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By John F. Elliott

STAFF: Editor, Gerhard Derge Acting Editor, Poul G. Shewmon Carnegie lnstitute of Technology Schenley Pork Pittsburgh 13, PO. Editorial Assistant, M. A. Redmerski Production Editor, Otto T. Johnson THE METALLURGICAL SOCIETY: Rich-ard C. Cole, President; Karl L. Fetters, Past-President; J. H. Scoff, Vice President; R. L. Henneboch, Treasurer, R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: R. E. Lund, Chairmon; T. E. Dancy, P. R. Gouwens, W. A. Krivsky, F. C. Longenberg, E. R. Morgan, R.R. Nosh, Poul Queneou, W.O. Philbrook, J. H. Scoff, L. L. Seigle, and M. E. Wadsworth. Review and selection of manuscripts is under the supervision of the following Publications Committees: Extractive Metallurgy Division: M. E. Wadsworth, Chairmon; R. E. Grace, Vice Chairman; D. H. Baker, Jr., G. M. Bell, D. H. Bridges, J. M. Cigon, G. W. Healy, R. A. Lewis, C. E. O'Neill, A. W. Schlechten, R. E. Shinkoskey, and W. W. Stephens. Iron and Steel Division: T. E. Dancy, Chairman; A. Muan, D.W. Murphy, R. D. Pehlke, J. M. Uys, J. 5. Wagstoff, and R. G. Word. lnstitute of Metals Division: R. R. Nash, Chairman, H. H. Johnson, Jr., Vice Chairman; M. R. Achter, P. A. Beck, J. J. Becker, G. F. Bolling, J. 0. Brittain, J. 8. Clark, R. 5. Davis, A. E. Dwight, R. W. Fountain, L. A. Girifalco, E. L. Harmon, J. J. Heger, A. A. Hendrickson, L. Himmel, J. P. Hirth, R. H. Richmao, H.C.Rogers, W. Rostoker, 0. D. Sherby. E. A. Steigawald, R. Steinitz, H. C. Stumpf, R. A. Swalin, W. A. Tiller, W. R. Upthegrove, D. Walton, H.W. Weart, and D. Wilsdorf. Published bimonthly by the American lnstitute of Mining, Metallurgical, and Petroleum Engineers, Inc 345 East 47th Street, New York 17. N. Y. Telephone PLaza 2-6800. Subscription $30 per year for non-AIME members in United States and North, South, and Central America; $32, foreign;$30per $7 50 for AlME members. Single copies, $6.00, single copies foreign, $6.50. The AlME is not responsible for any statement made or opinion expressed in its publications ... Copyright 1963 by the American lnstitute of Mining, Metallurgical, and Petroleum Engineers, Inc....Registered cable address, AlME New York . .. Indexed in Engineering Index, Industrial Arts Index, and Chemical Abstracts . . Second class postage paid ot New York, N. Y., and Ann Arbor, Mich. Volume 227, Number 4.

Jan 1, 1963

By R. W. Heckel, H. P. Cheskis, A. Lawley, M. R. Pinnel

THERE are discrepancies reported in the literature regarding the micro and macro stress-strain behavior of metals and alloys. In particular, Young's modulus and micro yield measurements often show significant variations depending upon the techniques employed.'-" The purpose of this note is to correlate measurements made with four techniques and to indicate where some of these discrepancies might arise. Allied use of these techniques can provide a complete and consistent characterization of micro and macro stress-strain behavior (over the strain range of 10-9 to 10--2 in. in.-') from a minimum number of samples. Techniques. The techniques employed for measuring stress-strain behavior involved the use of a) linear differential transformers, b) SR-4 strain gages, c) longitudinal resonance waves, and d) X-ray diffraction. Specimen geometries and preparations are summarized in Table I for each technique. Differential Transformer and Strain Measurements. An Instron universal testing machine, modified with an alignment device, was used to apply the load via parallel-jaw grips. The signal from the load cell was applied to the Y scale of a Moseley X-Y recorder (sensitivity of 10 lb load per in. chart). The elongation was monitored simultaneously with strain gages mounted on three sides of the rectangular specimen, and with two linear variable differential transformers (LVDT) mounted at 90 deg to one another on faces that also contained the strain gages, Fig. 1. The signal from one of the LVDT's was applied to the X scale of the recorder (sensitivity 40 µ in. elongation per in. chart) in order to trace a continuous load-elonga-tion curve. Concurrently, the strain on the same face (i.e., the face monitored by the LVDT) was recorded by the corresponding strain gage. A stress-strain curve was plotted from the load cell-strain gage data and was compared to the stress-strain curve (converted from load-elongation) plotted from the continuous load cell-LVDT trace. Identical Table I. Description of Specimens Used in the Present Study Material Dimerisions Preparation Condition 99.99 pct A1 tensile 318 by 3/16 by 3 in. as cast ingot; cut annealed specimen on diamond wheel 2024 A1 tensile 318 by 3/20 by 31/2 in. vacuum hot annealed specimen pressed sheets; cut on diamond wheel 99.99 pct Al 3116 by 3/16 by 2 in. cut from tensile prestrained dynamic modulus specimen after 10"* in. specimen test per in. 2024 A1 dynamic 3/20 by 3/20 by 2 in. vacuum hot annealed modulus specimen pressed sheets; cut on diamond wheel 2024 A1 X-ray gage section 112 by vacuum hot annealed specimens 1/4by1/20in. pressed sheets; cut on diamond wheel

Jan 1, 1970

By Rustum Roy, E. F. Osborn

THE investigation discussed in this paper concerns phase equilibria in the alumina-silica-water system. Studies in this system are part of a re¬search project sponsored by the Geophysics Branch of the Office of Naval Research2 directed toward increasing knowledge of the stability relations of metamorphic mineral assemblages. Inasmuch as metamorphic rocks consist largely of aluminosilicate struc¬tures, many of them hydrated, the system alumina-silica-water is a logical starting point for the systematic laboratory study of metamorphic mineral systems. Although logical, this is not, however, an easy approach to the problem because of the very great difficulty of obtaining transformations among structures in response to changes in temperature, pressure, and con¬centration. Commonly equilibrium among the phases in this system is exceed¬ingly difficult to attain. New laboratory techniques are required to produce certain structural rearrangements, such as inversion of diaspore to boehmite or the transformation of alumina-silica mixtures to andalusite or kyanite. Phase equilibrium data for the alumina-silica-water system are consequently only partly complete, and only a summary progress report is presented here. Crystalline phases in the alumina-silica-water system are numerous and many are common minerals. The oxide components exist as: quartz, tridymite, cristobalite, corundum, water, and ice. Binary compounds occurring naturally are: sillimanite, andalusite, kyanite, and mullite in the alumina-silica system and gibbsite, boehmite, and diaspore in the alumina-water system. The most abundant among the ternary compounds is the composition A12O3.2SiO2.¬2H2O, existing in the four structural modifications, kaolinite, nacrite, dickite, and halloysite. The hydrated form of halloysite, A12O3.2SiO2.4H2O, is here called endellite. Pyrophyllite, A12O3.4SiO2.H2O, is the third ternary compound of natural occurrence. In addition to these minerals, two other ternary crystalline phases have been encountered in this study. The first is a structure resembling montmorillonite and corresponding perhaps to the pure aluminian end member of the beidellite series. The other has a composition approximating A12O3.2SiO2.H2O but its composition and structure are still in doubt. LABORATORY PROCEDURE In these laboratory studies, a starting material such as an alumina-silica gel or one or more of the crystalline phases is wrapped in platinum foil,

Jan 1, 1952

By G. A. Beiswenger

The application of the law of supply and demand to the sale of crude oil is generally conceded, but the motives underlying the buyer's (refiner's) demands are not always obvious to the seller (producer). In some cases this obscurity has led to the conclusion that the refiner may be unnecessarily particular when he selects one crude and rejects another. This preference, however, is very largely the reflection of the refiner's product demands and the quality of the stocks obtainable from the selected crude. The purpose of this paper is to point out critical characteristics of the major classes of refined products and to show how crudes vary in their suitability for such products. With relatively few exceptions, available processing methods and addition agents make it theoretically possible to produce any type of refined product from any crude source, although it may not be economi-cally sound to do so. The widespread application of thermal cracking for converting higher boiling stocks into gasoline is well known. More recently cracking and refining in the presence of catalysts9 have been developed, as well as various processes for polymerizing lighter hydro-carbons into gasolines having desirable characteristics.6 For several years, selective solvents have been applied commercially to refining inferior quality kerosene, Diesel fuel and lubricating oil distillates .3 Improved methods for refining lubricating oils from crude residua,4 formerly suitable only for fuel, are now in use and a number of special solvent processes are available for dewaxing lubricating oils to low pour point.5 These improved refining methods have been developed not only to meet the demand for improved product quality but also to enable the refiner to obtain quality products from crude sources that would not yield such products by the older refining methods. In many cases, the utilization of these modern refining tools necessi-tates an appreciable expenditure for equipment as well as added manufac-turing costs, and their application therefore must be justified economically. Despite the availability of such tools, the added processing costs involved and yields obtainable may render their application entirely impractical. To illustrate this point, inspections of typical cuts from various crudes

Jan 1, 1940

By Ralph H. Sweetser

MUCH progress in -blast-furnace construction and in the manufacture of firebrick for furnace linings has been made since the publication of Bulletin 130 of the U. S. Bureau of Mines on "Blast-Furnace Breakouts, Explosions and Slips, and Methods of Prevention," by F. H. Willcox in 1917. At the time of publishing this report comparatively little information was available to blast-furnace men as to the fundamental facts relating to the character of blast-furnace refractories. Some of the accepted theories of only a few years ago have been completely reversed. The mortality of blast-furnace linings used to be so great that nearly every furnace plant had one or more complete linings in the brick shed ready for use in case of a lining suddenly "going out"; it was generally accepted that a furnace could not "keep her lines" more than two or three years at best, and often a hot spot in the shell would develop, or a breakout occur in the hearth or bosh within a year or two after blowing in on a new lining. In some respects these frequent relinings were not so detrimental as to he a complete loss because they afforded opportunities to take advantage of advances in blast-furnace practice. At present the cost of relining has greatly increased, but the life of a lining has also increased. Anything less than five years on a lining is now considered a short blast.

Jan 1, 1932

By Kenneth S. Ritchie

THE discovery well of the world's -deepest oil producing structure, University 1-B of Group No. One Oil Corporation, in the Big Lake oil field, Reagan County, Texas, has had a remarkable record. The well is outstanding for the following reasons: (1) It is the world's pioneer well to produce. oil in commercial quantities from a structure 8500 ft. below the earth's . surface; (2) this well was the only. producer from the 8500-ft. pay for a period of 17 months and 24 days; (3) the flow of the discovery well has been free from-the customary changes at the casinghead, with the exception of putting on a back-pressure of 185 lb.; and, (4) the well's daily production of oil and gas increased rather steadily for 17 months and 18 days from an initial of 40 bbl. per day to a maximum of 2926 bbl. per day, and then six months later, after a period of decline and self-readjustment to subsurface changes caused by six more deep producers, the well set its real record for one day's production of oil at 2950 bbl

Jan 1, 1931

By Charles Macdonald

WROUGHT-IRON eye-bars for bridges and roofs, designed upon what is known as the pin connection system, have been successfully manufactured in this country for some years. The most approved methods employed have been the hydraulic upsetting process, and by die-forging under a hammer. In upset eyes the fibre of the iron is necessarily much distorted ; and in bars of considerable size, this disturbance seriously impairs the strength of the connection. Mr. Collingwood, in discussing my paper on "Proportions of the Heads of Eye-bars," read before the American Society of Civil Engineers, Jan. 21st, 1874, submitted sketches of certain bars intended for the anchorage of the East River bridge, which had been exposed to the action of sulphuric acid a sufficient length of time to thoroughly cleanse the surfaces, and expose the condition of the fibre. These sketches are here reproduced for the purpose of illustrating the effect of this methpd of manufacture. In Figs. 1, 2, and 3, it will be observed that the fibres at A, and E, have been folded back upon themselves and otherwise twisted and disturbed, in a manner not calculated to inspire confidence in the integrity of the connection. To compensate for this defect, a large excess of metal is thrown into the eye; but a method of manufacture which involves such a necessity, even although it be the one giving the best results thus far, all things being considered, is far from being perfect.

Jan 1, 1879

By R. B. Snow

This paper describes a technique of polishing and etching specimens of open-hearth furnace slags or hearth aggregates for identification of the crystalline constituents —lime (CaO), tricalcium silicate (3CaO.SiO2), dicalcium silicate (2CaO.-SiO2), rnonticellite (CaO.MgO.SiO2), or forsterile (2MgO.SiO2), with especial em-phasis on the mineral merwinite (3CaO.-MgO.2SiO2). With proper standardization, this identification does not require the use of the petrographic microscope. The composition of basic open-hearth slags and furnace bottoms falls, almost without exception, within systems containing CaO, MgO, 'IFeO,,, MnO and SiOz, in which the number of basic molecules so greatly exceeds the orthosilicate ratio (two molecules of base to one of silica) that free basic oxides, and combinations between them such as alumi-nates or ferrites, are present in cooled specimens. Orthosilicates of (CaO + NgO) are the most common in such specimens, since in nearly all cases, except premelt slags, the molecular ratio of (CaO + MgO) to SiO, is more than 2 to I. When sufficient lime is available it combines with the silica to form dicalcium silicate (2Ca0.Si02), which contains little, if any, IvfgO, FeO or MnO in solid solution whereas the latter oxides combine to form the oxide solid solution known as periclase. If the lime present is insufficient to form dicalcium silicate (2Ca0.Si02) it combines with Mgo to form either merwillite or moIlticellite (SiOz); these minerals take little if any FeO or MnO into solid solution and the remaining MgO, FeO and hInO combine as periclase. This generalization seems to be valid for basic slags and furnace bottoms, since minerals such as Ca0.MnOSi02 and CaO.FeO.SiOz are found only in slags in which the lime-silica ratio is less than 2 and are not observed in 'pecimens from furnace bottoms. The identification of crystalline constituents in such materials, especially of fine crystals in the groundmass, is difficult under the petrographic microscope. They are often masked by their neighbors because of their small size in relation to the thickness of the thin section and because of the presence of Opaque Or colored constituents. The indices of refraction and the optical sign of the mineral are sometimes difficult to determine because of the small size or because Of twinning or of inclusions within the crystal. Moreover, the positive identification of merwinite (3Ca0.Mg0.2Si02) from its optical properties is usually difficult in the presence of dicalcium silicate (zCaO.SiO2). CaO, MgO, jCa0.Si02 and 2Ca0.SiOz in open-hearth 'lags have been identified for a number of years in the U.S. Steel Corporation Laboratory by the usual

Jan 1, 1948

By R. B. Snow

This paper describes a technique of polishing and etching specimens of open-hearth furnace slags or hearth aggregates for identification of the crystalline constituents —lime (CaO), tricalcium silicate (3CaO.SiO2), dicalcium silicate (2CaO.-SiO2), rnonticellite (CaO.MgO.SiO2), or forsterile (2MgO.SiO2), with especial em-phasis on the mineral merwinite (3CaO.-MgO.2SiO2). With proper standardization, this identification does not require the use of the petrographic microscope. The composition of basic open-hearth slags and furnace bottoms falls, almost without exception, within systems containing CaO, MgO, 'IFeO,,, MnO and SiOz, in which the number of basic molecules so greatly exceeds the orthosilicate ratio (two molecules of base to one of silica) that free basic oxides, and combinations between them such as alumi-nates or ferrites, are present in cooled specimens. Orthosilicates of (CaO + NgO) are the most common in such specimens, since in nearly all cases, except premelt slags, the molecular ratio of (CaO + MgO) to SiO, is more than 2 to I. When sufficient lime is available it combines with the silica to form dicalcium silicate (2Ca0.Si02), which contains little, if any, IvfgO, FeO or MnO in solid solution whereas the latter oxides combine to form the oxide solid solution known as periclase. If the lime present is insufficient to form dicalcium silicate (2Ca0.Si02) it combines with Mgo to form either merwillite or moIlticellite (SiOz); these minerals take little if any FeO or MnO into solid solution and the remaining MgO, FeO and hInO combine as periclase. This generalization seems to be valid for basic slags and furnace bottoms, since minerals such as Ca0.MnOSi02 and CaO.FeO.SiOz are found only in slags in which the lime-silica ratio is less than 2 and are not observed in 'pecimens from furnace bottoms. The identification of crystalline constituents in such materials, especially of fine crystals in the groundmass, is difficult under the petrographic microscope. They are often masked by their neighbors because of their small size in relation to the thickness of the thin section and because of the presence of Opaque Or colored constituents. The indices of refraction and the optical sign of the mineral are sometimes difficult to determine because of the small size or because Of twinning or of inclusions within the crystal. Moreover, the positive identification of merwinite (3Ca0.Mg0.2Si02) from its optical properties is usually difficult in the presence of dicalcium silicate (zCaO.SiO2). CaO, MgO, jCa0.Si02 and 2Ca0.SiOz in open-hearth 'lags have been identified for a number of years in the U.S. Steel Corporation Laboratory by the usual

Jan 1, 1948

By E. T. Turkdogan, L. J. Martonik, R. J. Fruehan

Electrochemical measuretnents of the solid oxide electrolyte galvanic cells CY-Cr2O3 I ZrO2 (CaO) 1 O (in Fe alloy) CY-Cr2O3 I Tho2 (Y2O3)I O en Fe alloy) have been made at 1600°C (2912°F) in order to test the Performance of such cells at liquid steel temperatures. The oxygen pvobe (cell) consists of a disk of ZrO2 (CaO) or Tho2 (Y2O3) electrolyte fused at one end of a silica tube filled with a mixture of Cr-Cr2O3 which is the reference electrode. Upon immersion in liquid steel, the electromotive force readings achieve a steady value within a few seconds, and remain steady for 30 win or more. The perforwzance of the probes has been tested using Fe-O, Fe-Si-O, Fe-Cr-O, Fe-V-O, and Fe-Al-O alloys; the oxygen contents of liquid steel derived from the measured electromotive forces are in satisfactory agreement with those determined by arulysis. Use of the probe in the deoxi-datiorz of steel, in laboratory experiments, is discussed. The results indicate that there is insignificant electronic conductivity in ZrO2(CuO) at oxygen activities down to those corresponding to 10 ppm in steel. At lower oxygen activities, probes tipped with ThOn (Y2O3) disks perform satisfactorily at oxygen activities down to 1 ppm O or less. THE key to the control of deoxidation of steel is a sensing device to measure rapidly the concentration of oxygen in liquid steel in the furnace, ladle or tun-dish at any desired stage of deoxidation. The analysis of the cast steel by the neutron-activation or vacuum-fusion method gives total oxygen as oxide and silicate inclusions. This analysis is important for guidance to steel cleanliness; however, such a postmortem is of little value in the control of deoxidation of liquid steel. At the General Meeting of the American Iron and Steel Institute in New York, 1968, Turkdogan and Fruehan' presented a paper on the preliminary results of the work done in this laboratory on rapid determination of oxygen in steel by an oxygen probe. Details of the work done in this laboratory leading to the development of a galvanic cell for the determination of oxygen in liquid steel, and the results of the tests made are given in this paper. It was through Wagner's contributions, since the early Thirties, to the physical chemistry of semiconductors in general that it ultimately became possible to construct galvanic cells for application at high temperatures. In 1957, Kiukkola and wagner2 successfully demonstrated the use of several solid electrolytes in measuring the free energies of several chemical reactions, in particular, the use of lime-stabilized zir-conia in high-temperature oxidation reactions. Starting 7 years later, a number of papers appeared in the technical literature3-' demonstrating possible applicability of galvanic cells for the determination of oxygen in liquid steel. In the earliest work, Japanese investigators3j4 experimented with various types of reference electrodes, e.g., graphite-saturated liquid iron at 1 atm CO or Ni-NiO mixtures; the results obtained, though promising, were not of sufficient accuracy. Except for the work of Baker and West,6 all other investigators5,7,8 showed that ZrO2(CaO) electrolyte could be used for this purpose. The main part of the galvanic cell used by Fischer and ~ckermann' and by schwerdtfeger7 (the latter work was done in this laboratory), consisted of a ZrO2(CaO) tube, -1 cm ID, closed at one end, with a platinum contact wire fixed mechanically inside the closed end. The tube was flushed with a gas of known oxygen partial pressure, e.g., air, CO-CO2 or H2-CO2 mixtures; gas along with the platinum lead wire served as the reference electrode. The oxygen contents derived from measured electromotive forces agreed reasonably well with the oxygen contents determined by vacuum-fusion analysis. It is evident from recent investigations that the electromotive force technique using a solid oxide electrolyte is fundamentally well suited for the determination of oxygen in liquid steel. However, it is equally clear that the cell arrangement of the type as commonly used is in need of considerable improvement, as it exhibits several shortcomings for industrial and even laboratory use. 1) Because of its size, the zirconia tube, though stabilized, has a poor resistance to thermal shock. 2) Fine pores and microcracks, which are invariably present in zirconia tubes, are detrimental to the satisfactory operation of the cell, particularly when gas reference electrodes are used. 3) Air or carbon dioxide reference electrodes give rise to high electromotive force readings; as a result, the determination of oxygen in steel becomes less accurate. For higher accuracy, the oxygen partial pressure of the reference electrode should be in the range similar to that of oxygen in steel. 4) Even in laboratory experiments, difficulties are experienced when flushing the tube with gases and maintaining the proper gas flow rate. Fischer and Ackermann,' who used air as the reference electrode, reported that when the flow rate was too low, furnace gases would leak into the electrolyte tube, therefore lowering the oxygen potential and measured electromotive force. The required flow rate in order to avoid leakage depended on the tightness of the electrolyte tube which varied with different tubes, thus making it difficult to predict in advance the required flow rate. However, if the flow rate is too high the inside wall of the electrolyte tube would be cooler than the wall

Jan 1, 1970

By Gene D. Clayton, Robert R. Dimock

A time-consuming and expensive preshearing program to minimize the adverse effects of blasting on slope stability at Kennecott Copper Corp.'s Ruth Pit in east-central Nevada has been eliminated in favor of down-the-hole, nonelectric delayed blasting which can produce a smooth wall effect and improve blast fragmentation. The new blasting approach resulted from a Kennecott engineering investigation aimed at improving the stability of the extremely variable rock conditions found throughout the pit by reducing the vibrational energy imparted to the walls with conventional bench blasts.

Jan 4, 1977

By Charles Macdonald

Wrought-iron eye-bars for bridges and roofs, designed upon what is known as the pin connection system, have been successfully manufactured in this country for some years. The most approved methods employed have been the hydraulic upsetting process, and by die-forging under a hammer. In upset eyes the fibre of the iron is necessarily much distorted ; and in bars of considerable size, this disturbance seriously impairs the strength of the connection. Mr. Collingwood, in discussing my paper on "Proportions of the Heads of Eye-bars," read before the American Society of Civil Engineers, Jan. 21st, 1874, submitted sketches of certain bars intended for the anchorage of the East River bridge, which had been exposed to the action of sulphuric acid a sufficient length of time to thoroughly cleanse the surfaces, and expose the condition of the fibre. These sketches are here reproduced for the purpose of illustrating the effect of this method of manufacture. In Figs. 1, 2, and 3, it will be observed that the fibres at A, and E, have been folded back upon: themselves and otherwise twisted and disturbed, in a manner not calculated to inspire confidence in the integrity of the connection. To compensate for this defect, a large excess of metal is thrown into the eye; but a method of manufacture which involves such a necessity, even although it be the one giving the best results thus far, all things being considered, is far from being perfect.

Jan 1, 1879

By J. W. Putman, N. J. Grant, D. S. Bloom

SEVERAL recent determinations of the melting S point of pure chromium have been reported which give values of 1845°C1; 1895°C,² 1930°C,³ 1860°C,' and 1890°C.5 because of this wide spread of values, it appeared desirable to make one additional attempt to obtain a more accurate, reliable figure. bloom and Grantx recently reported a phase transformation in chromium:.--- it was desired to check this, too, in the course of checking the melting point. To accomplish this, a much higher purity chromium was required. Electrolytic chromium containing about 0.5 pct 0 was crushed to a finer size and was then annealed in highly purified, dried hydrogen at 1375°C for 100 hr. This treatment produced chromium with about 0.008 pct 0, 0.002 pct N, and negligible carbon. The balance of the impurities was 0.3 pct Fe, 0.03 pct Si, 0.004 pct S, and less than 0.001 pct Mo. This chromium was melted in a stabilized zirconia crucible under pre-purified argon, using induction heating. Temperature measurements were made with annealed wolfram-molybdenum thermocouples and a Leeds and Northrup Speedomax Recording Potentiometer. The thermocouples were annealed for 1 min in hydrogen at a temperature of about 2400°C. Each leg of the thermocouple was immersed in an ice-water mixture using mechanical connectors to the lead wires. The thermocouple tip was immersed in the molten chromium in a zirconia protection tube which introduces an error of about 3°C as a temperature drop through the walls of the tube. The weight of chromium was about 183 g. The dimensions of the melt in the crucible were about 1.25 in. diam x 2 in. high. The tip of the thermocouple was held about ½ in. from the bottom of the crucible. Two new thermocouples were used with the above set-up giving the results shown in Table I. Since this chromium is purer than that used by Greenaway, Johnstone and McQuillan,' by Carlile et al.,4 and other investigators,²,3 it is believed to be the more accurate. Thermocouple aging effects which are believed responsible for the high value of 1930°C³ were avoided in this work. This value of 1903°C is correct to about ±10°C. The right hand column lists the temperature of the a ? ß transformation on heating and the ß ? a on cooling.3 A sample curve is shown in Fig. 1. The value so determined is 1840°C + 15°C. Fig. 1 gives adequate evidence that there is a transformation in chromium at high temperatures.' References 'H. T. Greenaway, S. T. M. Johnstone, and M. K. McQuillan: High Temperature Thermal Analysis USing the Tungsten-Molybdenum Thermocouple. Journal Inst. Metals (November 1951) 19, p. 109. ²J. W. Putman, R. D. Potter, and N. J. Grant: The Ternary System Chromium-Molybdenum-Iron. Trans. A.S.M. (1951) 43, p. 824. ³D. S. Bloom and N. J. Grant: Chromium-Nickel Phase Diagram. Trans. AIME (1951) 191, p. 1009; Journal of Metals (November 1951). ' S. J. Carlile, J. W. Christian, and W. Hume-Rothery: The Equilibrium Diagram of the System Chromium-Manganese. Journal Inst. Metals (1949) 76, p. 169. 5G. Grube and R. Knabe: Ztsch. Elektrochemie (1936) 42, p. 793.

Jan 1, 1953

By L. H. Van Vlack, T. Y. Tien, R. J. Martin

The phase relationships of the MnTe-MnS system were studied by DTA procedures. There is an eutectic at 810°C with about 10 mole pct MnS-90 mole pct MnTe. An eutectoid occurs at about 710°C with approximately 7 mole pct MnS where the MnTe(NaCl) solid solution dissociates on cooling to MnTe(NiAs) and MnS. There is very little solid solubility of MnTe in MnS. ALTHOUGH MnS may exist in three different crystal forms,' only the NaC1-type phase is stable.2 Above 1040°C, MnTe also has the cubic NaC1-type structure. Below that temperature, MnTe changes to the NiAs-type structure.3 This phase transition is rapid for both heating and cooling. As a result the high-temperature crystal form of MnTe cannot be retained at room temperature. Because MnO, MnS, and MnSe are all stable with the NaC1-type structure, and MnTe has this structure at high temperatures,4 solid solution formation could be expected among these compounds. It is interesting to note, however, that a complete series of solid solutions exist only in the MnS-MnSe system,' and that the solid solution is quite limited in the MnO-MnS system.' The MnSe-MnTe system possesses a complete series of solid solutions at high temperatures with separation at lower temperatures.7 Although ion size may be critical in the miscibility of MnO-MnS, it is quite possible that the bond type plays a more important role with the miscibility of MnSe-MnTe. This would permit us to speculate that the miscibility gap would be extensive in the MnTe-MnS system. EXPERIMENTAL Preparation. The samples were prepared by mixing and compacting MnTe and MnS powders. The MnS was previously prepared through the sulfur reduction of Mnso4.8 The MnTe had been prepared by mixing and compacting double vacuum distilled metallic manganese and high-purity tellurium in stoichiometric ratio modified with 1 wt pct excess tellurium. The compacted powders were put in a graphite crucible which was sealed in an evacuated vycor tube. The free space in the vycor tube was made minimal to reduce the loss of tellurium. The sealed assembly was then heated slowly to about 500° C where the free manganese and tellurium reacted vigorously, melting the MnTe which formed. Only one phase, MnTe, was detected by X-ray powder patterns and metallographic techniques. Each compact of MnTe-MnS was placed in a graphite crucible and then sealed in an evacuated vycor tube. The samples were heated at 1250°C for 4 hr and furnace-cooled. Microscopic examination revealed no third phase beyond MnS and MnTe. A typical microstructure is presented in Fig. 1. Identification. X-ray powder patterns were obtained using 114.6 mm Debye-Scherrer camera and Fe-Ka radiation. Mixtures of cubic MnS and hexagonal MnTe were observed in all of the compositions prepared. No lattice parameter change was noticed among different compositions, indicating no solid solution could be retained at room temperatures between these two end-members. A lattice parameter of 5.244Å for MnS was obtained by the Nelson and Riley9 extrapolation method using the diffraction lines of (h2 + k2 + 12) equal 12, 16, 20, and 24. The values, a = 4.145Å and c = 6.708Å, for hexagonal MnTe were obtained from the (006) and (220) lines in the back-reflection region. These values agree well with the values reported by Taylor and Kag1e.10 Differential Thermal Analysis. A differential thermal analysis procedure was used to determine phase relationships since the high-temperature equilibrium conditions could not be retained for examination at room temperature, even when the sealed samples (~0.5 g) were quenched in water. The samples were sealed in an evacuated 4 mm vycor tube with a recess in the bottom to accept a thermocouple. An Al2O3 reference was similarly prepared and the two placed within a piece of insulating fire brick to dampen spurious temperature changes within the furnace. The furnace was controlled by a mechanically driven rheostat which increased the temperature at a rate of about 15°C per min. Known phase changes in the Pb-Sn system1' and the a-to-ß quartz inversion12 were used for calibration

Jan 1, 1969

By P. Greenfield, P. A. Beck

The phase is a hard and extremely brittle material with a tetragonal crystal structure, containing 30 atoms per unit cell' It occurs in many binary and ternary alloys of the transition elements. The existence of twelve a phases has been reported in binary alloys of metals from the group vanadium, chromium, molybdenum, and tungsten with metals from the group manganese, iron, cobalt, and nickel. It is a characteristic fact that the composition of the o- phases in the various binary systems is not the same. Rather, there is a gradual shift in composition, for instance in the series of chromium a phases, approximately as follows: CrMn,, FeCr, Cr3Co,. In recent years several ideas have been put forward to account for this variability of composition. SullyZ proposed that a was a type of electron compound, characterized by 1.7 electrons per atom in excess of the number required to fill the Pauling atomic orbitals. These excess electrons were supposed to just fill the first Brillouin zone of the u structure. However, later work indicated that the phase is ferromagnetic at low temperatures, so that a- is unlikely to be a full zone compound.~ Another proposal,* which is also based on the structure of the transition elements advanced by Pauling, and in fact leads to essentially the same a compositions as Sully's theory, suggests that the u phase is characterized by a constant number of electron vacancies per atom. The electron vacancy numbers N,. used were originally the same as those in the Pauling theory, but were later modified empirically vn order to bring about better agreement with data for the p phase in certain ternary systems. For alloys, N,, was calculated on the assumption of simple additivity from the electron vacancy numbers of the components, as follows: N,. = 4.66 (Mo + Cr + V) + 3.2 (Mn) + 2.2 (Fe) + 1.71 (Co) + 1.6 (Ni). On this basis a reasonably constant value of N, = 3.4 was obtained for all of the binary u phases and a fairly constant value of N,, = 3.1 for the various p phases. More recently, Bloom and Granta pointed out that a similar correlation with the total number of 3d and 4s electrons per atom is also fairly well fulfilled and concluded that no reference need be made to the Pauling theory. This proposal does not lead to the same binary a compositions as the one described above, so that the relative merits of the two proposals may be determined on the basis of direct comparison with experimental composition data. The purpose of the present paper is to provide such a comparison. Since the experimental data for the composition ranges of several of the known u phases were rather incomplete, it was decided to carry out new experimental determinations for many of the binary systems. Experimental Procedure The alloys were prepared by induction melting in recrystallized alumina crucibles, either in vacuum or in helium atmospheres. Some aluminum was picked up from the crucibles in the alloys of high vanadium content, but this was minimized by keeping the alloys in the molten state for as short a time as possible. The maximum aluminum impurity was 0.13 wt pct by chemical analysis, in an alloy containing over 50 wt pct V. In general, the as-melted compositions agreed accurately with those obtained by chemical analysis. In the case of manganese, however, losses inevitably occurred; consequently all manganese alloys were analyzed. Specimens of all alloys were annealed at temperatures ranging from 1000" to 1300°C in an atmosphere of purified 92 pct helium and 8 pct hydrogen mixture. All manganese alloys were sealed in quartz tubes under vacuum before annealing. The specimens were held at temperature for between four and eight days before being quenched into cold water. Alloys were prepared for microscopic examination by mechanical polishing, usually followed by electrolytic etching. X-ray diffraction specimens were prepared by crushing the homogenized alloys, and by reanneal-ing the obtained powders in evacuated quartz tubes for a few hours at the temperature of the lump anneal. X-ray diffraction patterns were made with unfiltered chromium radiation, using an asymmetrical focusing camera of high dispersion. Using microscopic and X-ray techniques jointly, the accuracy

Jan 1, 1955

By Y. Jeannin, C. Mannerskantz, F. D. Richardson

Measurements have been made between 1040o and 1300°C of the equilibrium between chromium metal, chromic oxide, hydrogen, and water. The results are in closer agreement with those deduced from recent thermal data than with previous equilibrium values. They lead to the equation ?G°1300°-1600°k = -266,700 + 59.95T ± 300 cal for the formzation of a mole of Cr2O3 from chromium and oxygen. This same equilibrium has been studied with the chromium dissolved in solid iron, and in this way chromium activities in Fe + Cr alloys have been established. The measuremenis show that there are substantial positive deviations from ideality in the a, and b phases, and support the results obtained by Heymer and Kubaschewski against those of other investigators. There is considerable disagreement between existing data,1"4 which is referred to in the Discussion, concerning the equilibrium Cr2O3 + 3H2 = 2Cr + 3H2O [l] There is also substantial disagreement between the results obtained by various investigators5-' who have measured the activities of chromium in its alloys with iron by the Knudsen effusion vapor pressure method. In view of the importance in metallurgical processes of chromium and its oxide and of Fe-Cr alloys, an attempt has been made to study equilib- rium [I] both with pure chormium metal and with chromium alloyed with iron, at temperatures between 1040o and 1300oC. From the work with the alloys it is possible to derive the chromium activities from the relationship

Jan 1, 1963

By Oliver Bowles

AUTOMOTIVE TRANSPORT by highway, which has become indispensable to modern life either in peace or war, involves the use of powerful machines, many of which travel at high speed. To start, accelerate, and stop each motor vehicle demands the use of clutch and brake. Friction is applied intensively to both these mechanisms, and their linings must therefore be of materials that will resist wear and that will not ignite with the heat of friction. Asbestos, that curious fire-resisting: natural fiber that may be woven into unburnable cloth, is eminently suitable for this special' use, and no satisfactory substitute for it has yet been found Because- asbestos is regarded as absolutely essential to all types of motor transport on land, and in addition is indispensable to. many .other kinds of machines and equipment, the situation of the- United State's with respect to supplies of-raw-material-is of special interest: From the standpoint of national self-sufficiency, conditions are far, from satisfactory, for United States mines furnish only three to four percent of the total domestic require-

Jan 1, 1938

By J. J. Friel, E. S. Erickson

Dolomite-fluxed pellets of various compositions were made from magnetite concentrate, hematite concentrate and a concentrate containing a natural mixture of both. Physical properties and reduction test results were used to ascertain proper compositions and firing temperatures. These pellets were subjected to physical tests and to reduction tests. Petrographic and electron microprobe examinations were made to evaluate the effect of composition and fining on the phase assemblage. We interpreted our test results in terms of chemistry and microstructure and related these to properties. This approach enabled w to determine the composition best suited to each of the three concentrates. Compared with acid pellets, dolomite- fluxed pellets of the optimum compositions had similar physical properties but swelled less, softened at a higher temperature, and reduced faster and more completely.

Jan 1, 1983

By Scott Tzcrner

WITHIN recent years people have begun to realize the importance and significance of the mining and allied industries. The leading part the engineer plays in civilization is becoming recognized. However accurate quantitative knowledge of the industrial importance of mining is still seldom possessed except by those close to this business. It is true that there are a few who go to the extreme and represent the whole progress of civilization as a reflection of man's gradual mastery of mineral utilization, but on the whole, the magnitude of the-industry is underestimated. In this paper I shall call attention briefly to the importance of mining in the United States, in Canada, and in the world. Ordinarily, the annual primary mineral production of the United States is about $5,500,000,000. The average for the last 5 years has been a little over that, but last year, sadly enough, it was less than 31/4 billion. Just now, we are on the decline, and have been for the last two years. In Canada, the 5-year average was about $268,000,000, and last year it was 227 million. Due in part to gold mines (in 1930, for the first time, Canada's gold production exceeded that of the United States), the Canadian average is holding up better than ours. Average world mineral production over the last -5 years has been estimated at about $12,000,000;000 whereas in 1931 it was less than than 8 billion.

Jan 1, 1932

Jan 1, 1897