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By Lombard Squires, W. K. Lewis, W. I. Thompson

Clays consist predominantly of hydrated silicates of alumina. The formula is frequently assumed to be A1203 . 2Si02 . 2H20,'and certain of I. North Carolina. Low plasticity. 11. Same as I, after washing. Low plasticity. III. Tennessee. Good plasticity. IV. Pennsylvania flint fireclay. Low plasticity. V. Laredo, Texas. Very plastic. CaO/Na2O corrected for GO2. VI. San Antonio, Texas. Fine grained, highly plastic. Moisture and CO2 were determined together at 18.8 per cent. VII. Selected crude bentonite, California. " Data from R. Ries: Clays. John Wiley & Sons, New York, 1927. them undoubtedly have substantially this composition, but in general the ratio of silica to alumina is considerably higher. However, they always contain water of chemical constitution, as shown by Table 1.

Jan 1, 1935

By W. A. Tiller, D. H. Lane

A simple zone melting technique for investigating the effect of ultrasonic irradiation upon ingot solidification is described. The effect of i) ultrasonic power level, ii) freezing velocity, iii) constant or variable frequency, iv) direction of irradiation, and v) transducer-cozlpling bar joint upon the grain size of type 316 stainless steel have been investigated. The results of this study support the postulate that the ultrasonic vibrations increase the nucleation probability in the layer of liquid adjacent to the freezing interface. In the first paper of this series,l the possible mechanisms whereby ingot structure may be altered by irradiating a solidifying melt with ultrasonic vibrations have been discussed. A new technique for efficiently introducing the ultrasonic energy into the solid-liquid interface region was presented and applied to ingot preparation by the consumable-electrode arc-melting technique. The experimental results support the postulate that the ultrasonic vibrations may refine the ingot structure by increasing the nucleation probability in the zone of liquid adjacent to the solid-liquid interface. The present paper describes the application of the same technique to a relatively simple laboratory-scale zone-melting apparatus. This apparatus is found to be well suited to the detailed study of ultrasonic technology in this area and allows one to determine, in particular, the minimum ultrasonic power level needed to produce a certain grain size in a particular material. The results of this study support the nucleation mechanism for grain refinement, but do not provide any deeper insight into the specific nucleation mechanism responsible for the effect. EXPERIMENT The apparatus used in these experiments is shown in Fig. 1 and illustrated schematically in Fig. 2. The material to be studied, type 316 stainless steel, was in the form of a 3/4-in. sq bar 30 in. long. This bar was placed in a square open-topped mold with open ends made from high-purity graphite coated with a flame-sprayed Al2O3, skin. Surrounding the crucible was a molybdenum susceptor with 3/8-in. diam holes spaced at 1-in. intervals along its length to serve as sight ports. A tapered transducer horn was brazed to one end of the specimen. The entire assemblage was enclosed in a quartz tube, the transducer itself projecting out one end and resting in a cooling tank. A vacuum seal between the coupling bar and the end plate enclosed one end. A similar plate and seal enclosed the other end. The system is gas tight and can be operated under vacuum or an inert atmosphere. For these experiments, flowing argon at 15 in. of Hg pressure was used. The heat source for melting the stainless steel specimen was a 2-in. long 3-kc induction coil placed around the quartz tube; this source heated the susceptor, inductively melting about a 3-in. zone of the sample by radiation. To move the molten zone at a specified rate, the induction coil was moved down the tube at this rate with the aid of a simple pulling device. Thus, the sample could be irradiated at varying ultrasonic frequencies and power levels and could be solidified at varying rates. The power input to the transducer was measured using a "John Fluke Model 120 VAW-Meter." 1 The power delivered to the interface region is probably only about 50 pct of that measured on the VAW-meter. In a typical run, when the ultrasonic power was turned on, the interface of the molten zone closest

Jan 1, 1961

By W. J. Rude

LARGEST of the known commercial deposits of pebble phosphate are those found in Polk County, Florida. The phosphate bed, commonly known as the matrix, will consistently average 6 to 9 ft. in depth, and is found under 3 to 60 ft. of over-burden. The phosphate pebbles, white and black in color, varying greatly in grade, are found imbedded in a matrix of sand and clay; and range in size from the fines to pebbles 1 1/2 in. in diameter, although the average coarse size is approximately 1/2 in. in diam¬eter. On some of the washers all material under 14 mesh is lost. High-grade phosphate (75 per cent plus of bone phosphate of lime, CasP2Oa) is generally soft, the pebbles breaking up during the mining operation and in pumping; low-grade phosphate, 67 to 69 B.P.L., is black in color with hard pebbles with no loss encountered in pumping.

Jan 1, 1941

By J. F. Elliott

PRESENT knowledge of the usual metallurgical slags indicates that they are, for the most part, rather complex in behavior and as yet there is no ready means for describing, in a simple manner, the behavior of any one of them. One of the best known slag systems is the iron oxide-silica-lime ternary which is the basic "solvent" in a number of important metallurgical refining operations, the basic open hearth being one of the most important. In this operation, the slag dissolves such components as sulphur, phosphorus, manganese oxide, and magnesia. Considerable study of this slag system and the behavior of these additions has been carried out in the past by a number of authors, as has been summarized in several critical reviews.','2 However, except for determination of the activity of iron oxide, only a limited amount of effort has been directed towards developing, from these data, an understanding of the general behavior of the basic solvent. Reported here are the results from a series of calculations based on data from the literature which permit a semiquantitative evaluation of the activities of iron oxide, silica, and lime (plus magnesia) in the ternary system at 1600°C. The preliminary results, which were reported briefly at a symposium held by AIME in 1953, have been revised and are completed. The steps in the calculation are as follows:* I—establish the activity curves and the curve of the excess molar free energy of mixing at 1600°C for each of the binary systems, 2—construct the activity surface of iron oxide for the ternary from the data on the binary systems and information available in the literature for the ternary area, 3—determine the surface of excess molar free energy of mixing for the ternary system from the activity surface of iron oxide and from the molar curves obtained for the binary system, and 4—differentiate the ternary surface of the molar excess free energy of mixing to obtain the ternary surfaces for the logarithm of the activity coefficients for silica and lime (log rslo, and log rc.~). Si0,-Fe,O: Schuhmann and Ensio have measured the activity of iron oxide in simple iron oxide-silica slags when in equilibrium with y iron. Their data recalculated to 1600°C are shown in Fig. 1. Also included is a point representing a measurement by Gokcen and Chipmana of the activity of iron oxide at 1600°C at the point of saturation with solid silica. For convenience and in accordance with other treatments,' the calculations are based on the hypothetical component, FelO, which is obtained by converting all the analyzed iron in the slag to FeO. In spite of Schuhmann and Ensio's conclusion that the activity of iron oxide in the system does not vary with temperature over the experimental range of 1258" to 1407"C, the data are corrected to 1600°C assuming that temperature does have an effect. It was felt to be most reasonable to assume that the term log rr.10 is a linear function of the reciprocal of the temperature. Reyu has indicated that an effect of temperature on the activities in this system is to be expected from the Schuhmann and Ensio data. In essence, the correction consists of multiplying the experimental value of log rf,,o by the ratio of the experimental temperature in Kelvin to 1873°K. The magnitude of the correction is not large, being approximately 11.5 pct of the experimental value of log rve10. A very minor correction was necessary to compensate for the fact that the slags were in equilibrium with y iron in the experiment, while at steel-making temperatures they would be in equilibrium with liquid iron. Data for the correction were obtained from Darken and Gurry. The standard states established are pure liquid iron oxide (FelO) in equilibrium with pure liquid iron (with the appropriate amount of oxygen in solution) and pure liquid silica. The method of plotting in Fig. 1 is convenient for the calculation of the activity of liquid silica and permits a reasonable extrapolation for the activity of Fe,O in the ranges where no experimental data are available. The uncertainty in the extrapolation to infinity at one terminal where Nvelo = 1 for the usual Gibbs-Duhem integration is reduced considerably by this method. The region of two coexisting liquid phases is estimated to range from 1.8 to 41.7 mol pct Fe,O. The nature of the activity curve for the single-phase region indicates that the activity of iron oxide across the two-phase region is very close to 0.39. Computation of the function log ~F,,o/(1— NF,,o)' for this region (dashed line) in conjunction with the curve through the adjusted experimental data indicate the best probable value of 0.382 for alPe,o in the two-phase area. The line from 0 to 0.018 Nf~~o is obtained by assuming that the component follows Henry's law. In this range, the value for log rveto is 2.59. Appropriate mathematical manipulation of the plotted linet yields the activity curves for the The curve AF", the excess molar free energy of mixing (actual minus ideal), as shown in Fig. 3 is also computed from Fig. 1. This curve is required for subsequent calculations. CaO-Fe,O: The phase diagram for the lime-iron oxide system when in equilibrium with liquid iron is not well known but there appears to be no intermediate compound present. This fact as well as the activity values for Fe,O extrapolated to the CaO-Fe,O binary from Taylor and Chipman' tend to indicate somewhat negative deviations from ideality for the activity curves for the two components. Strong indication of this is evident in Fig. 1 where are plotted the points computed from the estimated activities of Fe,O for the binary system.' It appears that the best line through the data is a horizontal straight line. Because of the general indication of the slight negative departure from ideality, the line is extrapolated horizontally to NF~,o = 0. It is con-

Jan 1, 1956

By Herty, C. H.

Three distinct processes take place during the conversion of iron ore to steel. First: the raw ore is reduced to metallic iron in the blast furnace and during this reduction certain constituents are dissolved in the iron, either through the solution of a solid into a liquid phase, as in the case of carbon, or by reduction of an oxide existing in the slag to the metallic element of that oxide, with subsequent solution of the metallic element in the iron. Thus by the process of solution and reduction, a pig iron results which contains about 4 per cent carbon, 1 per cent silicon, 1 to 2 per cent manganese, 0.1 to 0.4 per cent phosphorus, and 0.03 to 0.10 per cent sulfur. To obtain a sufficient yield of iron from the ore it is necessary that the reducing process be carried as far as possible, with the result that the impurities mentioned accompany the reduced iron. Second: to convert this iron into steel it is necessary to oxidize a part of the iron in eliminating the impurities to the extent desired for the particular product being made. In eliminating these impurities by oxidation a certain amount of iron oxide (FeO) dissolves in the steel. This dissolved FeO reacts with the metalloids, except sulfur, and to eliminate them to the desired extent it is necessary to leave a considerable amount of FeO in the metal. The reaction of iron oxide with silicon, manganese, and phosphorus results in the formation of the oxides of these elements. The oxides enter the slag and the extent of elimination of the elements depends on certain equilibria between the slag and the metal. The reaction of FeO with carbon results in the formation of the gases CO and CO, which, after saturating the metal, pass into the furnace gases. Third: after the iron has been purified to the desired extent as far as the elements listed are concerned, it is necessary to deoxidize the bath to remove the FeO, which is the vital factor in gas formation as the steel solidifies.

Jan 1, 1957

By Homer Griffield Turner

The nature and comparative features of anthracite and bituminous coals have been discussed by the writer in two previous papers.' Although this paper is offered as a further contribution to the subject, it seems desirable at the outset to repeat some of the descriptive matter of the early works in order to show the actual connection between various constituents of both coals and the new photomicrographs and other physical and chemical properties. Structure of Anthracite and Bituminous Coals A lump of bituminous coal (Fig. 1) is readily seen to be composed of layers differing from one another in texture, luster and thickness. There are, in general, three kinds of layers, although only two are usually seen. One is deep black, very compact, and has a bright luster; another is grayish black, has a duller luster and is less compact; the third is black, dull and porous in appearance, but because of its thinness is not often seen except on parting surfaces. This last material is charcoal. American students of coal morphology use the names anthraxylon, attritus, and fusain to designate these three constituents of laminated coal. Anthraxylon refers to the brightest bands, attritus to the duller layers, and fusain to the charcoal. Close examination of a lump of bituminous coal shows the brightest deep black layers to be embedded in the duller grayish black laminae. These deep black layers are lens-shaped and vary in thickness from thin sheets to over half an inch. They are often so continuous through the lump that their tapering terminae are not noticeable. On careful examination the duller grayish black laminae (Fig. 7) are seen to contain many very thin sheets of this very bright black material. The charcoal

Jan 1, 1930

By John V. Beall

GOING west from Denver on Route 6, the direct road to Grand Junction, one gets the first glimpse of mining a few miles east of Denver near Idaho Springs where the workings of defunct gold mines are visible on the sides of mountains along the highway. One enterprising company is turning a profit by showing tourists through the mine and mill and then selling them gold samples on the way out. We have always known that mining people are ingenious, but this proves it. About five and a half hours fast driving west from Denver brings one to Rifle, Colo., which is the site of the oil shale mine, retorting plant, and refinery of the U. S. Bureau of Mines. As you drive up to the mine, you can see a portal high on the face of the cliff in front of you where the mine surface plant literally hangs by its toenails. Below, the retorting plant and refinery gleam in the sunlight. Up at the mine, Fred Wright will show you how the oil shale is extracted in two benches (a third bench would be used for commercial mining) by the room-and-pillar method. In mining the top level, an underground crew of thirteen men have been able to produce 1500 tons of shale in each eight-hour shift. To do this, the mine is thoroughly mechanized. The mining method is de- scribed in the September issue of Mining Engineering.

Jan 1, 1949

By DR. DOUGLAS

Discussion of the Paper of Dr. Douglas, presented at the Toronto Meeting of the Institute, July, 1907 (Trans., xxxviii., 455 to 471). EDGAR HALL, Silverspur, Queensland, Australia (communication to the Secretary*) :-Dr. Douglas has written on this subject before, and his influence has had a powerful effect on the side of freedom among the younger generation of engineers. Moreover, it is not the first time that he has attributed the decline of the copper-smelting industry in Swansea to the secrecy maintained by the firms there engaged in smelting-operations. In this latter statement I think his conclusions are open to criticism. Whether the firms referred to have suffered by their secrecy is their own business-I. bold no brief for them ; but that the decline of the copper-industry at Swansea was inevitable seems to me to be proved conclusively by Dr. Douglas's own writings. In his paper on The Copper Situation,1 Dr. Douglas says "In comparing iron and copper mining, . . . it must be remembered that 2 tons of average iron ore from the most prolific source now available will make 1 ton of metal; whereas from 33 to 75 tons (say an average of 50 tons) of copper ore must be mined to produce 1 ton of copper." And further: "Last year's production of iron was made from approximately 50,000,000 tons of ore. Our copper mines, to yield a production of 900,000,000 pounds, must have handled approximately 22,000,000 tons of ore, or nearly half the quantity raised from our iron mines." Is not this the key to the whole situation ? In transporting the 50,000,000 tons of iron-ore, 25,000,000 tons of the metal iron were carried so much nearer to the market, but the transportation of 22,000,000 tons of copper-ore would have carried only 450,000 tons of the metal copper nearer to its ultimate destination. The small percentage of copper available in its ores makes

Sep 1, 1908

By A. U. Seybolt

RECENTLY, cases of coexisting ordered and disordered phase equilibria have been reported among face-centered cubic metals,1"3 but not on body-centered cubic systems.4 McQueen and Kuczynski5 showed a single line as the boundary between ordered solid solution of Fe3Al type and corresponding disordered solution in the Fe-A1 phase diagram based mainly on dilatometric and magnetic measurements. Such a single line would indicate a second or higher order transition. or an absence of coexisting order and disorder. The writer found previously a two-phase equilibrium region at 800°C consisting of ordered and disordered solid solutions of Fe3Si in a matrix of approximately 1-6 wt pct Si (Fe3Si is of 14.3 wt pct Si). A similar two-phase region of ordered and disordered Fe3Al solid solutions might be expected if the similarity between Fe3Si and Fe3Si structures hold true. In the present investigation, a wire of 22 at. pct Al, balance Fe and 0.0513 cm in diameter was subjected to electrical resistivity measurement in vacuum as a function of temperature between 300 and 800°C, see Fig. 1. There was excellent agreement between data taken on heating and on cooling: no hysteresis was observed. The Curie temperature was determined to be 640 °C which agrees with the finding by McQueen and Kuczynski.5 But in addition, there were two transitional points in the resistance-temperature plot at 510oC and 400 "C. The former is thought to be a connection with the transition from disordered state to a coexisting order and disordered equilibrium state; while the latter, from such coexisting state to ordered state. Fig. 2 shows a phase diagram where the suggested two-phase region lies between dotted lines. The solid lines are those of McQueen and Kuczynski.5 Since these authors found only a single-phase boundary between ordered and disordered Fe3 Al, it would seem likely that the dilatometric method used by these authors was not sufficiently sensitive to resolve the ordering reaction into the two-phase boundaries. In addition, their phase diagram conflicts with the statement they make on P. 1 of their paper: "The sharpness of the peaks indicates that ordering to Fe3A1 is a first order reaction." The suggestion of coexisting order plus disorder in Fe3A1 must be considered tentative until confirmed by high-temperature X-ray examination. If

Jan 1, 1961

HE purpose of this chapter is to present a general outline of the basic open-hearth process for the benefit of students, practicing open-hearth operators, and metallurgists who wish to review the subject. The discussion is limited to a description of the sequence and purpose of the operations, illustrated by data and examples. Subsequent chapters deal with more detailed and fundamental studies of the subject. The function of the basic open-hearth furnace is to convert various types of ferrous material into finished steel of given composition and quality. In comparison with other steelmaking methods, the basic open-hearth process is one of the most versa- tile, both from the standpoint of the raw materials that can be used and the types of steel that can be produced. The process can be considered as a sequence involving melting, refining, and deoxidation. With some types of liquid-metal charges, the melting stage is not present, but refining and deoxidation in varying degrees are fundamental features of the process. GENERAL DISCUSSION OF BASIC OPEN-HEARTH PROCESS The first consideration in open-hearth practice is the type of charge on which the operation is based. This consists of three components-fluxing, oxidizing, and metallic materials. Fluxes. In the basic process the fluxing material is primarily lime, added in the form of either limestone (CaC03) or burnt lime (CaO). This is supplemented by magnesia (MgO) and lime from the furnace bottom and banks. The function of these fluxes is to form a slag with the silica (SiO2) , manganese oxide (MnO), iron oxides (FeO and Fe2O3), and phosphorus oxide (P2O5) that are produced by the oxidation of varying amounts of the silicon, manganese, iron, and phosphorus in the charge during melting and refining. The slag, composed of the basic fluxes and the neutral and acid oxides, floats on top of the steel bath when the charge is melted. The composition of this slag depends on the amount of each slag-forming element present in the charge and on the extent of oxidation of these elements during the course

Jan 1, 1951

By D. R. Hay, E. Scala

Electrotransport has been superimposed on the rate-limiling- step in zone refining which is the impurity diffusion through the liquid at the solid/liquid interface. The efficiency of zone refining is increased and relative resistivity ratios (P300°k/P4 2°K) he increased by 50 pel in tungsten for a given number of posses using- the electrotransport field-aided method. The effiect of zotze refining in the presence of an electric field on the relative resistivity ratio is examined as a function of its intensity and polarity. THE effect of electrodiffusion on the effective distribution coefficient of zone refining has been discussed by Pfann and Wagner.' Control of the distribution coefficient in zone refining is of twofold interest. A distribution coefficient of unity can be increased or decreased, making possible the transfer of some previously inseparable solutes. The general efficiency of zone refining can also be increased. In the conventional zone-refining process impurities are removed by their retention in the molten zone and subsequent deposition at the end of the rod after a complete passage of the zone. In higher-melting-point systems a second mechanism may also operate, the volatilization of impurities from the molten zone. It has been suggested by schadler2 that, in refractory metals, vacuum distillation plays the predominant role in purification. In Koo's results,3 the resistivity ratio decreased beyond a zone-refined length of 6 in. from the starting end, indicating that some purification does in fact occur by true zone-refining action. Hay and scala4 showed that the degree of purity as measured by the relative resistivity ratio method depends on the square root of time in the molten zone (number of passes) and thus appears to be limited by diffusion in the boundary layer at the solidifying interface assuming good mixing in the body of the molten zone where a linear rate would prevail. The final concentration of impurities in electron-beam floating-zone purification depends very much on the operating conditions and results obtained by various investigators2,3,5 are difficult to correlate. The diameter of the starting material, operating vacuum, and rate of traverse are among the factors to be considered. There are, nevertheless, some general observations to be obtained from the literature. Lawley5 reviewed the literature up to 1962 and concluded that the major contaminants generally remaining in tungsten after electron-beam zone refining are molybdenum and carbon. Molybdenum due to its high melting point and distribution coefficient of nearly unity would be expected to be difficult to remove by either volatilization or zone refining. Carbon is not only a common contaminant in vacuum systems, but is also very difficult to remove by conventional vacuum melting. even with vacuums of 10-7 mm Hg. For each of those impurities removed by zone refining the equation of Pfann and Wagner may be applied: It relates the effective distribution coefficient k to a superimposed driving force which accelerates the solute away from the interface with a terminal velocity L" and to the more conventional zone-refining parameters; v = rate of traverse, t = thickness of the diffusion layer at the solidifying interface, D = diffusivity of the solute in the molten zone, and ko = equilibrium distribution coefficient of the impurity.

Jan 1, 1965

By Raymond E. Davis

LET'S imagine we are at the Grand L Coulee Dam, where daily 15,000 barrels of low-heat Portland cement and 27,000 tons of processed aggregate in various sizes are mixed to produce 30,000 tons of concrete. Inspect the autographic records which show for each 4-cu-yd. mixer batch of concrete the weights of its constituent materials including its several sizes of aggregate, cement, and water, and which also show the period of mixing and the consistency of the mix. Watch the inspectors sample and test the aggregate for gradation and moisture content of sand, and sample the concrete for homogeneity. Watch the huge buckets deposit the concrete in the forms. It looks too dry to handle, but the concrete vibrators make it melt away. Just enough vibration fully to com- pact the mass, but not enough to produce segregation of the materials; the inspector says when. See the sprinkler system covering all hardening concrete with a spray so that it may not thirst for water. Watch the cleaning of the top of an old lift preparatory to placing a new lift; the sand blasting; the blow-down; the mop-up; the minute inspection.

Jan 1, 1939

By J. N. Roberts, K. V. Gow

In a recent review of the field of plastic deforrnation of metal single crystals, Maddin and chenl indicated the need for systematic investigations of the crystallography of the slip process with special attention to: a) The effect of the orientation of a crystal on the appearance of slip lines, b) The effect of high temperatures on the slip systems of aluminum, c) The effect of strain rate on the crystallography of slip. The present paper deals with the effect of temperature and strain rate on the mechanism of deformation of aluminum single crystals similarly oriented for single and duplex slip. The work of several investigators has shown that in aluminum at high temperatures other slip systems in addition to the predicted {I l l) <101> may operate. The most generally reported additional systems

Jan 1, 1959

By E. H. Dix

The work of Merical and other investigators indicates that the phenomenon of age-hardening in alloys of the duralumin type is primarily dependent upon the variation in the solubility of copper with temperature. In addition to copper, however, these alloys contain small amounts of magnesium, silicon, manganese and iron, which may affect the age-hardening either directly or indirectly. The effect of these elements on the solubility of copper and on the manner in which this solubility varies with the temperature is of considerable interest, therefore. The effect of magnesium is of especial interest because apparently it exerts a marked effect on the natural or room-temperature aging of alloys of the type described.2 A series of investigations3 has been in progress in the research laboratories of the Aluminum Company of America to determine the functions * Metallurgist, Aluminum Research Laboratories. f Metallurgical Division, Aluminum Research Laboratories. Formerly with Metallurgical Division, Aluminum Research Laboratories. 1 P. D. Merica, It. G. Waltenberg and H. Scott: Heat Treatment of Duralumin. U. S. Bur. Stds. Sn. Paper 347 (1910). 2 M. Gayler: Constitution and Age-Hardening of Alloys of Aluminum with Copper, Magnesium, and Silicon in the Solid State. Jnl. Inst. Met. (1922) 28, 213. W. Fraenkel: Vergutbare Aluminiumlegiengen. Ztsch. Melallkunde. (1920) 12, 427. E. H. Dix, Jr.: Note on the Microstructure of Aluminum-Iron Alloys of High Purity. Proc. Amer. Soc. Test. Mat. (1925) 26, Pt. 2, 120. E. H. Dix, Jr. and H. H. Richardson: Equilibrium Relations in Aluminum-copper Alloys of High Purity. Trans. A. I. M. E. (1926) 73, 560. E. H. Dix, Jr. and W. D. Keith: Equilibrium Relations in Aluminum-manganese Alloys of High Purity. Proc. Inst. Met. Div., A. I. M. E. (1927) 315. E. H. Dix, Jr. and A. C. Heath, Jr.: Equilibrium Relations in Aluminum-silicon and Aluminum-iron-silicon Alloys of High Purity. Proc. Inst. Met. Div., A. I. M. E. (1928) 164. E. H. Dix, Jr. and F. Keller: Equilibrium Itelations in Aluminum-magnesium Alloys of High Purity. Proc. Inst. Met. Div., A. I. M. E. (1920) 351. E. H. Dix, Jr., F. Keller and R. W. Graham: Equilibrium Relations of Aluminum-magnesium Silicide Alloys of High Purity. Trans. A. I. M. E., Inst. Met. Div. (1931) 404. W. L. Fink and K. R. Van Horn: Constituents of Aluminum-iron-silicon Alloys. Trans. A. I. M. E., Inst. Met. Div. (1931) 383.

Jan 1, 1932

By T. Egleston

THE works of the Ore Knob Copper Company are situated in the county of Ashe in the northwestern part of the State of North Carolina, about ten miles from the Virginia line, at an elevation of 4600 feet above the sea. The nearest railroad station is at Marion, Smythe County, Virginia, about forty-five miles distant. The roads from the railroad to the works have been constructed by the company for the transportation of their material, and are very hilly, and in certain seasons of the year in bad repair. Transportation is therefore always limited and never easy, although it is done by contract at a very low price. The main difficulty with the transportation is not so much its cost as the fact that it puts a limit to the production of the works. These unfavorable conditions make it necessary for the owners of the mine to smelt their ores and to send to market nothing except the metal, which alone will bear the cost of transportation. The mine was opened previous to 1860, but has only been worked systematically during the last five or six years. The vein is a fissure vein from ten to twenty feet in thickness in the gneiss of the

Jan 1, 1882

By T. Egleston

The works of the Ore Knob Copper Company are situated in the county of Ashe in the northwestern part of the State of North Carolina, about ten miles from the Virginia line, at an elevation of 4600 feet above the sea. The nearest railroad station is at Marion, Smythe County, Virginia, about forty-five miles distant. The roads from the railroad to the works have been constructed by the company for the transportation of their material, and are very hilly, and in certain seasons of the year in bad repair. Transportation is therefore always limited and never easy, although it is done by contract at a very low price. The main difficulty with the transportation is not so much its cost as the fact that it puts a limit to the production of the works. These unfavorable conditions make it necessary for the owners of the mine to smelt their ores and to send to market nothing except the metal, which alone will bear the cost of transportation. The mine was opened previous to 1860, but has only been worked systematically during the last five or six years. The vein is a fissure vein from ten to twenty feet in thickness in the gneiss of the

Jan 1, 1882

By Albert E. Wiggin

PagE I. Early History of Boston & Montana Mill at Great Falls (1891 to 1905). 210 a. Original Mill Built in 1891.........210 b. Coarser Concentration Tried...211 c. Screen Sizing of Fine Jig Feed Introduced..211 d. Installation of Finer Grinding.......211 e. Steam Stamp Tried in Place of Blake Crushers..... 211 j. Mill Increased from Three to Six Sections........ 213 g. Tonnage Increased from 300 to 450 Tons per Section... 212 h. Round Tables Replaced by Wilfley Tables....212 I1. Hancock Jig Replaces Evans Jig...212 a. Description of Hancock Jig...213 - b. Tests Made on- Hancock Jig..213 1. Treating Natural Feed..215 2. Treating Sized Feed..215 3. Treating Classified Feed .215 c. Tests Made on Evans Jig...216 III. Richards Pulsator Classifier System...218 a. Experimental Work.....218 b. Installation of System in Section No. 4,....... 220 IV. Woodbury Classifier and Jig System.............222 V. The Great Falls System................ 222 a. As Installed at Anaconda............ 224 1. Coarse Crushing and Jigging Division...... 225 2. Hancock Jig Division........... 226 3. Fine Middling Division.......... 229 4. Table Division............. 230 5. Slime Division.........230 b. Special Features of Great ails Flow sheet....... 231 1. Development of Hancock Jig Flow Sheet..... 231 2. Development of Finishing Table Flow Sheet.... 232 3. Treatment of Coarse Middling Table Products .. 232 4. Results of Test Made on 500-Ton Section at Great Falls Mill...........234 VI. Comparison of Great Falls and Evans System at Anaconda.... 236

Jan 1, 1914

By Edward J. Felten

THE oxidation resistance of chromium and Fe-Cr alloys is increased by small additions of yttrium or other rare earth metals.1,2 In addition, the presence of the additives increases the resistance of these alloys to spalling of the external oxide above 1000°C. This ability to prevent spalling appears to be related to the formation of an internal oxide in alloys containing yttrium or the other rare earth metals. The internal oxide is found in the form of a filamentary growth concentrated in the grain boundaries of the unoxidized metal. In alloys containing yttrium this internal oxide was found to be either Y2O3 Or YCrO3.&apos; In an earlier report,&apos; the growth of the external oxide was found to be controlled by diffusion through the oxide layer. Thermal balance studies were used to establish the kinetics of external oxide formation. In this related study the rate of growth of the internal filamentary oxide has also been studied. The results obtained indicate that the growth of the internal oxide is also diffusion controlled. Internal oxidation appears to occur in at least two ways. Using copper alloys containing small amounts of silicon, Rhines 3 found that between 600" and 1000oC a subscale was formed which consisted of particles of silica dispersed in the metallic matrix. The conditions requisite to internal oxidation as suggested by Rhines are: 1) a solubility of oxygen in the alloy, 2) the ability of oxygen to diffuse at an appreciable rate into the alloy, 3) the possibility of the formation by the alloying element of an oxide more stable than the oxide of the host metal, and 4) a relatively low solubility of this oxide in the metal. These conditions are fulfilled for a number of other copper alloys.3-5 Furthermore, the relationship between the depth to which the internal oxide is formed and the oxidation time follows the simple parabolic law.6 The activation energy for copper containing small amounts of silicon, germanium, iron, or manganese as calculated from Rhines data6 is about 48 kcal per mole. In some cases the internal oxide is found segregated at the grain boundaries, especially near the the surface. Observations of this type of oxide formation have been reported by stead,7 Rhines,* and Lustman. Evans" cites these cases as examples of the simultaneous movement of anions and cations during oxidation. Furthermore, Evans states that the presence of a minor constituent with a high

Jan 1, 1962

By H. C. Theuerer

GeC14 may be purified by extraction with HCI and chlorine. The process is as effective for the removal of AsCI:, as the more cumbersome distillation methods usually used for this purpose. GERMANIUM for semiconductor use contains impurities at levels no higher than a few parts in ten million. Material of this quality is obtained from highly purified GeC1, by hydrolysis to the oxide and reduction of the oxide in hydrogen. When purifying GeCl,, AsC1, is the most difficult impurity to remove. This is usually accomplished by multiple distillation procedures.1-3 AsC1, may also be removed from GeC1, by extraction with HC1.1-4 Reducing the arsenic to low concentrations is not practicable, however, because of the large number of extractions needed. This paper discusses a new method for the removal of arsenic from GeC1, by extraction with HC1 and chlorine. The method is rapid, leads to little loss of germanium and is at least as efficient as the distillation procedures currently being used. Theory of Extraction Procedures In the simple extraction of GeC1, with HC1, the following reaction occurs ASCl8G8C1 D AsCl3rc1 at equilibrium CA/Cn= K, where K is the distribution coefficient, and C, and C,, are the molar concentrations of AsC13 in HC1 and GeCl,, respectively. The materials balance equation for this reaction is VACA + vncn = VnC,, where V, and Vn are the volumes of HC1 and GeCl4, respectively, and C, is the initial concentration of AsC13 in GeC1,. From this it can be shown that for multiple extractions where C,, is the concentration of AsC13 in GeC14 after n extractions, and r is the ratio of V, to V,,. It is assumed that r is maintained constant, that equilibrium is established during each extraction, and that K is independent of the AsCl3 concentration. By saturating the system with chlorine, the following reaction occurs in the aqueous phase AsCl3 + 4H2O + Cl2 D H5AsO4 + 5HC1 at equilibrium K&apos; = ------------ ai - a4 h2u - aet2 where a is the activity of the various components. The effect of this reaction is to reduce the concentration of the AsC1, in the aqueous layer and, therefore, to promote further extraction of this component from the GeC1, layer. If the arsenic acid remains entirely in the aqueous phase, the net effect of this reaction is to promote the removal of arsenic from the GeC11. The materials balance equation for extraction with HC1 and chlorine with the foregoing reaction is, then, VaCC + VACA + VACn = VnCo where C,. is the molar concentration of H3AsO, in the HC1. With the added assumptions that the activities of AsC13 and H8ASO4 in the aqueous phase are equal to their molar concentrations, it can be shown that for n extractions Cn/Cu = (1/rkK + rK + 1) n where k - K1 a4h2o - acl2/aoncl. It can be seen by comparing Eqs. 1 and 2 that if k is large, the removal of AsC1, by HC1 extraction will be greatly improved by the addition of chlorine. Dilution of the HCI used in the extraction with chlorine would also favor the separation. This, however, would increase the loss of GeCl,, which is undesirable. Experimental Procedure Germanium prepared from oxide of semiconductor purity is n-type with resistivities greater than one ohm-cm. The resistivity is controlled by the donor concentration, which is —lo-: mol pct. Germanium prepared from material with added arsenic will have lower resistivity commensurate with the arsenic concentration. With such material, at arsenic concentrations above 10-1 mol pct the resistivity is controlled by the added arsenic, and effects due to other impurities initially in the oxide are negligible. In this investigation GeO, of semiconductor purity was converted to GeCl,, and -0.01 mol pct As was added. This material was used for the extraction experiments and the purification attained determined by a comparison of the resistivity data for samples of germanium prepared from the initial and purified GeC1,. A method for calculating the arsenic concentration from the resistivity data is discussed later. The details of the experimental procedures used are as follows: Two hundred and thirty cu cm GeC1, were prepared by the solution of GeO, in HC1, followed by

Jan 1, 1957

By J. W. Downey, R. A. Morris, M. V. Nevitt

An experimental survey has determined the occurrence of Ti2 Ni-type phases in binary and ternary alloys of Ti, Zr, or Hf with first, second, or third long-period transition metals and also in ternary systems in which 0 is the third component. The existence of eleven previously unreported isomorphs is cited and some approximate phase boundaries are given. Lattice parameters are reported for the new phases. The periodic table relationships involved in the occurrence of the phase are discussed. A previous paper&apos; reported the occurrence of a group of Ti2Ni-type phases (structure-type E93) containing Zr in combination with Rh, Ir, and Pt, and Hf in combination with Rh, Pd, Ir, and Pt, and cited evidence to show that all of the Zr phases and the Hf-Pd phase are not binary phases but occur only when 0 is present. More recently one of the present authors found that in the ternary systems of Ti and 0 with Cr, Mn, Fe, Co, and Ni the occurrence of the Ti2Ni-type phase could be correlated qualitatively with valency electron concentration, and that the role of 0 appeared to be that of an electron acceptor.&apos; This paper describes the results of a broader investigation of the occurrence of Ti2Ni-type phases in binary and ternary systems containing Ti, Zr, or Hf. EXPERIMENTAL PROCEDURE Alloys were prepared by arc melting. The purity of the metals Zr, Rh, Hf, Ir, Pd, and Pt was given in the previous paper.&apos; The additional materials used for this work were metals with a minimum purity of 99.9 pct and reagent grade ZrO2, TiO2, Cr2O3, and NiO. Chemical analysis of several alloys in each system indicated good agreement between intended compositions and cast-button compositions. For the heat treatment precautions were taken to avoid oxygen contamination. The specimens were wrapped in Mo foil and sealed in fused quartz tubes at a room temperature pressure of 1 x mm of Hg. These capsules were then annealed in a vacuum furnace at an external pressure of 5 X mm of Hg. Since the major constituent in most of the alloys studied was the brittle Ti2Ni-type phase, Debye-Scherrer patterns with sharp lines could be obtained with powder crushed from the annealed solid samples without being reannealed. Metallographic, X-ray diffraction, and density determination techniques previously described1, 2 were used. RESULTS AND DISCUSSION Zr-Rh-O, Zr-Ir-Oand Zr-Pt-O Systems-Figs. 1 through 3 show the approximate boundaries of the Ti2Ni-type phase fields at the temperatures indicated in the ternary systems Zr-Rh-O, Zr-Ir-O and Zr-Pt-0. In each isothermal section the Ti2Ni-type phase field is labeled E and the unidentified binary phase found in the previous work&apos; is labeled ?. The dotted lines, which are not phase boundaries, correspond to the composition (Zr2 B)1-xOx. In each system the Ti2Ni-type phase field is displaced to the high-Zr side of this composition line. However, the departures from Zr2B stoichiometry for the metal components are not as high as Zr3B, as was inferred from the previous work. Lattice parameters of the Ti2Ni-type phases in the alloys shown as triangular data points in Figs. 1 through 3 are given in Table IA. The probable compositions of the Ti2Ni-type phases have been estimated from the isothermal sections. Although there are a few exceptions that probably result from uncertainties in phase boundary location and from the effect of variation of oxygen content, the generalization can be

Jan 1, 1961