this process. Tantalum carbide melts at approximately 3800°C, which makes it one of the highest melting materials known. The compound exists over a rather wide range of carbon Content.3-7 At the peritectic temperature, 3240°C, the phase extends from about 36 to 50 at. pct C. Although the compound can exist with a substantial carbon deficiency, the high carbon phase boundary remains near the stoichiometric composition over the entire temperature range; i.e., no carbon excess is observed. The structure of TaC is the NaCl type wherein carbon atoms normally occupy the octahedral sites in a somewhat expanded fcc lattice of tantalum. Decrease of the lattice parameter with decreasing carbon suggests that the removal of carbon introduces octahedral vacancies into the lattice. I) EXPERIMENTAL DETAILS AND RESULTS Inert-Marker Experiments. In a compound such as TaC the interstitial element would be expected to diffuse more rapidly than the metal. This was confirmed by an inert-marker experiment, following Srnigelskas and irkeendall.8 Ideally, the markers should be placed at the interface between a slab of low-carbon TaC and graphite, and their movement during subsequent inter-diffusion measured. Unfortunately, no solid could be found which is unreactive in contact with carbon at the high temperatures employed in these experiments. In order to circumvent this problem, a specimen was designed in which the markers consisted of several small canals running just below the surface of a tantalum slab. This specimen was prepared by machining grooves on the surface of the tantalum slab and then diffusion-bonding a thin plate of tantalum to the slab over the grooves. The surface of the plate was then ground down until the distance between the canals and surface was as small as possible (about 0.01 cm). Thus, the canals would lie entirely within the TaC phase after a short period of diffusion. The diffusion anneal consisted of immersing the metal sample in high-purity graphite powder and heating for approximately 10 hr at 2500°C under vacuum. At this temperature, the vapor pressure is sufficiently high and the transfer of carbon from graphite sufficiently rapid to allow the surface of the diffusion sample to attain the stoichiometric carbon concentration very quickly. Conclusions regarding the relative diffusion rates of carbon and tantalum in the compound layers (TaC and Ta2C) can be drawn from the location of the canals after the diffusion anneals. If the growth of the layers is governed mainly by the diffusion of carbon, as expected, the canals should remain close to the sample surface. If the diffusion of tantalum contributes appreciably to formation of the compound layers, the distance from the markers (canals) to the surface should increase. Fig. 1 shows, diagrammatically, the appearance of the specimens after diffusion, and Table I presents the depth below the surface at which the

Jan 1, 1967

By Thomas E. Ban, Charles D. Thompson, Charles A. Czako

Continuous sintering-a metallurgical process for more than 50 years-has broadened from its origin in nonferrous metallurgy to present-day applications in ferrous, chemical, and nonmetallic fields. During the past year, self-fluxing sinter production has been a subject of active interest to iron metallurgists in North America. Accomplishments however, have come predominantly from Europe and proper interpretation of these reports requires an understanding of European raw materials and European economics. The technology, of course, can be applied universally.

Jan 10, 1959

By Richard H. Bube

Photoelectronic radiation detectors may be conveniently classified as homogeneous intrinsic, homogeneom extrinsic, or junction type. Highly photosensitive homogeneous intrinsic photodetectors may be prepared from a number of different II-VI, III-V, or IV materials. Such materials require the presence of specific imperfections that can act as sensitizing centers to provide long majority carrier lifetime. Homogeneous extrinsic photodetectors are of interest primarity for infrared detection, and consist principully of germaniuim and silicon with suitable inpurities. A vaviety of junction photodetectors exist, with silicon us the most common material for them all. The following extrema in performance are found: 1) highest photoconductivity gain in homogeneous intrinsic photodetectors; 2) smallest response time (highest frequency response) in p-i-n junctions; 3) largest gain-bandwidth product in avalanche diodes. ALTHOUGH the total number of materials exhibiting photoconductivity effects is very large, only a relatively few of these have appropriate properties for a practical photoelectronic radiation detector. In fact if one surveys the commercial detectors currently available, one finds that the field is dominated by some ten or fewer materials. These are summarized in Table 1 in terms of the other important variable in detector fabrication, the structure of the material, i.e., whether the material is used as a single crystal or in polycrystalline form, and whether the material is used as a homogeneous detector or whether the detector depends upon the existence of a junction or barrier in the material. The principal wavelength range for each type of material is also shown, together with an indication of the utilization of intrinsic or extrinsic excitation. For the purposes of the present comparison of various detectors, it will be convenient to discuss two main topics: homogeneous photodetectors and junction photodetectors. The performance of a photoelectronic radiation detector is measured in terms of two parameters: the photoconductivity gain, and the response time of the detector. A convenient figure-of-merit is given by the ratio of gain to response time, often called the gain-bandwidth product. The photoconductivity gain is a device parameter since it varies in many cases with the applied voltage and the detector geometry, and should be distinguished from the actual photosensitivity of the material involved. This photosensitivity can be conveniently given as the product of free carrier lifetime and mobility in the material. The photoconductivity gain is defined as the number of charge carriers which pass between the electrodes per second for each photon absorbed per second, where G is the photoconductivity gain, is the pho-tocurrent in amperes, e is the electronic charge in coulombs, and F is the total number of electron-hole pairs created in the photo conductor per second by the absorption of light. The gain may also be expressed as the ratio of the lifetime of a free carrier to the transit time for that carrier, i.e., the time required for the carrier to move between the electrodes. For a material in which one-carrier conductivity dominates, where T is the lifetime of a free carrier, ttr is the transit time for this carrier, p is the carrier mobil-ity, V is the applied voltage, and L is the electrode spacing. From Eq. [2] it follows that the photoconductivity gain is proportional to the photosensitivity of the material (tP), the proportionality constant being The photosensitivity of a material, and hence the photoconductivity gain of a device utilizing the material, depends on the lifetime of the free carriers as a critical parameter. In a homogeneous material this lifetime is determined by the nature of imperfections in the material, and in an inhomogeneous material the lifetime is determined by the specific junction structure. The speed of response, the other basic photodetec-tor parameter, is determined by factors quite similar to those important for photoconductivity gain. Imperfections are of primary importance in homogeneous materials, and the structure of the junction is a determining factor in junction devices. For infrared detectors it has become common to define another quantity designed to indicate directly how effective the detector is in distinguishing between a small photoconductivity signal and random noise due to the detector and its environment. The detectivity D* is given by

Jan 1, 1968

By W. A. McCurdy, Joseph W. Leonard, William F. Lawrence

INTRODUCTION Utilization from the Point of View of the Preparation Engineer The primary interest of the coal preparation engineer is in process design, operation, and maintenance to produce an acceptable product that can be sold at the greatest possible profit. Because of emphasis upon these interests, attention to other potential values of coal is sometimes neglected. The intent of this chapter is to alert the preparation engineer to the utilization possibilities of the product as well as the tributary coal flow moving through a modern coal preparation plant. The basis for any unrealized potential derives directly from the coal seam itself. Most coal seams consist of coal bands and benches sandwiched together in layers that differ visually from each other in physical structure and luster. Randomly selected physical and chemical ranges determined from layers of coal in a single seam can easily differ by as much as 30 Hardgrove grindability indices, 0.30 of a specific gravity point, 20 percentage points of ash, 6 percentage points of dry volatile matter, and 10 percentage points of total su1fur.l Similar wide variations exist for calorific value, seam moisture content, and, undoubtedly, for any other conceivable coal test parameter that might be used for comparative purposes. These observations all point to the long-established fact that coal is not homogeneous, as conventional analytical methods might tend to indicate, but is instead a highly heterogeneous substance.

Jan 1, 1979

By Ralph A. Sherman, J. M. Pilcher

BY surface treatment of coal is meant the application of a material, either solid or liquid, to the surface of pieces of coal. The purposes of surface treatment are varied. They may be to identify or "trade-mark" the coal, to modify the burning characteristics, the coking tendencies, or the behavior of the ash, to prevent the freezing of wet coal, or to control the dust. The control of dust is the usual purpose of surface treatment. TRADE-MARKING COAL The application of color to the surface of coal for the purpose of identification and registration of the trade-mark has been practiced to some extent. In 1928, the Glen Alden Coal Co. began to color its coal and adopted the trade-mark, "Blue Coal." The Old Ben Coal Co. later followed a similar practice with "Green Coal." A commoner means of identification of coal has been the stenciling of designs or pasting labels on large lumps or in the distribution of small cardboard tags through the smaller sizes. The details of the method used to color coal have not been revealed. Usually all of the coal is not treated, because of the expense. Only enough pieces are colored to show clearly when distributed through the coal.

Jan 1, 1943

By Hansheinz Portisch, Harold Margolin

A surface expansion was found to occur sometime after etching in Ti-A1 alloys containing 9.5 to 12.5 wt pct Al. The structure formed, grew, and disappeared with tzrrze. The surface expansion was followed by microscope observations and interferometric and lattice parameter measurements. Activation energy measurements for the growth of the "expansion structure" and chemical analysis indicated that the phenomenon occurred as a result of hydrogen pzckup during etching. It is proposed that hydrogen initially enters octahedral sites of Ti3Al coherent with a Ti and later shifts to the tetrahedral sites. It is postulated that expansion occurs when hydrogen enters the tetrahedral sites. The expansion structure disappeared, it is proposed, because of diffusion of hydrogen from the surface into the body of the alloy and because of loss of coherency of Ti3Al. In examining Ti-A1 alloys, Ence and arolinl observed markings on the surface of specimens. These markings did not appear after electropolishing only, but rather appeared only after etching. The markings appeared to grow as a function of time after etching and later seemed to disappear. Although the markings had some similarity to precipitates, showing, frequently, a Widmanstatten type of arrangement, the observation that other microstructural markings continue to be seen within the new structure suggested that it was actually not a precipitate. The source of this structure was unknown and an attempt was made in the present investigation to develop some understanding of its nature. It has been labeled expansion structure. 1) EXPERIMENTAL PROCEDURE A) Alloys. Alloys in the range 6.5 to 14.5 wt. pct A1 were studied. Bars, 4 in. sq, forged from Bureau of Mines (73 Bhn) titanium consumably arc-melted 4-lb ingots,' as well as 50-g arc-melted buttons of desired aluminum contents were used. The 50-g buttons also used Bureau of Mines titanium (73 Bhn) and aluminum of 99.99 pct purity. Buttons containing up to 8.5 wt pct A1 were hot-rolled from a furnace at 900' . Those with higher aluminum contents were hand-forged on a titanium anvil, and heated with an oxygen-hydrogen torch in the region of 1200" to 1300°c. Frequent reheating kept the samples at the desired temperature range. After a reduction of about 30 pct, the samples were water-quenched. To eliminate any contamination picked up either during hot rolling or forging, at least 1 mil of the surface of the sample was taken off. B) Heat Treatment. Prior to heat treatment all alloys were vacuum-annealed to remove hydrogen. Samples were annealed at 900' until a vacuum of 10'5 mm Hg was established. After this treatment, the samples were wrapped in molybdenum sheet and heat-treated in argon-filled quartz capsules, which were broken under water or iced brine at the conclusion of the heat treatment. All heat treatments under dynamic vacuum were performed in a rapid-quench furnace. This consisted of a molybdenum-lined quartz tube attached to a vacuum system and through a stopcock to a beaker of water. At the completion of the heat treatment the vacuum stopcock was closed, the furnace shut off, and dropped below the quartz tube. Then immediately the inlet stopcock was opened and water admitted until the tube was filled. The steam formed was allowed to escape through the inlet stopcock. This method was used in heat treatments up to llOO°C. C) Metallography. Specimens for metallographic examination were ground, then electropolished using a Disa Electropol machine with a perchloric acid electr01te. Specimens were etched with R-etch.3 A standard etching time of 3 min was used, with the specimen being agitated during immersion. D) Sample Preparation for X-ray Analysis. Samples 0.2 to 0.5 mm in diam were produced from heat-treated rods which were turned to 2 mm diam on a lathe and then rotation-etched. An etchant consisting of 1 pt HF, 7 pt HN03, and 12 pt HzO was satisfactory. With the rod rotating in a vertical position at 50 to 100 rpm, a needle with uniform dimensions could be obtained. Care had to be taken to insure that the rod was at the center of rotation, otherwise cavitation developed. If a small unevenness developed, it was possible to grind it off with a fine emery paper. E) X-ray Diffraction. All X-ray work was done on a North American Phillips X-ray diffraction apparatus and a Jarrell Ash microfocus X-ray unit. The Phillips unit was used with a copper target and nickel filter. The Jarrell Ash unit was fitted with a cobalt target and iron filter. For the Phillips unit 35 kva and 20 ma were used, whereas for the microfocus unit with the 100-p fixed-focus gun 40 kv and 1.5 ma were used. It was found that alignment of cameras on the Jarre11 Ash unit was very critical. The X-ray beam contains an intense area which is not the beam center. The cameras were aligned with the intense region by monitoring the beam coming out of the camera with a Geiger counter. Adjustments were made until a maximum intensity was obtained. A Phillips diffractometer with a Brown chart recorder furnished some of the lattice parameter data. The divergence slit up to 80 deg 28 was I deg; above 80 deg, a 4-deg opening was used, while the scatter slit was1 deg and the receiving slit had a 0.003-in. opening. The general scanning rate was 1 deg per min, while peaks of special interest were rescanned at -j deg per min. For elevated-temperature X-ray diffraction a Uni-cam High Temperature Camera with a film diameter

Jan 1, 1969

By A. Bauer, P. Calder, N. H. Carr, G. R. Harris

Smallwood mine is part of the Iron Ore Company of Canada's Carol Lake operation and is situated in Labrador, 240 miles north of Sept-Iles, Quebec. Last year, 15 million tons of crude ore were crushed to yield 6.3 million tons of concentrate and pellets. This year the figures will be 17 million of crude and 7 ¼ million tons of concentrate and pellets, which is the full plant capacity. Carol Lake ores consist primarily of specularite and magnetite mixed with quartz. Since both rotary and jet piercing drills are used, it is often desirable in planning to know in which regions of the orebody, or new orebodies, a particular drill will be most economic. This makes it necessary to establish a correlation between drillability and pierceability and some physical rock property. For the rotary drills a good correlation was found with penetration rate and grinding factor index. The jet piercers were found to have a reciprocal relationship in the sense that the best rotary ground was the worst jet ground and vice versa. It is also indicated how an economic comparison could be made using these penetration rate versus grinding factor index curves, the hole size distribution curves for single pass and chambered holes, and the mine distribution curve for grinding factor index.

Jan 9, 1965

By W. J. Schuster

Safety in coal mines depends largely upon adequate training of the foreman. Although management must provide modern and safe equipment and at all times keep mines in first class condition from a safety viewpoint, final results will be determined by the quality of supervision. HANNA COAL CO., Division of Pittsburgh Consolidation Coal Co., operates three large underground mines in eastern Ohio. The section of Pittsburgh No. 8 coal seam in which these mines are located varies in thickness from 52 to 64 in. It is immediately overlain by a stratum of shaly material 12 to 15 in. thick locally known as draw slate, which is structurally very weak and which disintegrates rapidly upon exposure to atmosphere. Immediately above the draw slate as it is normally found is a band of extremely high ash material 6 to 12 in. thick known as roof coal or rooster coal, and above this is a stratum of conglomerate material varying from 4 to 10 ft in depth. Overlying the conglomerate is a relatively thick stratum of limestone, the first stable material above the Pittsburgh coal seam in eastern Ohio. With the method of full-seam mining that has been adopted, draw slate is shot down, loaded with the coal, and removed in the preparation plants. The roof coal then becomes the permanent roof. The major problem in mining the No. 8 seam in eastern Ohio is control of the roof. Since the strata above the draw slate contains no material with a structure firm enough to provide self-support, the roof begins to sag in a relatively short time after the coal and draw slate have been removed. The problem thus becomes one of getting temporary safety posts under this roof as quickly as possible to prevent a break or separation from occurring either in the roof coal or in the conglomerate above it. Haulage System The Pittsburgh No. 8 seam in eastern Ohio is relatively level, with only minor local dips. Throughout the Hanna Coal Co. mines, entries are generally 12 ft wide. Rooms are driven on a 60" angle on 30-ft centers and are 22 ft wide. No attempt is made to extract the 8-ft pillars between. The entire length of main line haulage is gunited in one mine, and a major portion in another. Two of the mines have single-track main haulage roads with passways. The third, a new mine, is double-tracked, and the roof is supported by steel crossbars, 60 lb or heavier, spaced on 4-ft centers and lagged. In recent years timbering on main line and secondary haulage roads has been accomplished by one of two methods: 1—crossbars are supported on a small section of post set in a hitch hole in the rib, or 2—or a hole is drilled in the rib about 12 in. below the roof, of sufficient depth to fasten securely a short length of 40-lb rail, the bottom of the rail facing the roof, on which a short post is set directly under the crossbar. At present the hitch-hole timbering method is favored. At two of the mines the main line haulage locomotives are 26-ton, 8-wheel units. These locomotives are of the axleless type, each wheel being individually mounted on the frame. The motorman's compartment is encircled by 3-in. armor plate for the protection of the occupants. At the third underground mine conventional 15-ton locomotives are being used. However, these locomotives have been completely rebuilt in the company's shops. Equipment has been streamlined and quarters have been provided for two people, who are protected by heavy steel plate in much the same way described above. This modernization program has been completed on all secondary haulage locomotives at the three mines, and the company is well on the way to similar equipment of the 6-ton section locomotives. The following additional features have been included in their modernization: 1—additional support for the motors to prevent their falling to the middle of the track and derailing the locomotives should a break occur in the suspension bar support; 2—installation of additional bracing to prevent brake rigging from becoming displaced and causing derailments; 3—enclosure of all electric wiring in conduit or raceway; 4—provision of an enclosed compartment for the storage of re-railers, jacks, and other equipment, so that they need not be carried on the outside of the motor; and 5—redesign of the end of the locomotive opposite the operator's compartment to prevent anyone's mounting from that direction. It is interesting to note that some

Jan 1, 1955

Jan 1, 1953

By A. G. Starliper, H. Kenworthy, A. Ollar

Vapor pressure determinations were made on synthesized germanium sulfides. Germanium and cadmium were removed from sphalerite concentrates by fuming. The fume was retreated to separate some of the cadmium from the germanium and, at the same time, upgrade the germanium to more than 5 pet content. MANY sphalerite concentrates contain certain impurities which have economic value as byproducts. These may include the volatile sulfides of germanium, cadmium, and lead. The objectives of the research reported in this paper were to study the fundamental volatility characteristics of germanium sulfides, to increase the recoveries of ger-

Jan 1, 1957

By R. Y. Williams

In the United States, fully 98 per cent. of the anthracite and bituminous coal tonnage obtained from underground operations is mined by the room-and-pillar system. Under this system, the total cost of the coal f. o. b. railroad cars contains as its greatest single item the money paid for "labor." Each labor dollar in an average bituminous mine may be subdivided into 85 c. paid for work done inby the gathering turnouts (including all work at the face), and 15 c. outby that point (including all work in and under the tipple). In an average anthracite mine, the corresponding figures are 70 c. and 30 c., the larger breaker force accounting mainly for the difference between these and the bituminous figures. The next largest single item after "labor" is usually "supplies and power;" and a division of this item inby and outby the gathering turnouts shows somewhat the same relative proportions as has been noted under the case of "labor". During the past 10 years, the chief advances made in the coal industry have been to obtain economies through complete mechanization covering that portion of the work which lies outby the gathering turnouts. These results have been accomplished by applying scientific principles to railroad yard layout, to cleaning and sizing machinery, to dumping facilities, to roller-bearing haulage equipment, and to heavy-rail, well-ballasted trackage. But these improvements, while gratifying in their resulting economies, apply only to 15 to 30 per cent. of the important cost items. Obviously, then, the big problem before the engineers of the coal industry today has to do with the methods of mining and the layout inby the gathering turnouts. Four years ago, Weston Dodson & Co., Inc., determined to have an exhaustive study made of the conditions which must be met in order to gain complete face mechanization, and in order that such a mining layout would be based on correct underlying principles. The result of that study, which was made by the writer, led to the adoption of a method of longwall mining wherein the roof is worked on the caving system and is supported as an overhang along the face by steel jacks.

Jan 1, 1928

By Frank R. Van Horn

It is customary to ascribe two general modes of occurrence to natural gas, namely, shale gas which, as the name indicates, is found in shale, and reservoir gas, which occurs in sandstone, conglomerate and dolomitic limestone. Both of these types are found in the Cleveland district. The shale gas has been produced on a small scale for a long period of years, probably dating back as far as 1883. Shale gas is a low-pressure gas, small in volume with variable pressure, and is limited to no definite horizon. It is generally independent of oil, may last for a long time, and is not dependent to any great extent on the structure of the rocks. There are many such wells in the district which range from 400 to 1,840 ft. in depth, although most have been completed at about 800 ft. This indicates that the wells pass through the Cleveland and Chagrin shales into the Huron or Portage shale of the Upper Devonian. During the last 2 years great interest has developed in a deeper-seated reservoir gas. What is commonly called reservoir gas is generally a high-pressure gas occurring in large volume at a definite horizon. Oil may, or may not, be associated with the gas, and in most regions in which reservoir gas is found, the geological structure is of great importance. This type of gas occurs in all large fields such as those of West Virginia which have been supplying Cleveland until the recent discovery of local gas at great depths in commercial amounts. Historical Outline The oldest well producing reservoir gas in the district was drilled in 1886 in Newburg for what was then known as the Cleveland Rolling Mill Co. This well was 3,000 ft. deep, and was thought to have reached the "Clinton" formation. Two "sands" showing small amounts of oil were recorded in the Niagara limestone at depths of 2,658 and 2,686 ft. This is about the horizon of the so-called Newburg sand which has proved to be of some importance as a source of gas and oil by recent drilling operations. The rock pressure was reported to be 400 to 500 lb. per square inch, but since the volume was only 14,000 to 16,000 cu. ft. daily, the well was not only considered unsuccessful but was thought to prove the absence of high-pressure gas in commercial quantities in the Cleveland district.

Jan 1, 1917

By C. G. Rhodes, D. Kramer

High-field critical transport current density (J) measurements at 4.2 °K as a Junction of applied magnetic field (H) were made on samples of cold-rolled and annealed columbium with H parallel to J. Microscopic examination of the samples revealed a well-defined planar fiber structure produced by the cold rolling. J was found to he lower when fibers are parallel to the direction of magnetic field penetration than when they are perpendicular. This effect may he a consequence of the interaction of flux movement with fiber boundaries. THE severe changes in microstructure brought about by cold working superconductors leads to profound changes in their superconducting behavior. In particular, the ability of a superconductor to carry a transport current with zero resistance (the maximum value of this current density will be called "J" in the presence of large external magnetic fields (to be referred to as "H") is greatly influenced by the microstructure. In the case of columbium, LeBlanc and Little1 and Autler et a1.2 have observed an increase in J due to cold work. LeBlanc and Little also observed an anisotropy in J in cold-rolled columbium strips, which Hake et al.3-6 have shown to depend upon the angle between H (H ? J) and the rolling plane. An increase in J due to cold work has been found in a variety of high-field superconducting alloys3'4'7-9 as has the anisotropy effect.10 First explanations of why cold work raised J invoked the idea that dislocations carried the high-field supercurrents,8,11 since cold working drastically increases the dislocation density and presumably the number of supercurrent paths. However, recent ideas on the nature of high-field superconductivity together with new experimental evidence reveal that the bulk of certain superconductors can remain superconducting in high fields while carrying high transport currents. These later developments have been discussed by Berlin-court and Hake12 and a comprehensive review has been prepared by Berlincourt.13 According to the ideas of Gorter14 and Anderson,15 one would expect that the influence of microstructure on high-field supercurrent density will depend on tine interaction between microstructure and penetrating flux and on the direction of the Lorentz

Jan 1, 1965

By Charles W. Dickson

CONTENTS. [ ] I.THE RELATION OF NICKEL TO PYRRHOTITE. Introduction. The Sudbury district is to-day one of the two great sources of nickel in the world. The peculiar geological relations of

Jan 1, 1913

By H. A. Meyerhoff, R. J. Colony

Deposits of iron are widely scattered in the folded Cretaceous rocks and the associated igneous intrusives of Puerto Rico. Most of them are too small for commercial development, but a few have aroused some scientific and economic interest, among them the large body of residual limonite at the west end of the island near Mayagüezl-6 (Fig. 1) and the mixed hematite and magnetite deposit on the southern slopes of the Sierra de Cayey, about four miles north of Arroyo.7"9 Neither of these orebodies has been developed, nor have investigations of the widely distributed deposits of magnetite, which include all the remaining occurrences of iron deserving of economic consideration, proceeded beyond the exploratory stage. With the possible exception of the mixed deposit near Arroyo, the magnetite is directly associated with andesitic and dioritic intrusives, which invade the Cretaceous rock section, and the bulk of it, occurring in calcareous sediments, is clearly of contact-replacement origin. The small deposit on Rio Portugües, north of Ponce, is found in a limestone band near its contact with an andesite dike.10,11 Two deposits of unde-

Jan 1, 1935

By H. A. Meyerhoff, R. J. Colony

Deposits of iron are widely scattered in the folded Cretaceous rocks and the associated igneous intrusives of Puerto Rico. Most of them are too small for commercial development, but a few have aroused some scientific and economic interest, among them the large body of residual limonite at the west end of the island near Mayagüezl-6 (Fig. 1) and the mixed hematite and magnetite deposit on the southern slopes of the Sierra de Cayey, about four miles north of Arroyo.7"9 Neither of these orebodies has been developed, nor have investigations of the widely distributed deposits of magnetite, which include all the remaining occurrences of iron deserving of economic consideration, proceeded beyond the exploratory stage. With the possible exception of the mixed deposit near Arroyo, the magnetite is directly associated with andesitic and dioritic intrusives, which invade the Cretaceous rock section, and the bulk of it, occurring in calcareous sediments, is clearly of contact-replacement origin. The small deposit on Rio Portugües, north of Ponce, is found in a limestone band near its contact with an andesite dike.10,11 Two deposits of unde-

Jan 1, 1935

By D. Webster

It has been found that cold work and annealing treatments greatly retard subsequent grain growth and re-crystallization in thoria-dispersed nickel and NiCr. It is suggested that this is due to cavities which form at the particle-matrix interface durilzg cold work. Some of' the cavities formed are stable at elevated temperatures and prevent the mouement of large-angle grain boundaries. The movement of these boundaries at elevated temperatures is known to start recrystal-lization and when they are pinned by voids recrystal-lization is made more difficult. TD Nichro,me had a maximun resistance to recrystallization when the initial structure was coarse-grained and had a low dislocation density. A precipitation reaction occurred between 700° and 1200° F in cold-worked TD Nichrome. It has been shown by Grant and his coworkers1-3 that a large part of the strength of dispersion-hardened materials is a result of the cold-worked structure produced during fabrication. In a comparison of the strength of cold-worked copper with and without an oxide dispersion, Grant4 has demonstrated that there is little difference in strength at room temperature. The function of the dispersion is essentially to maintain the cold-worked structure at higher temperatures than is possible in the base material. The dispersion accomplishes this by making recrystallization more difficult. The mechanism by which this is achieved is discussed in this paper. The fabrication history of the material has been found to greatly influence recrystallization behavior and this aspect is discussed in some detail. I) MATERIAL Three different thoria-dispersed materials were examined. 1) DuPont 2 pet thoria-dispersed nickel (TDNi) in 0.050-in. seeet. Thoria particle size is in the range 100 to 2500A. 2) DuPont 2 pct thoria-dispersed nichrome (20 pet Cr, 80 pct Ni) (TDNiC) in 0.125-, 0.060-, and 0.040-in. sheet. In the as-received condition these sheets have

Jan 1, 1969

T. L. Joseph (University of Minnesota, Minneapolis, Minn.)—Mr. Killian is to be commended for his inquiry as to why a decrease of 15.3 pct in coke consumption was accompanied by a decrease of only 1.9 pct in the CO/CO, ratio of the top gas. Although I encouraged him in his efforts to find a more significant and meaningful carbon-gas ratio, the method, calculations, and conclusions originated entirely with the author. Whether we agree entirely with the assumptions underlying his corrected ratio, I think we can all agree that a better ratio is needed, and that he deserves credit for recognizing the need and for doing something about it. To be most useful, the CO/CO, ratio for the top gas should reflect the way in which the carbon is gasified in the furnace, particularly the degree of oxidation and the extent of heat release. The effect of CO, from the decomposition of the limestone and the effect of the reaction of CO and water vapor in the upper part of the furnace on the quality of top gas should be isolated from the effect of more basic reactions such as ore reduction and solution loss. The reduction of sufficient iron oxide to produce a ton of pig iron and the accompanying changes in the proportions of the carbon gases can be expressed on a mol basis as follows: 16.5FeA + 16.5CO - 33FeO + 16.5CO, [1] 33FeO + 33.0CO = 33Fe + 33CO. [2] The CO, from eq 1 normally escapes from the furnace because it does not react with coke at the temperature of its release. However, as much as 50 pct of the CO, from eq 2 may react with coke because it is released at temperatures above 1000°C: 16.5CO. + 16.5CO2 = 33CO [3] Thus we see that the gasification of 16.5 mols or about 200 lb of C in solution loss will regenerate as much CO as is required for the last stage of reduction. The pronounced effect of reaction 3 on the final proportions of CO and CO, in the gas stream is obvious. It also follows that reaction 3 materially alters the heat release but it cannot be entirely eliminated in Lake ore practice. A previous study indicates that 100 lb of solution loss may be necessary to maintain the reducing power of the gas. A reduction of 100 lb from the normal level of 200 lb would mean that over 1,-000,000 additional Btu are released in the process. The 100 lb of additional carbon which will be burned at the tuyeres will release 437,000 Btu and the absorption of 583,000 Btu by eq 3 would be prevented. One of the chief objectives of sized ore burdens and more uniform distribution of the gas stream is to minimize solution loss by completing reduction higher in the furnace and in turn to release the maximum amount of heat from the carbon charged. It was odd, indeed, to find that the use of sized ore and sinter in the careful tests reported by Dobscha had changed the CO/CO2 ratio very little. The author has stressed the close correlation between his corrected CO/CO, ratio and production. A correlation of fuel consumption and the CO/CO, might be more logical. Fuel consumption on the prepared ore burden decreased 15.3 pct whereas the corrected CO/CO2 ratio decreased 19.0 pct. Although this agreement between the reduction in fuel and the reduction in corrected CO/CO2 ratio is not as close as the correlation with tonnage, it indicates the corrected ratio is superior to the normal ratio which decreased less than 4 pct. Some adjustment should be made for the reaction: CO + H2O = CO2 + H2 —700Btu [41 because there is evidence to indicate that about one half of the hydrogen is formed in the upper 21 ft of

Jan 1, 1953

By G. E. Agar, P. L. De Bruyn

Flotation is an important example of a chemical process by which one solid may be separated from other solids in a mixture. In contrast to other chemical processes such as leaching and smelting, separation of solids by flotation is characterized by the establishment of contact among three phases. In froth flotation these three phases are the solid to be floated, an aqueous electrolyte solution, and a gas, usually air. The gaseous phase may be re- placed by an organic liquid phase or this organic liquid phase may be added deliberately as a fourth phase. To gain an understanding of the flotation sys- tem, it is therefore necessary to study the chemical and physical properties of surfaces and to establish the effect of changes in composition of the bulk phases on the nature of the three interfaces, solid-gas, solid-liquid and liquid- gas. With very few exceptions inorganic solids are completely wetted by the aqueous phase so that the first step in flotation is to replace partially the solid-liquid interface by a solid-gas interface. This displacement process is accomplished by the addition of suitable reagents to the aqueous phase. The resultant surface reaction leaves the solid surface with a hydrophobic film. Although the primary objective of these reagent additions is to alter the solid surface, chemical reactions between the added chemical species and those species derived from the dissolution of the solids are unavoidable. For a quantitative description of such reactions and for the determination of the feasibility of a proposed reaction, we rely on available thermodynamic data. The application of thermodynamic principles to flotation systems has contributed much to our understanding of flotation. The changes in thermodynamic properties such as free energy and chemical potential are accessible to experimental determination, and a knowledge of their magnitude allows us to develop and predict a chemical mechanism oy which a solid becomes floatable. In this chapter it will be assumed that the reader has a working knowledge of the general principles of thermodynamics and solution chemistry. A complete discussion of the physical chemistry of flotation must include a treatment of solubility relations, complex ionic equilibria, reaction potential, and the elements of electrochemistry, especially those dealing with reversible electrical cells. The principles related to all of these features of the flotation system will not be discussed in this chapter. The discussion will be concerned with the thermodynamics and electrochemistry of surfaces and the electrical double layer model of the interface.

Jan 1, 1962

By C. N. J. Wagner, E. N. Aqua

The bee alloys of the terminal solid solution of rhenium in niobium were investigated by X-ray diffraclion methods. The analysis of the broadening of the powder pattern peaks from the niobium-rich alloys, cold-worked by filing, showed evidence for faulting on (211) planes. The alloys with larger rhenium concentrations were brittle, and fractured when filed. The analysis of the shapes of the diffraction profiles from powders produced by hammering with steel plates) of these brittle alloys indicated that the broadening was due predominantly to platelets bounded by clibe planes. This result was consistent with the Laue patterns from single-cleazlage facets which showed evidence for clearage fracture on {100} planes. The influence of faulting on the mechanical properties of face-centered cubic (fcc) metals and alloys, i.e., how faulting affects the various dislocation configurations in fcc metals, is well-known.' The important question is whether or not faulting occurs in body-centered cubic (bcc) metals and alloys, and, furthermore, if faulting does occur, to what extent it affects the mechanical properties. Theoretical calculations indicate that the stacking-fault energy is rather high in most bcc metals.2 The results of sev-eral studies using transmission electron microscopy have indicated that faults are present in well-annealed and lightly deformed bcc metals and alloys, such as tungsten,3 vanadium,4 and Mo-Re alloys.5,6 These faults, as have been observed, may be stabilized by the presence of interstitial (C,N,O) atom segregation to the extended dislocations. In addition, there is considerable X-ray diffraction evidence for faulting in bee metals,7-8 using the same techniques that were successful for the study of faulting in fee metals and alloys.7 This X-ray diffraction method is currently the only technique applicable for the investigation of faulting in metals with high stacking fault energies, i.e., when severe amounts of deformation are required to produce sufficient amounts of faulting to be detectable by X-rays. The thinned films of heavily deformed metals will become opaque in the electron microscope due to the high dislocation densities present. In a previous investigation of faulting8 in bee metals of group Vb and VIb, the authors observed that niobium was ductile when filed at room temperature, and showed the highest density of faults on the (112) family of planes. A niobium-base alloy system was therefore chosen to study the effect of alloying on the occurrence of faults in a bcc alloy. There is a large range of terminal solid solubility of rhenium in the alloys of the bee refractory metals. All of the Group VIb-rhenium alloys, i.e., Cr-Re, Mo-Re, and W-Re, exhibit solid solution hardening without loss of ductility.9 In fact, the ductility reaches a maximum for alloys with compositions near to the limits of solubility. This enhanced ductility has been attributed to the lowering of the stacking-fault energy in the alloy; i.e., the increased amounts of twinning provide an additional mode of deformation, resulting in the observed high ductility.' Because of this demonstrated effect of rhenium in bee alloys, it was decided to study a series of alloys of Nb-Re. Using the same X-ray diffraction methods as described in the previous investigation,' one is able to identify the possible causes of broadening of the powder pattern peaks, e.q., particle size, microstrains, stacking faults, and/or twin faults. The separation of these various contributions to the measured peak shape is accomplished by the Warren-Averbach analysis.7 I) EXPERIMENTAL PROCEDURE A series of seven bee solid solution alloys containing from 2.5 to 21.5 at. pct Re (remainder niobium) were prepared at the General Electric Research Laboratory. Buttons, weighing 25 g, were alloyed from electron-beam-melted niobium chips and random rhenium sheet by arc melting in a water-cooled copper crucible, under an argon atmosphere. The buttons were inverted and completely remelted to promote homogenization. The nominal alloy compositions are listed in Table I. Samples of the cold-worked alloys were obtained by filing to produce a powder for the X-ray study. Alloys too brittle to be filed were hammered with steel plates. The resultant filings or brittle impactings were screened through 150-mesh classifiers and compacted to the required shape for the diffractometer holder. The X-ray diffraction peaks were automatically recorded by fixed time counting at uniform 28 intervals, or by continuous registration with a ratemeter. In all cases, the (110)-(220) and (200)-(400) pairs of peaks and the (211), (310), (222), and (321) reflections were measured on a GE-XRD5 diffractometer using CuKa radiation with nickel filter or MoKct radiation and a LiF monochromator in the diffracted beam. The first part of the data reduction, completed with the aid of a series of programmed computations,10 was the analytical resolution of the Kol component of the diffraction profile. Subsequent computations were then made with reference only to the resolved Kol peak shape. These included the measurement of the

Jan 1, 1967