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By V. F. Parry, J. B. Goodman

The low-rank coals containing 10 to 50 pet natural bed moisture represent over half of the tonnage reserve of the available solid fuels of the United States, but only about 2 pet of United States coal production is derived from these fuels. Increased utilization of these large reserves will result if the bed moisture can be removed at the mine in high-speed low-cost processes. This paper presents a theoretical and experimental study of the factors affecting high-speed drying of coal dusts. The time required to heat particles of coal is proportional to the square of their diameter, and it is calculated that the probable time in minutes is equal to 6D2. In other words, a 11 a in. coal particle should be heated to drying temperature in 1.5 to 2.0 sec. Likewise, 1/8 in. particles should be heated in about 6 sec. The net heat required to dry subbituminous coal and lignite varies from 240 to 375 Btu per pound, depending upon the moisture removed, and this heat can be obtained from 42 to 61 cu ft of hot gases at 600°F.

Jan 1, 1949

By Edward L. Beutner, Robert M. Crump

Benson Mines low-grade iron ore reserve is a replacement deposit within the Grenville gneisses of the Adirondacks. The average grade of the crude ore is about 23 per cent iron. The iron minerals are principally magnetite and hematite disseminated throughout the gneisses as discrete grains about 1 mm in size. Both the ores that are beneficiated by magnetic means and the non-magnetic ores that are treated by a gravity method of concentration are found in stratigraphically different positions but are mined from one open pit, which is about 2.5 miles long and 800 feet wide and are treated separately. The gneisses are described and named according to the distinctive mineralogy of each. Recognition of the gneissic types permits the interpretation of the structure as a northward-plunging syncline overturned to the west. A large subsidiary anticline-syncline complex occurs on the east limb of the major syncline. Iron minerals in sufficient quantity to be considered ore are confined to areas where the footwall rock has been overturned to become the hanging wall.

Jan 1, 1968

By James Douglas

IN discussing the waste upon which hinges, or is supposed to hinge, so largely the preservation of our national resources, the conclusions reached would be more reliable if actual ex¬perience were consulted, and fewer deductions were drawn from general statements, which are often the product of the imagination. It cannot be questioned that the value of by-products has not been sufficiently appreciated by us, and that our, tardiness in recovering the useful ingredients of the escaping gas of our coke-ovens is one of the most glaring instances of shortcoming in that direction. And yet even for that sin there is some palliation in the immature condition of affiliated industries. I presume that it is admitted, without argument, that, except under very exceptional conditions, all the elements cannot be recovered from most of the ores or natural products. which we treat. While it is a shame that the by-products from our coke-ovens should be dissipated, Edward W. Parker's report to the U. S. Geological Survey for 1906' supplies a fairly good excuse in justification of this appalling waste. He says (pp. 773 to 774.)

May 1, 1909

By Nicholas J. Grant, H. C. Chang

TRANSCRYSTALLINE fracture surfaces of the cleavage type have been examined by microscopy and X-rays for several metals.' These investigations revealed that the fractured surfaces were not flat and invariably had cleavage and other deformation markings on them. On the other hand, the study of inter crystalline fracture surfaces has been limited. Perryman, in a recently published paper on the inter crystalline fracture of ß-brasses,' found that a thin layer of heavily deformed metal was invariably associated with these surfaces. Furthermore, the thickness of this layer was found to depend on the orientation of the grain boundary surface with respect to the applied stress. The mechanisms of grain boundary sliding and intercrystalline fracture have been presented in two previous papers,which described certain aspects of the deformation of a 20 pct Zn-A1 alloy. It is the purpose of this paper to present some observations on the structure of intercrystalline fracture surfaces and to correlate the structure of such surfaces with the mechanism of intercrystalline fracture. Experimental Techniques—The high purity 20 pct Zn-Al alloy was generously supplied by the Research Laboratories of the Aluminum Co. of America. Two sizes of specimen were used; the first had two parallel flat surfaces of dimensions 1x0.17x0.09 in. and the second was round with a 0.25 in. diam. A grain diameter of 1 to 3 mm was obtained by annealing the specimens at 1000°F for 24 hr. The specimens were then air cooled. The specimens were subjected to creep at 500°F and 2300 psi. The rupture times ranged from % to 3 hr, with one room temperature tensile test. It has been mentioned previous1y" that the intercrystalline fracture surfaces of this alloy, when tested under the conditions given above, are sharply defined. In the optical examination of the fracture surfaces, whenever possible, magnifications of at least X250 were used. The locations of the regions examined, both optically and by X-rays, were selected to give several fracture surface orientations with respect to the stress axis and to the specimen surfaces. This was possible for the X-ray studies since the grain diameters were large compared to the X-ray beam. A film to specimen distance of 3 cm, a 1 mm pinhole and Cr radiation were used for the Laue back reflection pictures.

Jan 1, 1957

By Kenneth S. Ritchie

TOO often, many foremen; superintendents, managers, and executives, "The Bosses" of the oil and mining industries, do not fully realize: (1) How much personal actions '.on the job" may reduce their effectiveness in getting work done; and, (2) The importance of harmonious relations with their fellow men. Today. these qualities of personality in the people entrusted with the positions of responsibility are more important than ever with the shortages of labor so critical in vital war production. Likewise, many engineers do not fully realize that their work is essentially executive in character; i.e., other people do the actual labor. Without their help. the engineer's work would not be done. A clearer appreciation of this fact would increase their interest: (1) in the nontechnical aspects of their work. and, (2)in their relations with others, particularly the individuals in their own organization. Consequently, these engineers would be more successful in equipping themselves for greater responsibilities and increased remuneration.

Jan 1, 1944

Page The Cobaltchromium Binary System (paper by A. R. Elsea, A. B. \Yesterman, and G. K. Manning, Met. Tech. June, 1948, Mechanism of Precipitation in a Permanent Magnet Alloy (paper by A. H. Geisler and J. B. Newkirk, Met. Tech. Aug. 1948, Tp 2444)................................................................................................. 300 Some Effects of Applied Stresses on Precipitation Phenomena (~aper by W. L. Finlay and W. R. Hibbard, Jr., Met. Tech. Sept. 1948, Tp 2470)....................................................................................... 301 Diffusion of Carbon in Austenite with a Discontinuity in Composition (paper by L. S. Darken, Met. Tech. Sept. 1948, TP 2443) 304 An Electron Diffraction Study of Oxide Films Formed on Nickelchromium Alloys (paper by J. W. Hickman and E. A. Gul- bramen, Met. Tech. June 1948, Tp 2372)..................................................................... 305 An Electron Diffraction Study of Oxide Films Formed on Copper-nickel Alloys at Elevated Temperatures (paper by J. W. Hickman and E. A. Gulbransen, Met. Tech. June 1948, TP 2391)................................................ 307 Decarburization of Chrome Nickel Alloys by Their Surface Oxides in High Vacua and at Elevated Temperatures (paper by E. A. Gulbransen, W. S. Wysong, and K. Andrew, Met. Tech. Sept. 1948, TP 2438)................................ 307 Fractographic Study of Cast Molybdenum (paper by C. A. Zapffe, F. K. Landgraf and C. 0. Worden, Met. Tech. Aug. 1948, TP 2421)................................................................................................. 308 Effect of Composition on Grain Growth in Aluminum-magnesium Solid Solutions (paper by L. J. Demer and P. A. Beck. Met. Tech. June 1948, TP 2374)............................................................................. 309 Effect of a Dispersed Phase on Grain Growth in Al-Mn Alloys (paper by P. A. Beck, M. L. Holzworth and P. Sperry, Met. Tech. Sept. 1948, TP 2475)................................................................................. 310 Statistical Rate Theory of Metals—Mechanism of Flow and Application to Tensile Properties (paper by J. W. Fredrickson and H. Eyring, Met. Tech. Aug. 1948, TP 2423)............................................................... 315 Nucleation of Slip Bands (paper by J. G. Leschen, R. P. Carreker, and J. H. Hollomon, Met. Tech. Sept. 1948, TP 2476) and.. 318 Transient Plastic Deformation (paper by R. P. Carreker, J. G. Leschen, and J. D. Lubahn, Met. Tech. Sept. 1948, TP 2477).. 318 Plastic Deformation of Large Grained Copper Specimens (paper by W. R. Hibbard, Jr., Met. Tech. Sept. 1948, TP 2469). ... 323 Plastic Flow in Anisotropic Sheet Steel (paper by L. R. Jackson, K. F. Smith, and W. T. Lankford, Met. Tech. Aug. 1948, TP 2440)................................................................................................. 323 The Effect of Thermal-mechanical History on the Strain Hardening of Metals (paper by J. E. Dorn, A. Goldberg, and T. E. Tietz, Met. Tech. Sept. l948, TP 2445)....................................................................... 325 The Room and Elevated Temperature Properties of Some Sand Cast Magnesium-base Alloys Containing Zinc (paper by T. E. Leontis, Met. Tech. June 1948, TP 2371)..............................................................., 327 The Low Temperature Properties of Tin and Tin-lead Alloys (paper by H. S. Kalish and F. J. Dunkerley, Met. Tech. Sept. 1948, TP 2442)............................................................................................335 Thermal and Electrical Properties of Ductile Titanium (paper by E. S. Greiner and W. C. Ellis, Met. Tech. Sept. 1948, TP 2466).................................................................................................... 335 Property Changes during Aging (paper by A. H. Geisler, Met. Tech. Aug. 1948, TP 2436)............................... 337 Factors Affecting the Tensile Notch Sensitivity of Magnesium Alloy Extrusions (paper by I. Cornet, Met. Tech. Aug. 1948, TP 2419)................................................................................................. 338 Effect of Grain Size on Tensile Strength, Elongation and Endurance Limit of Deep Drawing Brass (paper by H. L. Walker and W. J. Craig, Met. Tech. Sept. 1948, TP 2478)............................................................. 339 A Copper-base Alloy Containing Iron as a High-strength, Highconductivity Wire Material (paper by W. Hodge, R. I. Jaffee, J. G. Dunleavy, and H. R. Ogden, Met. Tech. Aug. 1948, TP 2422).............................................. 340 A High Strength-High Conductivity Copper-silver Alloy Wire (paper by W. Hodge, R. I. Jaffee, J. G. Dunleavy, and H. R. Ogden, Mel. Tech. June 1948, TP 2366)...................................................................... 340 The Effect of Chronlium on the Ma Point (paper by J. B. Bassett and E. S. Rowland, Met. Tech. Aug. 1948, TP 2417.... 341 The Kappa Eutectoid Transformation in the Copper-silicon System (paper by W. R. Hibbard, Jr., G. H. Eichelman, Jr., and W. P. Saunders, Met. Tech. Sept. 1948, TP 2441).............................................................. 343 Stabilization of the Ausknite-martensite Transformation (paper by W. R. Harris, Jr. and M. Cohen, Met. Tech. Sept. 1948, TP 2446)................................................................................................ 344 Secondary Hardening of Tempered Martensitic Alloy Steel (paper by W. Crafts and J. L. Lamont. Mel. Tech. Sept. 194,8, TP 2439)................................................................................................. 345

Jan 1, 1950

By Linney, Robert J.

REPUBLIC Steel Corporation's iron-ore properties in the Adirondacks consist of mines, mills, and sintering plants in the Mineville and Port Henry area and at Lyon Mountain. This article will deal with the properties in the vicinity of Mineville and Port Henry. In 1938, when Republic leased the Mineville- Port Henry operations from the Witherbee Sherman Corp., these properties had just come through some hard depression years. As a result, the mine development program was far behind schedule; most of the equipment needed replacement; and above all, the entire system of mining had to be completely changed to reduce operating costs. The concentrator had been in operation for many years; the process was dry and dusty. Machinery and equipment were either badly worn or entirely obsolete. The sintering plant, also long in operation, was badly in need of repairs.

Jan 1, 1943

By S. A. Hovanessian

The method of characteristics which reduces the Buckley-Leverett mnlineur, partial differential equation to two first-order, linear differential equations is applied to the solution of a waterffood recovery problem for multiple lines of producing wells and one line of injection wells. The application of the method is described by a numerical example, and a brief theoretical background is given. From the results of this study, it is concluded that the cumulative water injected and oil produced are the same for single and multiple sets of producing wells. INTRODUCTION In this paper, the method of characteristics is applied to the solution of a waterflood recovery problem with multiple lines of producing wells and one line of injection wells. The application of the method to this type of recovery problem considerably simplifies the procedure of obtaining a numerical solution. It differs from the method described by Kern1 because it eliminates the need for integration in obtaining saturation fronts. In addition, the saturation history at any location within the field is obtained from a single diagram (time vs distance with saturation as a parameter)'. The paper includes a brief theory of the method of characteristics and its application to the solution of oil recovery problems. A numerical example is worked out, and the cumulative oil recovery-vs-time curve for a system with multiple sets of producing wells is obtained. This curve is then compared with the recovery curve of a system with only one set of producing wells. From this study, it is concluded that the cumulative water injected and oil produced are the same for single and multiple lines of producing wells. However, the recovery time is considerably longer for multiple sets of producing wells.

By Malcolm T. Hepworth

RECENT interest in thermoelectric devices has been directed toward studies of the properties of thermoelectric materials of semiconducting solid compounds with little attention given to ionic and semiconducting liquids such as aqueous solutions, fused salts, and mattes. One type of thermoelectric system is the thermocell: a nonisothermal galvanic cell with two identical electrodes at different temperatures connected by an electrolyte bridge. An electromotive force, v, is generated which is a function of the electrode reactions and the properties of the electrolyte according to the Eastman' equation: where S* is the entropy change of the system arising from the electrode reactions and by heat transferred by ion migration and by thermal conduction. The quantity nF is the product of equivalents passed and Faraday's constant. A value of S* of 23.06 cal per "C is equivalent to 1 mv-Faraday per "C. The symbol, a, is used for dV/dT in analog to the See-beck coefficient of solid-state thermoelements. de Bethune2 has calculated the temperature coefficients of the electromotive force of a large number of nonisothermal aqueous cells from measurements on the nonisothermal temperature coefficients of the standard hydrogen electrode, combined with data on the isothermal temperature coefficients of half-cells tabulated in the literature. Values of these coefficients (a) in de Bethune's compilation ranged up to 3 mv per C. In particular he reported a value of +2.059 mv per "C at 25'C for the cell: Fe (aqueous, unit activity) (aqueous, unit activity) written for the hot-electrode reaction. The positive sign indicates that the hot electrode is positive (an "n-type thermocell"). In analog to a solid-state p-n system, it would be possible to couple two thermocells together to form a system in which the figure of merit could be calculated by adding the temperature coefficients according to the relationship described by offee:' where a is the Seebeck coefficient in volts per "C, p is the specific resistivity in ohm-cm, and K is the thermal conductivity in watts per cm "C. Even though ionic systems have rather high electrical resistivities compared with semiconducting and metallic systems, it was felt that a preliminary study of one ionic system should be made to establish some basis for evaluating the possibility of a p-n thermocell for energy conversion. Accordingly the Fe", Fe"' system was studied as a possible component for a p-n system. A glass system was constructed consisting of two vertical water-jacketed tubes connected by a horizontal tube, Fig. 1. Platinum-black electrodes 1 cm by 1 cm in dimension were inserted in each vertical tube with thermometers to register the electrode-compartment temperatures. The temperature of the electrode compartments was controlled by circulating water from thermostatted baths around the electrode compartments. The electromotive force of the cell was then read by a potentiometer for zero current as a function of the temperature of the hotter electrode. Current output of the cell for varying external loads was also measured. The cell resistance was measured by means of a bridge circuit with 10,000 cps signal and oscilloscope. Resistance measurements were converted to specific resistivity by calibrating the cell with a solution of known conductivity.

Jan 1, 1965

By Basil B. Zavoico

CRUDE oil production in the United States during 1938 reached approximately 1,214,355,000 barrels, an average of 3,327,000 barrels per day, or 5 per cent below the 1937 record output of 1,279,160,000 barrels. The decreased production did not prevent the stocks of all products from increasing to a total of 575,954,000 barrels by Sept. 30, an increase of 10,957,000 above the total on Jan. 1, or an average daily storage increase in all products of 40,135 barrels. The increase in total stocks was made entirely in the refined products, stocks of crude oil during the first nine months of 1938 having actually declined 7,155,000 barrels to 299,671,000 barrels, or an average daily decline of 26,209 barrels. The 1937 reversal of the preceding five-year trend of discoveries totalling less than withdrawals was continued through 1938 with indicated reserve addition from both new discoveries and extensions considerably in excess of the

Jan 1, 1939

By AIME AIME

ON the headwaters of the Hudson Riser, in a sparsely populated area of the north woods at Tahawus, N. Y., thirty miles from the nearest railroad, is the Maclntyre property of National Lead Co. Operations involve the mining and processing of titaniferous iron ore to produce ilmenite concentrate, and magnetite concentrate containing vanadium, for use in the production of iron, titanium, and vanadium in the war program. Accordingly, Maclntyre at present is classed as a war plant. More than 3000 long tons of ore is ruined daily by opencut methods and treated in an ore concentrating plant.

Jan 1, 1943

George E. Collins, Nacoochee, Ga. (communication to the Secretary): The results tabulated below were obtained at the Reynolds mill, White county, Ga. They were noted, not with a view to investigating the point discussed by Mr. Clark, but in course of a test on a working scale to determine the com parative saving from a given free-milling ore on copper and silvered plates respectively. In every case the bullion assayed was the result of a separate clean-up on a considerable quantity of ore. The ore varied widely in grade and in other respects, but the runs bracketed in the table were made at the same time, in adjoining batteries, and on similar types of ore. In a * Result modified by the addition to the bullion-shipment of a little impure bullion left over from previous clean-ups.. On these occasions, the strips of copper were removed from the tables, and: their lower surfaces were cleaned. Hence the higher yield reported.

Jan 1, 1900

By E. B. Brauer, W. Hurst, J. D. Clark

Because of drilling, completion, and workover practices, the permeability around a wellbore generally is different from the permeability of the formation. The zone with the altered permeability is called "skin" and its effect on the pressure or flow behavior of the well is called "skin effect". Hawkinsl has shown that the radius and the permeability of this zone are related to the skin by: If the permeability in the skin zone is less than that of the formation, the skin is positive; if it is more than that of the formation, the skin is negative. If the two permeabilities are equal, s is zero; that is, there is no skin. Van Everdingen2 and Hurst3 have given mathematical solutions to the case of a zone of reduced permeability around the wellbore. This skin effect is illustrated in Fig. 1. They treat the positive skin as a zone of reduced permeability of infinitesimal thickness around the wellbore. When applied to a well with negative skin, however, their solutions lead to the calculated flowing well pressure which is smaller than the formation pressure, i.e., an injection situation. This is a physical contradiction. In this paper, it is shown that this mathematical difficulty can be overcome by assuming an effective wellbore radius larger than the actual wellbore. Existing solutions2"4 are modified to include the effect of an enlarged wellbore radius, and thus enable the engineer to deal with negative as well as positive skins. Theoretical Development Van Everdingen and Hurst,4 through the use of Laplace transformation, obtained the following expression for transient fluid influx into a wellbore: The values for QtD, reported extensively by van Everdingen and Hurst,4 are obtained from the following integral:

Jan 1, 1970

By C. A. Stetefeldt

FoR the convenience of those who do not care to enter into the details of this long essay, I begin with a summary of the most important results it presents. The extraction of silver by the lixiviation-process from ores which have been subjected to a chloridizing-roasting, is based upon the fact that silver chloride is easily soluble in solutions of sodium or calcium hyposulphite, and that silver is precipitated from such solutions by an alkaline sulphide, with regeneration of the hyposulphite salts. In case the ore contains lead a large portion of the latter is and dissolved, lead sulphate being soluble in hyposulphite solutions. If, at the same time, copper is present, the sulphides precipitated from the solution, contain silver, copper, and lead, a combination of metals not desirable for subsequent treatment. Mr. E. H. Russell, of Park City, Utah, is the inventor and the patentee in the United States and several foreign countries of a new lixiviation-process, based upon the chemical facts discussed in this paper. Mr. Russell has discovered that lead can be completely separated from a sodium hyposulphite solution, as lead carbonate, by sodium carbonate or purified soda-ash, without precipitating any copper or silver. After decanting the solution from the lead carbonate, silver and copper are obtained from it in the usual way. This method of separating lead prohibits the use of calcium poly-sulphide as a precipitant for the sulphides, because any calcium entering the regenerated lixiviationsolution would also be precipitated as a carbonate with the lead by soda-ash. Hence, a sodium sulphide must be employed. A full investigation has demonstrated that this is by no means detrimental. Sodium sulphide and hyposulphite are more advantageously used in the lixiviation-process than the corresponding calcium-salts. Another defect in the lixiviation-process consisted in the necessity of a very perfect chlorination of the silver in the ore, because silver in

Jan 1, 1885

By E. Northcott, I. M. LeBaron

Before describing the electrostatic processing of feldspar, it might be well to review some of the basic definitions and terminology of feldspars. The feldspar minerals constitute a group of alumino-silicates of potassium, sodium, and calcium. Barium feldspar sometimes occurs naturally but is very rare. Hardness varies between 6 and 6.5 and specific gravity between 2.5 and 2.8. Color is generally white or pale shades of red, yellow, or green. The approximate chemical composition of the principal feldspars is given in Table I. The albite (sodium aluminum silicate) and an-

Jan 1, 1959

By John Boardman

THE latest metal-mine accident report available for the United States is that of the Bureau of Mines for the calendar year 1919. Quoting from Table 20, p. 53, of that report, we find that there were 468 men killed, 7 permanently totally disabled, 321 permanently partially disabled, 7848 injured seriously (more than 14 days disability), and 23,330 of 1 to 14 days disability. We have no records to show what the average days lost per case of accident is, but the records for the Anaconda Copper Mining Co. show that, leaving out the fatalities and total permanent disabilities, and counting those in which the lost time was one or more days, the actual days lost due to accidents, for the Butte mines and shops for five years, 1917-1921, were as follows: Accident Statistics, Butte Mines and Shops of A. C. M. Co. Rate Shifts Days Lost Year Accidents Total Shifts 10,000 Shifts Days Lost Per Acci-dent 1917 2,661 3,169,720 8.395 26,734 10.05 1918 2,765 3,545,149 7.799 39,199 14.17 1919 1,381 1,853,143 7.452 22,797 16.50 1920 1,376 1,879,410 7.321 20,164 14.65 1921 376 776,461 4.842 8,287 22.03 Total... 8,559 11,223,883 7.625 117,981 13.80 In order to place an economic value. on this loss, we will assume that all the 468 fatalities and the 7 total permanently disabled in the United States were com-pensated for at the rate which applies in the State of Montana, that is, $5000 each, and that the 8169 serious accidents in the United States were compensated for at an average of $70 per case, thus bringing the estimated compensation paid by metal-mining companies in the United States to the enormous total of $2,946,830 for the year 1919. The figure of $70 per case was obtained by dividing the total amount paid by metal-mining companies under Plan No. 1 of the Montana Compensation Law, for the first five years of its operation, by the total number of serious accidents for those years.

Jan 9, 1922

By B. Chalmers, S. Wojciechowski

THE structure of the equiaxed zone of several A1-Cu samples mechanically stirred during unidirectional solidification was examined. The stirring was produced by rotary oscillation of the mold about its vertical axis.' It was found that in Some samples the structure is not of the same type over the whole of the equiaxed zone; it consists of regions with two different etching responses. Fig. 1 shows this structure in a Al-1 wt pct ku sample. The lighter etching regions with a coarse structure form something like a network and the darker etching regions with a finer structure can be observed as the continuation of the coarse structure inside this network. The difference in size and shape of the dendrite branches (they are rounded in the coarser structure) is similar to that found by Williamson and Chalmers in ice crystals solidified in undercooled water: when the amount of undercooling was small, the ice crystals were more rounded and coarser than these solidified with a larger amount of undercooling.' It seems justified to conclude that the observed structure resulted from solidification under different thermal conditions: the coarser structure solidified first out of the "purer" liquid and with a smaller amount of undercooling and the finer was formed later out of solute-enriched liquid under conditions of much more rapid heat extraction. A considerable change in the heat flow conditions at the later stages of solidification can be easily understood by taking into account that the coarser crystals form a continuous network and the amount of trapped liquid is relatively small; hence the contribution of latent heat is much smaller in the later stages of solidification. The difference in structure and etching characteristic reflects a difference in composition between these two regions. It was found that the darker etching re- gions are harder (30.4 to 31.3 HV5) than the lighter etching ones (25 to 26 HV5). A similar type of structure was found in a A1-4 wt pct Cu sample grown by Czochralski method. Fig. 2 shows the structure in the lower part of a sample grown slowly and then decanted by a rapid removing of the sample from the melt. In a few places trapped liquid solidified in the same manner as in the sample shown in Fig. 1.

Jan 1, 1968

By T. C. M. Pillay, John Chipman

The Si-0 equilibrium in liquid iron was investigated in some detail by Gokcen and Chipman1 who reported equilibrium constants of the following reactions: In each case the thermodynamic equilibrium constant K was obtained by extrapolating K' to infinite dilution. Their results on reaction [I] were consistent with those of earlier observers, and there seems to be little doubt as to the approximate validity of the equilibrium product determined. On the other hand, the results on reactions [2] and [3] indicated unusual curvilinear relationships between the activity coefficients of silicon and of oxygen and the silicon concentration. Since a linear relation is observed in all other similar instances, it was concluded that some source of error had affected the gas-metal equilibrium relationships. Recently the authors undertook a restudy of these equilibria with the view especially to establishing the equilibrium constant of reaction [2]. Their experiments, however, were discontinued before a tbroughly satisfactory answer had been obtained and consequently have remained unpublished until the present time. Quite recently Matoba, Gunji, and Kuwana2 published the results of a very thorough study of these equilibria. It is the purpose of the present note to Compare these three sets of experimental data, a comparison which leads to Confirmation of the results of Matoba and coworkers. The experimental arrangements described by Dutilloy and Chipman were employed. A controlled mixture of Hz, H,0, and argon was led into the induction furnace over the surface of the Fe-Si melt contained in a silica crucible. On account of the slow approach to equilibrium, runs were continued for at least 8 hr and, in some cases, as much as 12 hr. Samples were taken by means of silica tubes at the start and during the final 4-hr period of each run. Out of twelve runs only seven appeared to have approached equilibrium with sufficient certainty to be reported here. The results of these experiments, all at 1600°c, are shown by the triangles in Fig. 1. Equilibrium was approached from both oxidizing and reducing conditions and the direction of approach is indicated by the shape of the triangle. Attempts to extend the study to higher silicon concentrations were unsuccessful on account of the transfer of silica from the metal bath to the upper portions of the crucible by means of a silicon-monoxide mechanism. Matoba, Gunji, and Kuwana used similar methods and approached equilibrium from both sides. Their results at three temperatures are shown by the solid lines of Fig. 1. A line corresponding to 1600 deg is interpolated from their equations and is shown by the dotted line. The results of Gokcen and Chipman at 1600 deg in the range 0.02 to 2.0 pct Si are also shown. At concentrations up to about 0.6 pct Si, these investigators approached equilibrium from both directions, and their results in this range appear to be trustworthy. Above 1 pct Si, however, all of their experiments involved oxidation only, as shown by a decrease in the silicon content of the bath. It now seems certain that they failed to reach equilibrium at these higher silicon concentrations and that the curvilinear relation shown by their results is incorrect. It is evident that their results in the lower silicon range are in good agreement with those of Matoba and coworkers. In fact, a straight line drawn through their results would parallel the dotted line and would differ from it by only 0.05 in log K. The new data also lie close to that line. It may thus be concluded that the three sets of data are in good agreement and that the equations proposed by Matoba and coworkers for reaction [2] are satisfactory . They take the limiting value of log K', at 0 pct Si as log K ,. The slope of each line gives the value

Jan 1, 1962

By G. R. St. Pierre, A. J. Wilhelem

In connection with the reduction of hematite or magnetite to metallic iron, it appeared desirable to study the rate of reduction of each oxide to the next lower oxide under conditions which excluded all other condensed phases. For this purpose, pellets of Fe,O,, Fe,O,, and oFeOo were prepared. A gas train for the preparation of Ar-Hz-H20 mixtures was employed to establish a continuous flow of a controlled atmosphere over a pellet suspended on a balance. In this manner the following individual reduction steps could be studied: For example, pellets of hematite were reduced solely to magnetite by adjusting the gas atmosphere such that it was oxidizing to wustite. In other words, the reaction was complete when the hematite pellet had been totally converted to magnetite. The pellets were prepared from Baker Chemical ferric oxide. The ferric oxide powder was moistened and handrolled. Air sintering at 950°C produced Fe,0, pellets with a density of 3.65 g per cm3. The pellets ranged in size from 0.6 to 1.2 cm diam. The magnetite and

Jan 1, 1962

By L. D. Jaffe

IN previous metallographic work on titanium and its alloys, difficulty has been encountered in distinguishing spheroidal particles of titanium hydride, dispersed in a-titanium, from other phases that may be present, such as p-titanium. This problem is common in examination of commercial unalloyed titanium.' In the course of an investigation of the Ti-H phase diagram, it was noted that titanium hydride, dispersed in a matrix of a-titanium, showed strong optical anisotropy when examined under polarized light. With sensitive tint illumination, particles of the hydride, when the stage is rotated, changed from bright yellow to bright blue in color. Since P-titanium is cubic, it showed no color change on rotation, remaining dark gray or blue-gray. Although a-titanium is hexagonal, it showed only a minor color change, going from pale pinkish-blue to pale purplish-blue. These colors could be modified somewhat by adjustment of the illumination. They were observed in specimens mechanically polished, both without etching and after etching with hydrofluoric acid-nitric acid mixtures in either water or glycerine. The strong color change of the hydride seems to offer a simple method for its metallographic identification. Optical anisotropy of titanium hydride is inconsistent with its accepted face-centered-cubic structure.' Samples of iodide titanium containing 6 to 40 atomic pct deuterium were prepared for diffraction studies. After deuterating and slow cooling' the samples were held 21 % hr at 400 °C, water quenched, held 61 hr at 100°C and quenched, then held 64% hr at 255 C and quenched. Debye ex-posures with MoKa X-rays and 1.111A neutrons were made at room temperature of samples as-deuterated and after the 100" and 255°C treatments. Table I shows the lines observed, in addition to those attributable to a-titanium. These data show that the hydride phase was not cubic, but probably tetragonal. The titanium atoms appeared to form a body-centered-tetragonal lattice complex, two titanium atoms per cell, with approximate dimensions: a = 3.12A, c = 4.18A, and c/a =1.34A. This is equivalent to a face-centered-tetragonal complex, four titanium atoms per cell, with approximate dimensions: a = 4.42A, c = 4.18A, and c/a - 0.946A. The presence of the 2.98 and 1.81A neutron lines indicates that the true Bravais lattice is not identical with this lattice complex, but may be primitive tetragonal with dimensions some multiple of those of the complex. The relative intensities of the hydride and a-titanium X-ray lines as functions of overall composition indicated that the hydride, presumably in equilibrium with the a at 100" to 255"C, contained more than 62 atomic pct H. Acknowledgments The experimental work covered in this report was done at Brookhaven National Laboratory, through the courtesy of D. Gurinsky. The cooperation of J. Sadofsky, 0. Kammerer, A. McReynolds, and A. Cendrowski is gratefully acknowledged.

Jan 1, 1957