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By J. E. Hilliard

Isobaric sections of the eutectoid region of the iron-carbon phase diagram have been exgerimentally determined at 35, 50, and 65 kb. The phase boundaries were located by metallographic analysis of specimens quenched after equilibriatwn at known temperatures and pressures. With increasing pres -sure a pronounced decrease in the solubility of FesC in austenite was observed together with a depression of the eutectoid temperature. These two effects resulted in a shift of the eutectoid composition toward a lower carbon content; at 65 kb the eutectoid was at less than 0.2 wt pct C. These results are in qualitative agreement with thermodynamic calculations. It has also been shown by calculations that Fe3C in contact with saturated austenite will be stable with respect to both graphite and diamond formation at all pressures above -3.5 kb. 1 HE investigation described in this article was part of a more general study of the effect of high pressure on transformations in Fe-C alloys. Thermodynamic calculations and exploratory runs made in 1959 at the start of the program indicated an appreciable change with pressure in the phase equilibria of Fe-C alloys. However, the calculations were not considered reliable enought to provide the quantitative information required for the interpretation of the effect of pressure on the kinetics of transformations. An experimental investigation was therefore made to determine a series of isobaric sections of the eutectoid region of the phase diagram at pressures up to 65 kb. EXPERIMENTAL PROCEDURE Materials. Seven alloys with analyzed carbon contents of 0.10, 0.20, 0.38, 0.60, 0.77, 0.93, and 1.20 wt pct C were prepared from Ferrovac" iron and high-purity graphite induction melted in magnesia crucibles under argon. The ingots were hot worked and swaged down to 0.19-in.-diam rod which was then centerless ground to a final diameter of 0.125 in. Samples for chemical and spectrographic analyses were taken from each end of the rods. The prin- cipal impurities were found to be Ni, Al, Co, and Si which were present in amounts up to 0.03, 0.02, 0.01, and 0.01 wt pct, respectively. Specimens were prepared by slicing the ground rods into pills 0.06-in. thick which were silver plated to reduce decarburization during the equilibration. Silver was chosen for this purpose because of its very low solubility for carbon and its mutual immisicibility with iron. High-Pressure Apparatus. The high-pressure runs were carried out in the "Belt" apparatus.' As shown in Fig. 1, this consisted of a cylindrical cell compressed between two Carboloy punches loaded by a uniaxle press. Radial support to the cell was given by the "belt" which was a Carboloy die heavily prestressed by a series of steel binding rings. Laminated gaskets of lava and metal separated the punches from the inner surface of the "belt". A cross-section of the high-pressure cell is shown in Fig. 2. Two specimen pills were located inside a resistance heater of 0.20-in.-diam Nichrome tubing. The ends of the tube were sealed with alumina and lava pills tamped in place after the

Jan 1, 1963

By Edward M. Kawenski

Float dust deposits in return airways in bituminous coal and lignite mines present a special explosion hazard. Research is in progress at the Bureau of Mines experimental coal mine to evaluate the degree of the hazard and to develop measures for preventing dissemination of dust into the ventilating air current. To determine the extent of this hazard prevailing in operating coal mines, 711 dust samples were collected in 50 mines located in the major coal fields of the United States. The mean quantity of coal and the incombustible content of the dust in the samples were determined. The term "float dust" is used to designate particles smaller than 74 microns in diameter (particles passing a No. 200 sieve) which have settled from the air current. Dust usually found in roadways and in working places is coarser than float dust, and is termed "coarse dust" (particles passing a No. 20 sieve). Variations in amount and incombustible content of coarse dust in a midwestern mine were studied previously.

Jan 1, 1963

By R. S. McClain

Continuous-circuit flotation and batch-scale precipitation tests were made by the Bureau of Nines to determine rejection of carbon and recovery of fluorine and aluminum compounds from aluminum reduction plant residues, About 40 to 60 pounds each of aluminum fluoride and cryolite are lost for each ton of aluminum produced. Gasoline and turpentine were satisfactory for floating carbon from both fresh water and saturated solution systems. Soluble fluorine and aluminum compounds were recovered by precipitation with sodium aluminate and carbon dioxide. Over 99 percent of the carbon was removed by flotation. Fluorine and aluminum recoveries up to 77 and 63 percent, respectively, were obtained in a combined precipitate and nonfloat product, In the fresh water system the combined product was mostly cryolite with some gibbsite. In the saturated solution system the product was mostly sodium fluoride, some cryolite, and minor amounts of gibbsite.

Jan 1, 1963

By d&apos, Kathleen J. Amico

THIS SUMMARY appears in Minerals Yearbook volumes I and III, which cover mineral production in the United States, its island possessions, the Canal Zone, and the Commonwealth of Puerto Rico, as well as the principal minerals imported into and exported from the United States. The several commodity and area chapters contain further details on production. A summary table comparing world and U.S. mineral production also is included. Mineral production may be measured at any of several stages of extraction and processing. The stage of measurement used in the chapter is normally what is termed "mine output." It usually refers to minerals in the form in which they are first extracted from the ground, but customarily includes for some minerals the product of auxiliary processing operatons at or near mines.

Jan 1, 1963

By D. J. Bauer

Solvent extraction techniques were used to determine the extraction sequence of yttrium and the rare-earth elements in an amine solvent extraction system. Single-stage extraction with Primene 81-R resulted in separation factors of 3.8 between yttrium and dysprosium and 25 between yttrium and cerium. Yttrium was concentrated in the aqueous phase. EDTA and DTPA, as aqueous phase counterextractants, enhance separation factors in mine-rare-earth sulfate systems. Yttrium separation from heavy rare-earth elements exhibits marked sensitivity to the position of yttrium in the selectivity scale of the rare-earth elements with the sequestrants. Yttrium-ytterbium separation is more effective with EDTA, whereas yttrium-dysprosium separation is more effectively increased with DTPA.

Jan 1, 1963

Flat jack stress determinations in selected colliery roadways have revealed a range of measured stress from 330-p.s.i. tension to 3,750 p.s.i. compression. Photoelastic examination of loaded plastic and actual rock mo.odel mine openings has shown that the primary horizontal stress required to attain these measured stresses would be from one to three times the superincumbent vertical load.Examination of roof movement with a. borehole oxtensumeter and a series of anchors at various horizons to 30 feet in a. vertical roof borehole showed that when a standing face waa.s advanced the roofmovement was practically confined to the lower two feet. The ma.j ority of this movement occurred during the 36 hours after mining at this face commenced.The use of a. radioactive isotope and a. scintillation counter in a. pair of parallel bcreholes promises to be sensitive and accurate method of roof bedding plane crack detection.

Jan 1, 1963

By W. L. Anderson

Standard tellurium analytical procedures were modified to obtain the greater sensitivity needed to support a survey of tellurium resources by the Bureau of Mines. Resulting volumetric and spectrophotometric methods for determining tellurium in all types of tellurium-containing materials are described. Sample decomposition and preliminary separations of interfering selenium, gold, and silver are the same in both procedures. The volumetric method is applicable to samples containing a minimum of 10 parts per million of tellurium, In this method the tellurium is reduced to elemental form, and the colloidal suspension is titrated with 0.01 normal iodine solution. The weight of sample for analysis, from 0.25 to 10 grams, should be selected so that the sample contains 0.1 to 5 milligrams of tellurium. To insure accuracy, duplicate samples should be run and the results averaged, particularly on samples of low tellurium content: The limit of determination is 0,001 percent tellurium, which is equivalent to 0.1 milligram of tellurium when using a 10-gram sample. The spectrophotometric method is particularly applicable to low-tenor materials containing from 0.5 to 50 parts per million of tellurium. Up to 10 gram samples are required for making accurate determinations in the low-concentration range. The sample used should contain between 5 and 100 micrograms of tellurium. The turbidity of a colloidal suspension of tellurium prepared from such a sample is determined in a spectrophotometer .t at a. wave-length of 440 millimicrons, and this value is compared with those of standard samples containing known amounts of tellurium.

Jan 1, 1963

By L. H. Adami

This paper reports the results of solution calorimetry conducted to obtain the heats of formation of crystalline FeS04?6.952H20 and FeS04?1.008H20, from. which values were derived for the stoichiometric compounds FeS04?H20 and FeS04?H20. Also included are derived values of the free energies of formation and dehydration. This work was undertaken primarily to fill a need for data for pure, easily obtainable ferrous compounds that are suitable for use as calorimetric intermediates, The ferrous sulfate hydrates meet the essential requirements for this use.

Jan 1, 1963

By C. W. Spencer, J. T. Smith

GRAIN-BOUNDARY surfaces are penetrated by a liquid phase when the liquid-solid interfacial tension is less than one-half the tension of the grain-boundary surfaces. Grain growth may occur in the presence of this liquid phase. burke1 reports that grain growth of this nature has been observed in two-phase ceramic systems. He suggests that the presence of a grain-boundary liquid may accelerate or decelerate the

Jan 1, 1963

By C. W. Grate

Cooperative Education is by no means a new idea. The first such program was instituted at the University of Cincinnati in 1906 by the late Dean Herman Schneider with twenty-seven engineering students participating. Today, more than fifty years later, there are in excess of one hundred institutions' with some such program in which thousands of students, are participating in the fields of Liberal Arts, Engineering, and Business Administration. At the same time, according to a conclusion reached during a study of work-study college programs, copyrighted in 1961 by Thomas Alva Edison Foundation, and from which we quote; "We were amazed at the lack of-information about cooperative education among school and college staffs and students, among parents and employers, and on the part of the public generally."

Jan 1, 1963

By H. A. Hancock, L. M. Pidgeon

Equilibrium carbon monoxide pressures were measured over the reaction between chromium oxide and a number of solid ferrochromium alloys in the composition range 0.4 to 4.8 pct C and 0 to 49 pct Fe. Measurements were also made for the carbides Cr23C6 and Cr7C3 which agreed well with previous investigations. Between 1050°and 1400°C the pvessures varied from 0.1 to 56 mm and increased markedly with the iron and carbon contents of the alloys. The data were used to estimate the activity of carbon in the alloys and to calculate the equilibrium conditions for the decarburization of a useful range of ferrochromium alloys. WHEN ferrochromium is produced by the reduction of chromite with carbon in an electric arc furnace it invariably contains up to 10 wt pct C. For many purposes such as the production of stainless steel, it is necessary that the carbon content be as low as from 0.02 to 0.05 pct. Thus an important part of the ferrochromium industry consists of the production of low carbon ferrochromium. The classical Bessemer steelmaking technique cannot be used to oxidize low carbon contents in chromium and ferrochromium alloys without also oxidizing the chromium. Recently a new commercial process2-4 has been introduced for oxidizing carbon from high chromium content alloys which consists of heating the solid alloy with such oxidizing agents as Cr2O3, Fe2O3, or SiO2 in a retort at reduced pressures. By maintaining the carbon monoxide pressure below the equilibrium value for the system, the carbon can be removed as carbon monoxide without oxidizing the chromium. The equilibrium conditions for the decarburization of solid chromium carbon alloys have been determined by Boericke5 who measured the carbon monoxide pressure over the reaction between the various chromium carbides and chromium oxide. A typical reaction is shown below. Cr23C6 + 2Cr2O3 =u 27Cr + 6CO [1] These values are not applicable to the decarburization of commercial ferrochromium alloys which invariably contain major amounts of iron. The present investigation was therefore undertaken to measure the change in the equilibrium carbon monoxide pressure brought about by additions of iron to the Cr-C-0 system, thus extending the work of Boericke into the region of the production of low carbon ferrochromium. MATERIALS AND METHOD Materials. Measurements were made on two carbides of chromium, Cr233C6 and Cr7C3, and fifteen Fe-Cr-C alloys. The chromium carbides were made

Jan 1, 1963

Mineral engineering is defined as those engineering activities that relate to the discovery, development and utilization of mineral resources. Using petroleum engineering as an example, it is shown that the breadth of the field to be studied is a major educational problem. Breadth of field is aggravated by the rapidity with which technological demands may change. At present, special short courses serve to update engineering education. Recent experience suggests an increased rate of change for the future. The fact that engineers have typically human needs and goals, and the fact that engineers respond to these in our free society, introduces a third class of problems. One approach to the solution of these problems is the unified engineering curriculum based on a core of subject mat-ter common to all engineering. Experience suggests that the unified curriculum is an effective method to minimize the importance of the first two problem areas presented, and shows a degree of success in handling some problems within the third area. Perhaps, for the good of all segments of society, it is best to have both career-oriented and unified curricula represented by educational institutions of high quality.

Jan 1, 1963

By Robert A. Rapp

The standard molar free energy of formation of MOO,was determined between 750o to 1050o C in galvanic cell measurements involving the solid electrolyte Zr0.85 Ca0.15 O1.85. Use of the reference electrodes Fe + FexO and Ni + NiO Provided two independent determinations of FoMoo2. The data may be represented by the equation FMoO2 = -137,500 +40.0T(°K) which is in good agreement with previous CO/CO, gas equilibrium measurements of Gleiser and Chipman. The standard molar free energy of formation of molybdenum dioxide has recently been reported over a large range of high temperatures from the calorimetric experiments of King, Weller, and christensen.' Gleiser and chipman2 have also recently determined ?FmoO2 from 926o to 1068oC in CO/CO2 gas equilibrium measurements. Earlier gas equilibrium studies have been made and reviewed by Gokcen.' Over the temperature range studied by Gleiser and Chipman their values for ?FoMoO2 differed from the calorimetric data by about 700 cal. This investigation was undertaken to resolve this difference and thereby establish the two phase mixture of Mo + MOO, as an electrode of well-known oxygen potential for galvanic cell applications at very high temperatures. The galvanic cell technique involving the Zr,.,, Ca,0.15 01.85 solid electrolyte was introduced for the

Jan 1, 1963

By Carlos E. Roggero

The influence of high temperatures on the zinc roasting practice has been investigated by full-scale tests in fluid bed reactors operating at temperatures from 950° to 1150°C. It was definitely shown that, throughout the range, an increase in tem perature resulted in a 2 to 3 pct increase in zinc solubility because of decreased content of zinc fer-rite and lowered sulfide sulfur. The former is attributed to thermal decomposition of ZnFe,O,, and the latter to increased oxidation rates, ad longer retention times. Data on the gveatly increased volatilization of lead, cadmium, and silver above 1000°C, are presented. A considerable fraction of the iron present in the feed was also transferred at high temperatures from the coarse roaster discharge to the flue dusts. AS part of its metallurgical complex1-3 situated in a 12,000 it Andean valley at La Oroya, Peru, Cerro de Pasco Corp. (a wholly owned subsidiary of Cerro carp.) operates a 150 short ton per day electrolytic zinc refinery. Electrolysis is carried out at a cathode current density of 65 amp per sq ft with an electrolyte content of 55 g per liter of Zn and 150 g per liter of su lf uric acid. Due to the high iron content of the marmatitic concentrate used, a large fraction—about 15 pct—of the zinc reports in the leach residues. To minimize such losses, efforts have been exerted toward improving calcine solubility. One method, as noted in the literatre,, is to retard zinc ferrite formation by decreasing the roasting temperature. Unfortunately, such a procedure tends either to reduce the roaster throughput or increase the sulfide sulfur in the calcine. Consequently, this approach was discarded in favor of experimental work in the opposite direction, i.e., high temperature roasting. Full- scale tests were promising and resulted in the granting of a patent to Cerro de Pasco carp.' After a brief account of plant equipment and operating procedure, this paper describes the tests made and attempts to assess the results obtained. GENERAL PLANT LAYOUT AND OPERATION The Roasting Plant, see Fig. 1, comprises an agglomerating plant feeding three fluid bed roasters with a combined capacity of 10,000 tons per month. The Peruvian patent rights on this process were purchased from the New Jersey Zinc Co. The concentrate, assaying: is pelletized to a -3 +14 mesh product and fed to the fluid bed roasters. The roaster exhaust gases pass through a waste heat boiler, cyclones, a fan, and an electrostatic precipitator. Approximately half of the dust collected in the cyclones returns to the pellet-izing plant as one of the binding ingredients, the remainder joins the cooled bed discharge ('overflow') and is conveyed to the grinding plant. The -35 mesh product obtained, together with the dust collected in the electrostatic precipitator constitute the feed to the leaching plant. Batch leaches are made in vessels with mechanical and air agitation, the residues are separated and washed in Burt Filters, and pumped to storage ponds. THE FLUID BED ROASTERS Two reactors are as shown in Fig. 2, and the third,' of about the same configuration, is approximately 40 pct smaller. The total grate and freeboard (just below the gas outlet) areas measure 170 and 426 sq ft respectively. The feed, continuously weighed and controlled by Merrick Weighto-meters fitted with variable speed motors, enters the reactors at the top of the expanded bed level. The coarse calcine overflows through the opposite end by

Jan 1, 1963

Alkaline leaching with sodium carbonate solution adjusted to pH 9·5 to 10·0 preferentially dissolves thorium from a mixture of rare earth and thorium hydroxides. Rare earth sodium carbonates form in the alkaline leaching stage.These are converted to rare earth oxides for use as optical and ophthalmic polishing agents. Quadrivalent cerium is extracted under similar alkaline leaching conditions.INTRODUCTIONAustralia has made significant contributions to mineral chemistry and mineral dressing. As often happens with an industrially immature country, research investigations often outstrip the ability or desire of commerce to exploit them. It is wrong to think exclusively in terms of export of raw materials. Imagination assists in developing world trends. The chemical utilization of mineral sands has interested a group of investigators, chiefly at the Commonwealth Scientific and Industrial Research Organization (C.S.I.R.O.) and, more recently, in the mining industry itself. From an international point of view the highlight of this work was Newnham's (1960) process for the separation of hafnium from zirconium. Earlier work at C.S.I.R.O. investigated the chlorination of rutile, zircon, and monazite. Assuming that titanium tetrachloride would be available in large quantities in the post war years, extensive work was done by Kraitzer, McTaggart, and Winter (1948) on organic compounds of titanium. This work led to the development of heat resistant paints, plastic compositions, and improved organic protective coatings that predated overseas work by up to seven years. (Post, Shiihara and Schwartz, 1961; Anon, 1955). Contributions were made to the production of refractory hard metals (Kraitzer, 1949; Kraitzer and Newnham, 1956). Pilkington and Wylie (1947) and Urie (1947) investigated the production of rare earths from monazite by an acid process.

Jan 1, 1963

By Robert C. Meaders

In this paper, autogenous grinding is defined as the combined crushing and grinder of a run-of-mine ore or the product from a primary crusher, in a single stage grinding mill. This is in contrast to pebble milling where pebbles are substituted for steel balls to grind a ball mill size feed. The autogenous mill to compete in efficiency with normal methods of crushing and grinding must not use greater power, must use less labor and steel, and must produce an equivalent product.

Jan 1, 1963

By Ken-ichi Hirano, B. L. Averbach, Morris Cohen, N. Ujiiye

The influence of plastic deformation in compression on the self-diffisivity of a iron has been measured in the temperature range of 742º to 885°C. The diffusivity is enhanced in proportion to the strain rate, but this dependence decreases with increasing temperature. The magnitude of the strain is relatively unimportant in this connection. Strain rates from 0 to -2 x 10-3 sec-1 were investigated, with a corresponding increase in diffusivity up to 3 x 103 times. The results are analyzed in terms of vacancy diffusion and the excess vacancies introduced during dejornzntion. It is concluded that grain boundaries are the main vacancy sinks in polycrystalline iron and that the vacancy lifetime is therefore dependent on the grain size. A typical vacancy lifetime at 800°C with a nzean grain-boundary intercept of 0.3 cm is of the order of 1 sec. LATTICE imperfections are considered to be the dominant mechanism of diffusion in close-packed crystals. Vacant lattice sites are usually the most important defect, but the enhancement of diffusion along grain boundaries and other short-circuiting paths has been well documented. Inasmuch as plastic straining produces a variety of defects, it would be expected that the application of stresses sufficient to cause plastic flow during a diffusion run might result in an increase in the self-diffusivity. Enhanced self-diffusion in a iron under compressive creep has been observed by Buffington and Cohen' and subsequent coworkers.2 Lee and Maddin3,4 have also found an enhancement in the self-diffusivity of silver single crystals undergoing torsional deformation. On the other hand, Darby, Tomizuka, and Balluffi5 have not observed any significant diffusion increase in single crystals of silver deformed either in tension or in compression, although the results in this case may have been affected by the occurrence of recrystallization. With poly crystalline silver, however, Forestieri and Girifalco6 have found en- hanced diffusion during compressive creep. A small decrease in the self-diffusivity of zinc single crystals under compressive loading has been reported,7 but the applied stresses in these experiments were too low to cause appreciable plastic deformation. For the cases in which enhanced diffusion has been found, a number of common effects have been noted. Usually, the ratio of the diffusivity during straining, Ds, to the diffusivity in the unstrained condition, D,, varies linearly with the strain rate, and does not seem to be a function of the plastic strain, at least up to ? = 0.2. Values of Ds/Du of the order of 100 have been reported'-4 but the enhancement decreases with increasing diffusion temperature. The activation energy for diffusion decreases markedly with increasing strain rate and approaches a level of roughly one-half the unstrained value. Most of the current explanations of these observations assume that excess vacancies are generated by the deformation, but rather large concentrations of excess vacancies and/or long lifetimes are required by these theories.',',',' Since the original work on iron, there has been an important improvement in the compressive-loading technique.2 The early data were also analyzed without taking into account the motion of the coordinate system in the specimens undergoing plastic deformation. This problem has now been solved by a number of investigators (see Refs. 11, 12, and the appendix of the present paper). Consequently, the strain-diffusion runs on iron for the Ds measurements were repeated and extended over wider ranges of temperature and strain rate. In addition, the original diffusivity data9 on the unstrained iron have been corrected for the divergence of the beam in the counting system and new data points have been added, resulting in somewhat different values for the self-diffusi-vities in a iron.10 The new values for Du are used in this paper. A comparison of Ds and Du confirms the large enhancement in the self-diffusivity of iron during compressive creep, as previously reported.',2

Jan 1, 1963

By C. A. Komar

The Bureau of Mines has undertaken an investigation to determine possible applications of acoustic energy at sonic and ultrasonic frequencies to improve ultimate recovery from oil reservoirs. A literature search was conducted to provide background information for initiating laboratory research. The purpose of the literature search was to review the uses that have been made of acoustic energy in the petroleum industry and to select procedures and techniques that could be applied to the solution of petroleum production problems. The characteristics (68)3 of ultrasonic energy make it potentially useful to a variety of industrial and experimental applications. Pulse techniques (99) are common in the testing of materials where inspection is accomplished by propagating an ultrasonic pulse through the material. Viscosity measurements (45) are made by interpreting changes in the absorption of sound as it is propagated through a flowing liquid. Cavitation phenomena (93) produced by high-intensity ultrasound in liquids have been used extensively in industrial cleaning, machining, impact grinding, and aluminum soldering operations.

Jan 1, 1963

By H. C. Chao, Y. E. Smith, L. H. Van Vlack

ThE phase relationships for the MnO-MnS system have been investigated only in the eutectic region. wentrupl reported a eutectic at 1280°C (2345°F) with approximately 50 wt pct of each component, as based on the earlier work of Andrew, Maddocks, and Fowler.2 More recently silverman3 corrected these figures to 2275° ±10°F (1246°C) with 63 wt pct MnS and 37 pct MnO. Neither Wentrup nor Silverman investigated the solid-solution limits in this system. However, Wentrup did suggest with his phase diagram sketch that the maximum solubility of MnS in MnO is 10 wt pct, and the solubility of MnO in MnS is nearer 20 wt pct, Fig. 1. These figures have been utilized in subsequent publications without further verification.4 There had been evidence found in this laboratory that the above solid-solution figures were high. An investigation was therefore conducted using the following procedure. Samples containing MnO and MnS were contained in platinum foil, heated just above the eutectic temperature in a purified nitrogen at- mosphere, and quenched into distilled water. The MnO had been prepared by calcining reagent grade MnCO3 in nitrogen at 1400°C. Only MnO was detected in subsequent X-ray diffraction analyses. The MnS had been prepared by sulfur deoxidation of reagent grade MnSO4 according to the reaction: MnSO4 + S2 ? MnS + 2SO2 The details of the sulfide preparation procedure, which utilized atmospheric sulfur pressures at 950°C, are discussed elsewhere.5 The sulfur content of the sulfide was determined to be 36.8 * 0.2 pct, which matches the stoichiometric value of 36.9 pct. No evidence of either MnO or MnSO4 was detected microscopically or by X-ray diffraction. The single-phase combinations of MnO and MnS at the eutectic temperature indicate the limit of solid solution as shown in Fig. 2(a) and (c), and the revised phase diagram is shown in Fig. 2(d). The melting temperature for MnO is that provided by Glasser.6 The eutectic temperature of 1232° ± 5°C and eutectic composition of 64 wt pct MnS are in close agreement with Silverman's correction of Wentrup's work. The maximum solubility of MnO in MnS was determined to be 1.7 ± 0.2 wt pct. The maximum solubility of MnS in MnO was determined to be 1.8 ± 0.2 wt pct. These figures represent the lower limit for the presence of liquid at 1260°C and are significantly lower than the earlier estimated solid-solution figures. The authors wish to acknowledge the support of U.S. Steel's Edgar C. Bain Laboratory for Fundamental Research. The comments and critical suggestions of Drs. A. S. Keh, R. Rickett, and R. B. Snow are appreciated.

Jan 1, 1963

By d&apos, John C. Entremont

Pure iron was inductively melted in small refractory crucibles and optical pyrometer and immersion thermocouple readings were simultmzeously taken. The resulting emissivities of the liquid iron surface obtained were found to be greatly affected by both the gaseous atmosphere and geometrical changes in the physical setup. Quantitative values for these effects are indicated. FOR many applications in both the laboratory and plant, optical pyrometry is still the best means of measuring temperatures in the incandescent range. A prerequisite in evaluating the correct temperature is a good value of the emissivity of the surface. To obtain the emissivity from the tabulated values of the literature can be very confusing and often far from correct. There are many reasons for these difficulties, and it is not within the scope of this paper either to enumerate or to discuss them all. Its purpose is to show quantitatively how several factors affect the apparent emissivities obtained from experimental measurements on liquid iron surfaces. The black body is the reference state for the quantitative values of emissivities and is defined1 as a body which absorbs all radiation incident on it, reflecting none; such a surface emits more radiation per unit area per unit time than any surface which reflects any radiation, and is given a value of unit emissivity. All bodies having reflective power thus have emissivities less than unity and are considered nonblack or grey bodies. The ratio of the radiant energy emitted by the flat, nonblack surface to that of a perfectly black surface of equal area and temperature is the emissivity of the surface. The above definitions are applied to flat, polished, opaque surfaces, very seldom encountered in actual measurements, and for this reason many authors have suggested that the word "emittance" be used for real bodies rather than emissivity. The emittance has reference to the material and its configuration rather than to its properties in the idealized state. Recent observations of molten iron in a small refractory crucible indicate that not only the configuration of its surface but the geometrical arrangement of its surrounding and the nature of the surrounding atmosphere have a pronounced effect on the emittance. Neglect of changes in such conditions may lead to errors as large as 40°C at 1600°C. Thus it is suggested that the term "apparent emissivity" be used and that it be recognized that its value pertains to a particular experimental arrangement only. As a result of not recognizing these differences in emissivities, which are obtainable from changes in the physical setup of an observation, many investigators have incorrectly quoted their values as those of the emissivities of particular materials rather than as an apparent emissivity for their particular arrangements. As a consequence, values of the emissivity of liquid iron ranging from 0.3 up to 0.55 are found in the literature. In an effort to establish an accurate optical temperature scale for liquid iron solutions in which de-oxidation studies were to be carried out, it was observed that the temperature relationship, obtained by simultaneously taking immersion thermocouple

Jan 1, 1963