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By V. Koump, T. F. Perzak, R. G. Olsson

The vate of dissolutioz of carbon in molten Fe-C alloys urns studied by votating- cylindrical g-vaphite sairlples in a stationary crucible containing the melt. The rate of dissolltion was determdined from the change in the bnth co)npositiorz. Alccss-tvansfev coeffi'cients, calcilated with the assurlption that the inte)yacial liquid ulas saturated with carbon, were found to be in agreement with an existing Correlation fov mass transfer jroni votating cylinders. It is corzcllrded tlat, itz the wnge of- Reynolds' numbers itzvestigated (790 to 18,000), the vate of dissolutio of carborz in Fe-C alloys is controlled by tile rate of carbon difirsion from the interface. The dissolution of carbon in molten Fe-C alloys has been the subject of a number of investigations. Most of these investigations have been inconclusive because of poorly defined experimental variables. Two of the more sophisticated studies are summarized below. Dahlke and Knacke' studied the phenomenon by, in part, immersing graphite rods into 0.5 pct carbon-steel for different lengths of time. Since the experiments were conducted in air or in CO atmospheres, the melt was strongly agitated by gas evolution. It was concluded that the change in bath composition as a function of immersion time was in agreement with the assumption that the dissolution process was transport-controlled. The hydrodynamic conditions in these experiments, however, were not well-defined and gave no indication of the nature of the dissolution process at higher fluid velocities. In a recent study Shurygin and ruk investigated the dissolution of carbon in molten Fe-C, Fe-Si, Fe-P, and Fe-Ni alloys. Small graphite disks were rotated in a crucible containing molten alloys under such conditions that only the lower face of the disk was exposed to the melt. The results of this investigation indicate that, over the range of velocities (100 to 1000 rpm) and bulk liquid concentrations (0.7 to 4.5 wt pct C) considered, the dissolution of carbon in the iron alloys is limited by the diffusion of carbon from the interface to the bulk liquid (a transport mechanism). For the particular geometry used by these authors, exact analytical solutions of hydrodynamic and diffusion problems are aailable. Hence the experimental results obtained by Shurygin and Kryuk permit the evaluation of diffusion coefficients of carbon in the four systems investigated. In the present investigation a series of experiments were conducted in which the rate of dissolution of carbon in Fe-C alloys was measured under conditions which permitted wide variation of the fluid velocity and the carbon concentration of the bulk liquid. Graphite cylinders were rotated at different speeds in a stationary concentric crucible containing various molten Fe-C alloys. THEORETICAL DEVELOPMENT In general, the resistance to mass transfer from a solid interface to a turbulent liquid is assumed to reside in a laminar boundary layer adjacent to the interface. If it is also assumed that the diffusion coefficient is independent of concentration, the steady-state rate of dissolution for the case of arbitrary liquid and solid densities can be obtained from the integration of the equations of continuity. The derivation is similar to that used by Lommel and chalmers4 for the case of pl = ps. The solution, expressed in terms where N = rate of diffusion of the solute from the interface. Exact analytical solutions of the hydrodynamic equation for the boundary layer thickness are available for only a limited number of geometries. Consequently, a mass-transfer coefficient, k, is usually

Jan 1, 1967

Fred. T. Greene, Rossland, B. C. (communication to the Secretary): At the beginning of his gaper, Mr. Herzig refers to an article of mine in the Engineering and Mining Journal of January 27, 1900. I would like to add that the method de-

Jan 1, 1901

By WILLIAM BOWIE

THE development of the isostatic idea during the last century would make an interesting paper in itself. But the various steps in the development have been covered in a number of papers and books which are readily available. Therefore this short paper should not give space to. the historical phases of the subject. Isostasy is really an old idea, but it is only in the last few decades that it has taken on any great prominence or importance in the study of earth phenomena. It is really remarkable how closely Dutton' sensed the isostatic principle 40 years or more ago. His general principles of isostasy as outlined by him have stood the test of time and fit in closely with the general ideas held today. It would seem, however, that some of his views with regard to the application of isostasy to geological processes must be modified or abandoned.

Jan 1, 1930

By F. E. Rizzo, L. R. Bidwell, D. F. Frank

THE poor high-temperature oxidation resistance of the refractory metals becomes an important problem as higher operating temperatures are sought. A meaningful analysis of their oxidation behavior requires a knowledge of the phases that can appear during oxidation as well as their relative stability. Although several extensive investigations have been carried out to obtain this information for the W-0 system,1-10 serious inconsistencies still remain. First, the standard free energies of formation (AG°) determined in recent studies which used the solid electrolyte galvanic cell technique6,7,9 differ significantly from those obtained primarily from gas equilibration measurements.1,3,4,10 The disagreement is especially large for the highest oxides. These data have been used to predict the decomposition temperatures of WO2. 72 and WO2.90.1 A considerable extrapolation is required, resulting in a large uncertainty in the decomposition temperatures. Second, Bousquet and perachon3 have presented convincing evidence, ob- tained by gas equilibration measurements, in support of the long-contested existence of W30. Phillips and chang,ll on the other hand, were not able to observe this phase under similar experimental conditions. The purposes of this work, which is part of a continuing investigation of the W-Mo system, were to resolve the discrepancies between the AGO measured by gas equilibration and solid electrolyte galvanic cell techniques, to extend the latter measurements to lower temperatures, to redetermine the WO2.72 and WO2.90 decomposition temperatures, and to apply the more sensitive electromotive-force method to the question of the existence of W3O. I) EXPERIMENTAL PROCEDURE The measurement of ?G° of reaction by the use of calcia-stabilized zirconia solid electrolyte galvanic cells has been described previously.12 The method is based on the measurement of the difference in chemical potential of oxygen between an electrode containing the two oxides of interest and a reference electrode of known oxygen activity. Two different types of cell holders were used in this study. The first type of apparatus has been described earlier." It consisted of two solid electrodes separated by a disc of electrolyte. Both electrodes were exposed to the same stream of purified helium. With this design a gaseous transport of oxygen between the two electrodes is possible. The second type of apparatus, which has also been described earlier,14 effectively separated the two electrode atmospheres. It utilized a closed-end impervious, calcia-stabilized zirconia tube that was open to the atmosphere. The tube served as an electrolyte for the cell and provided a means for separating the anode compartment, which was held under a static vacuum, from an air reference cathode. The cells and reactions of interest are described in Table I. High-purity tungsten metal was obtained from the Fansteel Metallurgical Corp. and the Allied Chemical Corp. Table II contains an analysis of each material. WO3 was prepared by oxidizing the metal in air at approximately 600°C in high-purity recrystallized alumina boats and by the dehydration of reagent-grade tungstic acid in alundum boats. The two methods of preparing WO3 resulted in slightly different purities.

Jan 1, 1968

By W. J. Reagan

A SURVEY of the literature on bottom-cast practice gives but scant information as to some of the real facts concerning this most interesting method of steel manufacture, and some of the information available is very misleading.1 An exceptionally good description of this method of pouring or teeming is to be found in an English publication2 on the heterogeneity of steel ingots. Quoting from this paper: (a) With bottom teeming, the metal rises steadily and progressively in the mold with the minimum possible agitation, the main force of the stream coming from the ladle being broken down or retarded by the down gate or runner. Further, the stream of metal from the ladle, under these conditions of casting, is invariably main-tained at a much more continuous rate and is steadier than with top teeming. (b) In view of the facts referred to in (a) it follows that with bottom teeming the metal is not exposed to atmospheric oxidation to anything like the same degree as with top teeming. In this paper it is intended to detail briefly some of the advantages of bottom-cast practice and to discuss the possibilities of iron-oxide control in the basic open-hearth furnace. A description of the type of charge, ingot mold set-up, etc., is found in detail in an earlier paper.3

Jan 1, 1934

By R. M. Board

This paper will focus on measurement and control of four main aspects of crushing, namely horsepower, bowl level, mantle position and feed rate, and will discuss related sensors and control techniques, some of them designed specifically for crusher control, that have proven successful and reliable in many installations.

Jan 1, 1982

By Emerson F. Heald

A systematic study was made of new and old data on chemical activities in Fe-Pt alloys at elevated ternperatuves. Experimental results may be expressed in terms of the excess free energy using Least-squares analysis of the data gave the following values for the constants: for the temperature range 1130° to 1350°C, and tentatively to 155O°C, B = -3.326564 and C = 0.221051; for the temperature range 650" to 850°C, B = -2.555690, C = 1.762735, and D =0.097196. In the study of iron-containing silicate systems, it is sometimes desirable to have a direct experimental measure of the activity of iron in the system. The well-known solubility of iron in platinum, often a headache in experimental work on iron compounds under reducing conditions, can be used to advantage in this respect. If the activity of iron in an Fe-Pt alloy in equilibrium with the silicate is known as a function of the composition of the alloy, chemical analysis of the alloy will give a knowledge of the activity of iron in all of the phases in the system. The present study was undertaken in order to elucidate the characteristics of Fe-Pt alloys as iron activity indicators. This work is intended to tie together some previous work, which may be summarized as follows. Larson and Chipman1 determined the activity of iron in Fe-Pt alloys at 1550°C by equilibrating platinum metal with calcium oxide-iron oxide-silica melts of known iron activity. Compositions of the resulting alloys were determined by chemical analysis. A similar study was carried out by Taylor and ~uan,' who worked at 1300°C. They brought the Fe-Pt alloys into equilibrium with iron oxide under conditions of known partial pressure of oxygen, and thus, from the work of Darken and ~urr~,~ conditions of known iron activity. Compositions were determined indirectly, by following the change in weight of the sample. Sundaresen et el* used the electromotive force of cells in which the alloy formed one electrode in order to measure the activity of iron in the alloy at 650" and 850°C. These temperatures were chosen to be above and below the first-order phase transition which takes place upon the ordering of Fe3Pt and the second-order transition which occurs upon the ordering of FePt3. EXPERIMENTAL 1) High Temperatures. The starting materials used were thin platinum foil, about 0.002 mm thick, and Fisher Certified reagent ferric oxide, Fez03, which had been heated for 24 hr at 1000°C. An intimate mixture of 80-mesh Fez03 and platinum platelets was placed in a thin platinum foil envelope. The latter was suspended from thin platinum wires in the hot zone of a vertical-tube, platinum-wound furnace of the type described by Muan and ~sborn.~ A capillary gas mixer similar to that used by Darken and Gurry3 was used to prepare a precisely known mixture of carbon dioxide and hydrogen, which was allowed to flow upward through the furnace tube. The partial pressure of oxygen in contact with the sample was thereby fixed at a value which was calculated from the charts prepared by porter? Temperatures were measured with a Pt-10 pct Rh-in-platinum thermocouple, which was calibrated using the melting points of gold (1062 .@C) and diopside, CaMgSizOB (1391.5"C). Temperature control was maintained to within i3"C with a Geophysical Laboratory proportional controller, using the furnace resistance as the sensing element. Samples were quenched by passing a small current through the platinum suspension wires, allowing the sample to drop into a bath of dibutyl phthalate at the bottom of the furnace tube. Prior to chemical analysis the samples were washed with acetone and dried. 2) Chemical Analysis. It proved possible, in almost all cases, to separate the Pt-Fe platelets physically from particles of iron oxide. The platelets were dissolved in a small volume of aqua regia, evaporated to dryness, and redissolved to 0.1 M HC1. In order to determine iron in the platinum alloy potentiometrically, it is necessary first to remove the platinum. A 10-cm column of Amberlite IR-120 cation exchange resin in the hydrogen form provided separation quickly and quantitatively: The mixture of iron and platinum in 0.1 M HC1 was added to the top of the column, and washed with about 100 ml of 0.1 M HC1. Under these conditions, the iron, principally in the form of cations such as FeC1" and FeCl;, is held quantitatively in the uppermost centimeter of the column. The platinum, in the form of anions such as PtC&- , is washed through without being adsorbed. After a qualitative test with stannous chloride indicated all of the platinum was removed, the iron was

Jan 1, 1968

By John L. Ham, Robert M. Parke

The melting point of molybdenum is 2625° + 50°C. Heretofore the metal has been considered too refractory to be melted in commercial quantities; hence, it has been formed into rod, wire, and sheet by the methods of powder metallurgy, wherein the temperatures do not exceed 90 per cent of the melting temperature. The manipulation of liquid metals at temperatures of about 2000°C. and above presents some difficult problems in heat transfer, in purification, and in container materials. For metals melting at such high temperatures, it is generally regarded as expedient to circumvent the more common melting and casting process by resorting to powder metallurgy. This circumvention is not accomplished without some penalties, the more notable of which are the relatively high cost of the powder metallurgy method and particularly the size limitations of its product. In an effort to overcome the inherent disadvantages of the powder metallurgy method, especially in respect to the limit of size, a project was begun in 1943 at the Climax Molybdenum Co. laboratory to develop a method of melting and casting molybdenum capable of producing larger bodies of molybdenum than were then obtainable. Later, from Feb. I, 1944, to Aug. 31, 1945, the project was under the supervision of the National Research Committee, Division One. In peacetime, too, there are needs for molybdenurn, which make consideration of another process desirable; for example, large parts for heat engines generally, the omnipresent demand for metal of higher quality and lower cost, and the development of molybdenum-base alloys. This paper describes methods for melting and casting molybdenum, with details of the special process needed to make molybdenum castings ductile, and reports some of the properties of what may be regarded as a new, or at least modified, form of the metal. First Process for Melting and Casting Molybdenum The maintenance of a temperature greater than 2625°C. in a 'pace large enough to melt several pounds of molybdenum may involve the loss of heat at a Very considerable rate. For melting molybdenum, therefore, the source of heat must be of high potential and of fairly high power. Evidently, also, the source of heat must not impair the purity of the product. The electric arc operating in vacuum appeared to meet these requirements and was accordingly the first choice as a source of energy. A number of arc devices for melting molybdenum were examined, and several were tried. In the first experiment, a 20-kw., 60-cycle-per-second alternating-current arc was operated between two horizontal and opposed electrodes of molybdenum- In this arrangement the falling droplets of molybdenum solidified below the arc in an irregular mass. This experiment did not produce a useful casting, but the data obtained indicated that

Jan 1, 1947

By John L. Ham, Robert M. Parke

The melting point of molybdenum is 2625° + 50°C. Heretofore the metal has been considered too refractory to be melted in commercial quantities; hence, it has been formed into rod, wire, and sheet by the methods of powder metallurgy, wherein the temperatures do not exceed 90 per cent of the melting temperature. The manipulation of liquid metals at temperatures of about 2000°C. and above presents some difficult problems in heat transfer, in purification, and in container materials. For metals melting at such high temperatures, it is generally regarded as expedient to circumvent the more common melting and casting process by resorting to powder metallurgy. This circumvention is not accomplished without some penalties, the more notable of which are the relatively high cost of the powder metallurgy method and particularly the size limitations of its product. In an effort to overcome the inherent disadvantages of the powder metallurgy method, especially in respect to the limit of size, a project was begun in 1943 at the Climax Molybdenum Co. laboratory to develop a method of melting and casting molybdenum capable of producing larger bodies of molybdenum than were then obtainable. Later, from Feb. I, 1944, to Aug. 31, 1945, the project was under the supervision of the National Research Committee, Division One. In peacetime, too, there are needs for molybdenurn, which make consideration of another process desirable; for example, large parts for heat engines generally, the omnipresent demand for metal of higher quality and lower cost, and the development of molybdenum-base alloys. This paper describes methods for melting and casting molybdenum, with details of the special process needed to make molybdenum castings ductile, and reports some of the properties of what may be regarded as a new, or at least modified, form of the metal. First Process for Melting and Casting Molybdenum The maintenance of a temperature greater than 2625°C. in a 'pace large enough to melt several pounds of molybdenum may involve the loss of heat at a Very considerable rate. For melting molybdenum, therefore, the source of heat must be of high potential and of fairly high power. Evidently, also, the source of heat must not impair the purity of the product. The electric arc operating in vacuum appeared to meet these requirements and was accordingly the first choice as a source of energy. A number of arc devices for melting molybdenum were examined, and several were tried. In the first experiment, a 20-kw., 60-cycle-per-second alternating-current arc was operated between two horizontal and opposed electrodes of molybdenum- In this arrangement the falling droplets of molybdenum solidified below the arc in an irregular mass. This experiment did not produce a useful casting, but the data obtained indicated that

Jan 1, 1947

By Ray Arms

This paper includes a brief classification of dry-cleaning devices, with a theoretical discussion of the principles involved. It outlines the methods of handling dust and screening difficulties at the McComas plant, as well as other plants that are being constructed and other dry-cleaning devices being developed. It describes the American Pneumatic Separator and discusses the sizing required, the effect of moisture in the raw coal, disposition of the middlings, and other aspects of the process. It gives s results of tests on various coals, and results of operation at Raton and McComas. DRY CLEANING, or pneumatic separation, is not, strictly speaking, a recent discovery. Among the archives of the Patent Office may be found many patents dating back as far as 1850 which cover early attempts to separate materials of varying specific gravity or of different shape by means of air. Hundreds of patents covering this art have been issued, which may be roughly classified into four general groups, as follows: 1. Stationary devices with pulsating air currents. The separating surface is usually riffled and air is supplied by bellows or compressors. This group' also includes air jigs, which have been used rather extensively. 2. Stationary devices with continuous air currents. These submitted the material to a continuous current of air, either horizontal or vertical. Chaff is blown from wheat by such a device. 3. Reciprocating or vibrating devices with pulsating air. A small group in which the pulsating air is supplied by bellows and some motion provided in the separating surface to move the stratified material to various discharge points. 4. Reciprocating or vibrating devices with continuous air supply. This is by far the most important group and all recent developments have been along this line. All of the above groups involve the stratification of material by air and include none of the dry methods that use other principles, such as coefficient of friction, magnetism, etc.

Jan 3, 1924

By C. W. Hall

Owin to its isolation and comparatively small tonnage, the Yoquivo district is not widely known; though financially important andgeologically, quite interesting. San Francisco de Yoquivo, the center of the mining district, is in the western part of the state of Chihuahua, Mexico; about 35 miles west of San Juanito, on the Kansas City, Mexico & Orient R. R. The town can be reached from the railroad by a good trail over a rugged country. The elevation of Yoquivo is 6500 ft., and peaks surrounding the town are 2000 ft. higher. The mining towns of Concheño and Ocampo are 25 miles northwest, and Uruachic is 20 miles southwest. The climate, temperate and healthful, is almost ideal. The rainy season begins in July and ends the latter part of September. There is usually, though not always, some precipitation in all months except April, May, and June. The mountains are covered with pine and scrub oak. Water, wood and lumber are plentiful for all ordinary purposes, and hydroelectric power is available for about six months of the year, when wood for steam power is utilized as an expedient. The district has been worked recurrently for over 60 years. The Yoquivo province lies on the steep western slope of the Tara-humara division of the Sierra Madre range of mountains. The province is traversed by many deep canyons, most of which flow west. The town is situated on the San Francisco arroyo, which makes a confluence with the Huevachic stream 236 m. southwest; the Huevachic in turn joins the Candemeña river farther down and these two drain the western flank of the Tarahumara mountains and form the headwaters of the Mayo river. The claims of the Yocluivo Development Co., which is the only organization in the district with a record of any considerable production, lie within an area roughly l½ m. square. Thc area extends from the San Francisco arroyo north, and from the Dolores arroyo west, and is confined to the andesite formation. General Geology The terrane about Yoquivo is composed of a series of Tertiary eruptives that consist of numerous phases of andesite and rhyolite, and

Jan 1, 1927

By Frank C. Canney

The word "other" in paragraph 4, line 11, column 1, page 205, should read "over;" the correct version of reason 2, this paragraph, is: 'L. . . 2) to evaluate the usefulness of certain geo-chemical techniques, V. C. Kennedy and S. W. Hobbs of the USGS had already studied the distribution of copper, lead, and zinc in the soils (both in background areas and over veins) and in the water and plants, providing a criterion for measuring the magnitude and effect of soil contamination; ...9 On page 206, in the top left hand corner of Fig. 1 (in the area bounded by 47°35' and 116°10), the reference to Fig. 3 is incorrect. The area of Pine Creek, South Fork Coeur d'Alene River, and portion of Big Creek (the area which includes, from left to right, Kingston, Pinehurst, Smelterville, and Kellogg) should be identified as that of Fig. 2A. The headings for columns 1, 3, and 4, Tables I and 11, page 209, column 2, were reversed when the paper was printed. The corrected tables are:

Jan 1, 1961

By Albert Sauveur

As director of the Division of Metallurgy of the Technical Section of the Air Service, American Expeditionary Forces, from August, 1917, to January, 1919, I devoted much time to the study of the steels best suited to the construction of aircraft. It became apparent at a very early stage of my investigation that the practice of builders varied greatly in regard to the number of different steels to be used, to the kinds of steels, and to their treatment. Some manufacturers employed as many as fifteen steels while the builder of one of the newest motors, favorably passed upon in the United States, assured me that two or, at the most, three kinds of steel were all he needed to produce satisfactory results. In the matter of treatment, the manufacturers were also greatly at variance. Some treated their steel with considerable refinement while others paid but scant attention to this feature. Some manufacturers case-hardened many parts, while others used the case-hardening process sparingly, if at all. Nickel-chromium steels were used at some works for case-hardening while at other plants this treatment was applied exclusively to carbon steels. Air-hardening nickel-chromium steel was used extensively by some and not at all by others. Considerable variance existed likewise in regard to the steels used for admission and exhaust valves. The conclusion was obvious, that no two manufacturers of airplane motors held like opinions as to the steels to be used or as to the treatment they should receive. Was it to be inferred from this that the many committees and associations that had been created, in part at least, for the standardization of aircraft steels had failed to make proper recommendations or that the manufacturers had ignored their recommendations ? Confining our inquiry to the committees and associations that had dealt with this question in England, France, and the United States, it was found that in Great Britain the British Engineering Standards Committee, now the British Engineering Standards Association, had devoted much time to the problem of satisfactory standards for aircraft steels. In April, 1918, this Association presented a set of specifications described as "British Standard Specifications for Aircraft Steels for Government Purchases in the United States of America." They included twenty-one different steels and, as the title indicates, were drawn for the

Jan 1, 1920

By Fred W. Gordon

The North Chicago Rolling-Mill Co., of Chicago, have four furnaces at South Chicago, built during 1881. Each furnace is 20 feet diameter of bosh, and 75 feet total height, the hearth being 11 feet diameter, and the top 15 feet 4 inches. They are blown through seven 7-inch tuyeres placed 5 feet 6 inches above the hearth level. Cubical contents, 15,000 cubic feet. Each furnace is supplied with 2 blowing engines, 84-inch blowing cylinder, and 36-inch steam cylinder, and 54-inch stroke. These two have one jet-condenser worked by an auxiliary pump. The blast for each furnace is heated by the aid of three Whitwell fire-brick stoves, each 21 feet diameter and 60 feet high. In the batteries of boilers furnishing steam for four furnaces there are 36 double-length boilers, 76 feet long, 48 inches diameter and 16,000 square feet heating-surface. The plant was designed to produce 3600 tons per week, or 900 tons for each furnace, and was fitted as above with such engines, boilers, and hot-blast stoves as were thought requisite for that production ; hence, calculated from the present make—not the least remarkable feature is the economy of construction—there are less engines, less boilers, and less hot-blast power for the iron made than at ally plant within my knowledge, or it could to-day be duplicated for less money per ton of iron made per week than could any plant now in existence, whether using fire-brick or cast-iron stoves for heating the blast. This is a practical demonstration of my assertion in a paper on fire-brick stoves, read before the Institute," that the application of fire-brick stoves in construction really lessens the first cost. In view of the statements just made, I must be most emphatic in assuring the members that nothing is strained or overburdened.

Jan 1, 1886

By Jed H. Mosgrove

One of the most interesting of all the subjects required of persons studying the different facets of coal mining is coal mine gases. Some mine gases have been a real problem since the very beginning of underground mining, and in the early days there was insufficient knowledge to cope with them. The history of mining shows that until about the last 50 years, much work was done primarily by the hand methods which are primitive by today's standards. Miners had to contend with gases without the aid of enclosed lighting, permissible mine machinery, sophisticated testing devices, and high-pressure ventilating fans. In early days the miners were not educated about the different mine gases nor did they have the technical equipment to determine the actual composition of the deadly atmospheres they encountered. They simply applied a descriptive term to each gas or mixture of gases depending on its effect on a person or the surrounding atmosphere. The gases or mixtures of gases were then referred to as "damps," a term which was probably derived from the German word "dampf," meaning vapors or gases. The more common damps encountered were : Blackdamp A condition of the atmosphere in which a miner's light would be extinguished and in which breathing would be difficult, sometimes even resulting in suffocation. An atmosphere deficient in oxygen which could contain a combination of any of the mine gases. Firedamp A flammable mixture of methane and air which would either burn or explode when ignited. White Damp A mixture of gases containing carbon monoxide, most often found in mines during fires or after explosions.

Jan 1, 1981

By R. F. Rolsten

VAN Arkel 1 prepared ductile tantalum by the thermal decompoiition of tantalum pentachloride on a resistively heated wire (2000° C) in an evacuated bulb maintained at 100°C. Burgers and Basart2'3 observed the formation of a mixture of tantalum carbide and free metal when a carbon deposition base was used. campbel14 suggested the thermal decomposition of the iodide if a lower decomposition tem- perature was desired. To date, the details for preparing high-purity iodide tantalum have not been disclosed. EXPERIMENTAL The tantalum to be purified was symmetrically placed around the clear quartz deposition surface centrally located within a 64 mm cylindrical Vycor bulb. The deposition vessel usually employed5 was modified6 by incorporating a reentrant fin,mer in place of the customary metal filament in the head

Jan 1, 1960

By A. C. Fraker, H. H. Stadelmaier

In the systems Mo-Fe-C, Mo-Co-C, and Mo-Ni-C the phase boumdaries of the cubic Ij carbides were determined at 1000°C and the variation of the lattice parameter with composition was measured. In the system Mo-Fe-C a single ternary carbide, Mo3Fe3C, was observed. In Mo-Co-C and Mo-Ni-C two new n phases of the type M12C were found: Mo6C06C and Mo6Ni6C. At 1000°C they coexist with the M6C phases MO3-4,CO3-2C and Mo3-4Ni3-2C, respectively. Mo3C03C and Mo4C02C are not separate phases but parts of a single M6C phase region, and the same is true of Mo3Ni3C and Mo4Ni2C. THE n carbide structure type has been known since it was determined by westgren' in 1933, yet reliable information on phase compositions of this type is ap-parently scarce. The following selection of suggested formulas illustrates the extent of the confusion con-cerning compositions: W2-3Fe4-3C,1W6Fe6C,2 W2_4Fe4-2C,3 (W,Fe)6C,4 Tj.-W4Co2C and nz-W6Co6C,5 n1-W3Co3C and n2-w4Co2C,5 W3C03C and w6Co3C2,7 MO3Fe3C,8n2-M04Fe2C,9 (MO,Fe)6C,4 MO3CO3C,8 n2-MO4CO2C.9 Many of these compositions obviously overlap, some disagree in carbon content. The use of the designations 77, and n2 is not consistent. There is uncertainty whether two carbides M6C coexist or whether there is only one M6C with a wide range of substitution of one metal for the other. The existence of M12C seems questionable altogether if one ignores the results of a neutron diffraction study of W6Fe6C supporting that particular metal to carbon ratio.'' More reliable information is available for the iso-typic oxides studied by Nevitt,11 Nevitt, Downey, and orris," and Meussner and carpenter.l3 That n car-bides and oxides are structurally identical, particularly with respect to the location of the metalloid atom, has been demonstrated clearly by Stadelmaier and Meussner14 and also by Parthe, Jeitschko, and sadagopan.15 Therefore the present paper, which attempts to establish the phase boundaries of n defini-tively for three carbon systems, has implications for the whole family of filled Ti2Ni types. EXPERIMENTAL PROCEDURE The samples were prepared in two stages. Pellets weighing 3 g were compacted from powders of the elements and presintered in a closed tube of fused silica that had been evacuated to lO-4 mm Hg. This was fol- lowed by arc melting the sintered samples under argon. Remelting the button once was sufficient to produce homogeneous specimens. The metal powders had the following minimum purities in wt pct: molybdenum 99.5, iron 99.0, cobalt 99.7, nickel 99.9, graphite 99.94. Carbon determinations by the gas volumetric method were obtained from thirty-one of the one hundred samples in the annealed condition. They were limited to compositions that were critical to placing a boundary line in the isothermal sections. The carbon losses were comparatively low and averaged less than 1.5 at. pct. For annealing, the samples were sealed in tubes of fused silica evacuated to 10-4 mm Hg. The annealing schedule was 20 hr at 1250°C followed by 150 hr at 1000" ±10°C. For the water quench the silica glass tubes were broken mechanically to speed the quench. The specimens were examined in the as-cast and annealed condition by standard metallographic techniques. Some of the as-cast and all annealed samples were studied by X-ray diffraction using a 114.6-mm powder camera with filtered Co radiation. The lattice parameters of the n phases were determined by graphic extrapolation to 8 = 90 deg on a plot against sin2 8. It is estimated that the maximum error in the lattice parameters is ±0.002A.. The phase fields were determined by the disappearing phase method, relying on X-rays for phase identification and on microscopy to detect small amounts of a phase. RESULTS Pertinent information on the binary side diagrams has been summarized by Hansen and Anderko16 and Elliott17 and will not be discussed further. Photomicrographs documenting the equilibria at 1000°C have been selected to avoid redundancy due to the similarity of the three systems. Thus there will be only one picture showing an equilibrium with Mo2C, and so forth. Molybdenum-Iron-Carbon. An isothermal section of most of the Mo-Fe-C system at 1000°C is shown in Fig. 1. No attempt has been made to distinguish between a and y iron or to determine their phase boundaries. A conspicuous absence is the phase Fe2 1Mo2C6 with the Cr23C6 structure, supporting the suggestion by Krainer4 that it decomposes by annealing at high temperatures. The only ternary phase is found in a narrow range around Mo3Fe3C (MO43Fe43C14). A microstructure with a two-phase mixture of Mo + n is seen in Fig. 2. The variation of the lattice parameter of n with the estimated composition is shown in in Table IA. The phase diagram does not agree with the results of Kuo9 who reported n2-Mo4Fe2C. Our lattice parameter Varies from 11.095A at the iron-rich end to 11.140Å at the molybdenum-richoend of the phase field whereas Kuo9reported 11.26Å for Mo4Fe2C. We are in agreement with the older work

Jan 1, 1970

By K. I. Savage, S. C. Sun

This paper describes a process developed to recover coal, clays and pyrite from coal wastes. The process consists of fine grinding followed by coal and pyrite flotation which leaves the clays in the flotation pulp. A bituminous coal refuse containing 10% sulfur and 30% carbonaceous material was treated by this method to yield a coal product containing 4% sulfur, 10% ash; a pyrite product containing 45% sulfur (84% FeS2), 1% carbonaceous material; and a clay product containing 2% sulfur (3.5% FeS2). The coal yield was about 89%. The pyrite yield was about 77%. The process steps may be entirely flotation, or gravity separation (hydrocycloning) may be used to increase the pyrite : coal ratio in the flotation feed. Cost estimates for the process show a profit of $2.28 per ton of low pyrite grade refuse, but these do not include labor, maintenance, overhead and plant depreciation. The development of this process consisted of three parts: (1) exploratory tests, (2) op-timazation tests and (3) confirmatory tests. The objectionable qualities that sulfur imparts to coal have been commented upon from early times, and they have become more objectionable as the uses of coal have grown. In whatever form coal takes — raw, carbonized or gasified —the sulfur content remains objectionable, and therefore its compounds are removed as completely as possible. It has long been known that sulfur occurs in coal in different forms. In 1861, sulfur was said to exist in the state of sulfuric acid in combination with a base; in combination with iron as iron pyrites; as bisulfides of iron; and in combination with the organic elements of coal.' Pyritic sulfur is a term loosely used to cover the sulfur associated with iron in its various forms. The mineralogically recognized forms are pyrite (FeS2), pyrrhotite (Fe 1-x S) and marcasite (FeS2). The particle sizes of pyrites vary widely. Isolated grains of marcasite smaller than 15 microns have been found disseminated through coal.2 Hair-like "veins" of pyrite filling cracks in vitrain have been found. At the other extreme, lumps or nodules of pyrites large enough for removal by hand picking have been encountered. Organic sulfur, unlike pyritic sulfur, does not exist as discrete particles, but is instead intimately associated with the coal structure and thus it is impossible to remove it or reduce its concentration by physical or mechanical means.2 In the preparation of coal for its various markets, the pyrite minerals (pyrites) are separated from the raw coal feed. This separation process concentrates the pyrites in the tailings or other waste products. It would be desirable to recover these pyrites for three reasons: (1) Pyrites are potential sources of sulfur and iron. In 1967, for the fifth consecutive year, Free World consumption of sulfur exceeded production.3 Propelled by the shortage, the domestic price of sulfur has risen from $24 to $38 per long ton (bright). (2) The refuse, when placed in piles, becomes ignited. The pyrites (FeS2) bum, giving off SO,. Thus, the pyrites are a cause of air pollution. (3) Also, the pyrites undergo chemical reaction when exposed to air. The refuse is leached by waters which result in stream pollution due to the water-soluble iron and acidic reaction products. Coal refuse also contains coal minerals and clay minerals. Therefore, any process for recovering the pyrites must successfully separate them from the coal and clay minerals. In the study discussed here, ten different bituminous coal refuse samples were successfully upgraded in pyrite content. These samples represented a wide variety of coal waste materials from Pennsylvania and other states. The variabilities of the sulfur and coal contents are shown in Table I. The extremes are Sample J, a high sulfur-low coal, and Sample B, a low sulfur-high coal. Definitions of some of the symbols or terms used in this report are given below: Mesh size—Tyler standard mesh screen sieves with an opening based on the square root of two. Fe —Indicates iron, as determined by a stannous reduction-dichromatic oxidation method. S—Indicates sulfur, as determined by the ASTM "Eschka" method for sulfur in coal.

Jan 1, 1969

By R. A. Wood, R. I. Jaffee, H. R. Ogden, D. N. Williams

Strain-induced porosity has been found to occur in titanium and other materials at tensile strains greater than the uniform elongation of the material. Porosity in titanium increases with increasing strain and temperature, being most severe at 300° to 800°F. Strain-induced porosity is believed to be a normal part of the mechanism of deformation in ductile materials. DURING the past few years there have been numerous references to the occurrence of voids in laboratory test specimens of metals subjected to strain.l-7 These voids have been referred to as intercrystalline cracking, strain-induced porosity, intergranular cav-itation, voids, and porosity. They appear to occur at grain boundaries or interfaces, and are generally associated with large amounts of strain and have been found mostly in creep specimens and to a lesser extent in tensile specimens. Because the phenomenon does not occur unless the material has been strained,

Jan 1, 1960

By J. W. Martin, L. K. Singhal

Grain boundary M23CB precipitates have been shown to form by a process involving the migration of an austenite grain boundary, and each plate of precipitate is in parallel orientation with one of the austenite grains constituting the boundary. The carbide distribution and morphology appear to be sensitive to grain boundary mis orientation. Some areas of austenite grain bowzdary permit the development of an array of M,C, particles, some of which are in parallel orientation with one grain and some with the other grain constituting the boundary. Massive carbide at grain boundary triple points is also shown to be in parallel orientation with one constituent grain. PREFERENTIAL precipitation during aging of carbides of the type (Fe,Cr)23C6, usually written MZ3C6, in grain boundaries of quenched austenitic stainless steels has been widely recognized. M23C6 has a complex cubic crystal structure' which contains ninety-two metal atoms and twenty-four carbon atoms per unit cell. Less energy is involved in forming grain boundary precipitates than in the formation of intragranular precipitates, and the process is further enhanced by the accelerated diffusion rates in the boundaries and by the probability of segregation of chromium atoms and carbon atoms to the region of the grain boundaries during prior solution heat treatment in order to reduce lattice strain. Early electron micrographic studies2, 3 involving either extraction replica or normal replica techniques established the geometric or dendritic form of the carbide particles, although this approach led to dis- pute as to whether the particles grew within the plane of the boundary or grew into the matrix.4-6 More recent thin-foil studies' have claimed to identify a discontinuous precipitation process involving M23C6 at grain boundaries, and the object of the present work was to attempt to clarify the situation using modern electron micrographic and diffraction techniques. 1) EXPERIMENTAL 1.1) Material. The steel selected for this work had a base composition of 24 pct Ni-25 pct Cr-3 pct Ti and contained about 0.04 pct C. The full analysis if given in Table I. This alloy was in the form of strip which had been hot- and cold-rolled to a thickness of 0.6 mm. 1.2) Heat Treatment. Specimens 4 cm long by 1 cm wide were solution-heat-treated for 3 hr in argon at 1150°C, followed by water-quenching. Specimens were subsequently aged in vacuo at 750°C for periods up to 500 hr. 1.3) Preparation of Electron Microscope Specimens. The heat-treated strips were cut bv spark machining into discs of 3 mm diam and 0.6 mm thickness. he-discs were dished on both sides using an electrolytic jet of 15 pct HCl electrolyte at 80 v. Final electro-polishing of the discs was carried out using 10 pct perchloric acid, 20 pct glycerol, and 70 pct ethanol at 10 v. The current density was kept below 300 ma. cm"2 by cooling the electrolyte to 0" to 5°C. As soon as a small hole appeared, the electropolishing was stopped and the specimen was quickly washed with ethanol.

Jan 1, 1969