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By H. I-Lieh Huang, O. D. Sherby, J. E. Dorn

RECENT investigations1-4 have suggested that the total plastic strain, C, for high temperature creep under a given stress can be correlated by means of a temperature-compensated time, te- where t is the duration of test, e is the base of natural logarithms, aH is the activation energy for creep, R is the gas constant, and T is the absolute temperature. A typical set of data on which this deduction was based is given in Fig. la. Inasmuch as the e-in t curves for the various temperatures are identical except for their displacement along the In t axis where f and are appropriate functions. If the increase in creep rate with an increase in temperature is exclusively ascribable to a single process involv- ing thermal activation, (T) should equal RT and therefore it = constant [2] where ?= te Assuming the validity of this relationship, ? = ?2 at the same strain, or where the subscripts refer to two alternate test conditions.

Jan 1, 1957

Born, March 28, 1853 Died July 23, 1916 On July 25, 1916, the Board of Directors adopted the following minute and directed that it be entered upon the records of the Board & published in the Bulletin of the Institute, and thereof be sent to the family of Mr. Kirchhoff: Charles Kirchhoff was one of the oldest, most widely known and most highly esteerned members of the American Institute of Mining Engineers. On his return in 1875 from a European course of study, to begin a highly successful professional career, he joined the Institute, then just commencing to acquire both national and international recognition. He became at once, and-for more than 40 years continued to be, its earnest , and active supporter, serving it as Manager, Councilor or Director for terms aggregating 9 years,-as Vice-President for 2 years, and twice as President for a year. During the critical period of the erection of the United Engineering Society's building, and the transfer of the Institute to permanent head-quarters therein, Mr. Kirchhoff was its efficient representative in the United Engineering Society, and on the Building Committee. In 1910, amid the congratulations of colleagues, employees, and innumerable friends, Mr. Kirchhoff retired from active business as Vice- President and General Manager of a great technical publishing company. Yet he sacrificed of his well-earned leisure yet one more year, to serve the Institute as President through 1911.

Jan 9, 1916

New York Meets first Wednesday after first Tuesday of each month. J. E. JOHNSON, JR., Chairman. EDGAR RICHARD, Vice-Chairman. D. M. LIDDELL, Secretary, 7 Wall St., New York, N. Y. C. A. BOHN, Treasurer. JOHN V. N. DORR, LEWIS W. FRANCIS. Boston Meets first Monday of each winter month. R. L. AGASSIZ, Chairman. JAMES G. CARLETON, Vice-Chairman. E. E. BUGBEE, Secretary-Treasurer, Mass. Inst. of Technology, Cambridge, Mass., W. E. C. EUSTIS. G. A. PACKARD. Columbia Holds four sessions during year. Annual meeting n September or October. W. H. LINNEY, Chairman. OSCAR LACHMUND, Vice-Chairman. LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash. STANLY A. EASTON, S. SHEDD. Puget Sound Meets second Saturday of each month SIMON H. ASH, Chairman. I. F. LAUCKS, Vice-Chairman. CHARLES SIMENSTAD, Secretary-Treasurer, 425 Lyon Bldg., Seattle, Wash. GLENVILLE A. COLLINS, JOHN N. POTT

Jan 7, 1917

By Zay Jeffries

THIS paper will include a brief discussion of Prof. Howe's paper on The Supposed Reversal of Inheritance of Ferrite Grain Size from that of Austenite.1 The general subject of grain refining in steel and iron will also be treated. The conclusions reached are stated in the following hypotheses which are discussed more in detail below. 1. The ferrite grain size in pure iron, the ferrite and pearlite grain size in hypoeutectoid steel, the pearlite grain size in eutectoid steel and the cementite and pearlite grain size of hypereutectoid steel are not inherited from the grain size of the mother austenite. 2. The only structural feature that is generally inherited from the austenite of hypo- and hypereutectoid steels on cooling through their transformation ranges is the position of the excess ferrite or cementite at the austenite grain boundaries, sometimes causing complete and sometimes incomplete networks which outline the old austenite grain boundaries. Rapid cooling through the transformation range will cause the non-inheritance of this structural (network) feature. 3. The austenite grain boundaries themselves are nearly always effaced in all steels and also in pure iron during the Ar transformations. 4. The grain-size refining of steel and iron is brought about by the combined. effect of non-inheritance of the transformation products on either heating or cooling, i.e., the austenite transformation .products do not inherit their grain size from the austenite on cooling through the transformation range for does austenite inherit its grain size from the products which form austenite on heating. 5. In general, in both iron and carbon steel the larger the austenite ,grain size, the larger will be the grain size of the transformation products on cooling. This, of course, assumes all other conditions constant except the austenite grain size. An exception is found to this general rule in very pure iron such as electrolytic iron. 1n this instance small austenite grains may form very large ferrite grains on cooling through Ar3.

Jan 11, 1917

By H. M. Howe

On commencing the construction of the Orford Company's copper smelting works, at Bergen Point, N. J., I endeavored to convince our President, Mr. W. E. C. Eustis, by actual tests, that at the pressure of from 15 to 18 ounces per square inch, employed by us in smelting, less power was consumed in delivering a unit of blast by a Baker blower than by a fan blower. I attempted to prove this in the following manner: Across the mouth of a No. 5) Baker blower I firmly fastened a board with two round holes, 6 inches in diameter, cut in it. The board was fastened so tightly that no air could escape except through the holes. I then drove the blower at several differerent speeds, observing the pressure at which the air excaped through the two openings for each different speed of the blower, and also indicating the engine, whose only work at that time was to drive the blower. From this I calculated the quantity of power required to deliver, with a Baker blower, sufficient air to keep the pressure at a given point, while it escaped freely through the two six-inch apertures into the open air; or, in other words, to deliver air at a given pressure through these two openings. From the total power so consumed it was, of course, necessary to deduct the power which was required to drive the engine itself. This was ascertained by removing from the engine the belt which drove the blower, and then noting the quantity of power consumed in simply turning the engine over without any

Jan 1, 1882

By A. T. English

X-ray dif action techniques were used to investigate ordering and domain coalescence for the B2 (CsC1) superlattice in this alloy. Essentially complete disorder is obtainable by drastic quenching. isothertmal ordering occurs very rapidly at temperatures between 565° and 680°C, only a few seconds being required for development of substantial long-range order. A very fine antiphase dormain structure, found in samples annealed for short times, undergoes coalescence with further annealing. Domain "size" is found proportional to (t)1/2 . This Yate law can be derived by adapting the formalism of Hillert's analysis 01- metallurgical grain growth. For this Purpose the material is descvibed in terms of a "Swiss-cheese " structure, consisting of two multiply connected, mutually intertwined domain volumes. The observed activation enevgy for coalescence, 70 kcal per g-atom, agrees with an estit~lated value ,for volume diffusion in disordered rrzaterial. It is suggesled that the experimental value vejlects the substantially disordered environment of mobile vacancies located in the moving antiphase domain boundary. The alloy Fe-Co-2V is bcc below about 900'C and orders into a B2 (CsC1) superlattice below about 730c It has important applications in magnetic components, including many requiring extensive cold rolling.* example, Marcinkowski and Brown6 observed a re1atively small as-quenched domain size of about 250Å in B2 Fe3A1. Since there appear to be no published data on domain coalescence in B2 alloys, this process was studied in detail. MATERIALS AND EXPERIMENTAL TECHNIQUES A commercial high-purity alloy, nominally 49 Fe-49Co-2V, was obtained from the Arnold Engineering Co. in the form of cold-rolled sheet 0.004 in. thick. Samples were annealed for 1 hr at 800°C in dry H2 to produce disorder and quenched into iced brine. They were then annealed in a nitrate-nitrite salt bath for various times at temperatures between 525° and 625°C. Estimates of the LRO parameter S and the APD size D were made using established X-ray diffraction techniques. Superlattice peaks are best observed using CoKa radiation, for which the value of (fFe-fCo) is maximized. Peak-to-background intensity ratio was improved by filtering CoKß from the incident beam to eliminate sample fluorescence, and by using a pulse-height analyzer. The LRO parameter S was computed from the ratio of integrated intensities I 100/I 200- Owing presumably to systematic errors associated with the presence of crystallographic texture and X-ray extinction, only rough agreement was obtained between experimental and theoretical (absolute) intensity ratios. For this reason certain experimental refinements (e.g., use of balanced filters) were considered superfluous and were omitted. Emphasis was placed on maximizing intensity in order to reduce the time taken to accurately determine the contour of the very small (loo), peak. This was done by point counting 105 counts at appropriate intervals. Background intensity averaged about 1200 cps.

Jan 1, 1967

University of New Mexico, Albuquerque, N M Requests for publications should be addressed to the Librarian of the University Papers of the Geological Series of the University are bound in volumes: Vol 1, vol 2, pt 1, and vol 2, pt. 2, and vol. 3 are out of print, but separates of the following papers may be had at a uniform cost of 25 cents each. Vol. 1? No. 1, Geology of the environs of Albuquerque (1898); 2, Occurrence of copper and lead in the San Andreas and Caballo Mountains (1898), 3, Geological reconnaissance in western Socorro and Valencia counties (1898); Geology of the San Pedro and Albuquerque districts (1898). , Vol 2: No. 1, Geology of the Albuquerque Sheet (1900); 2, Miscellaneous economic papers by Herrick (1900); 3, Geological reconnaissance in western Socorro and Valencia counties (1900); 4, Geology of the White Sands of New Mexico (1900); 5, Identifi¬cation of an Ohio coal measure's horizon in New Mexico (1900); 6, Cyanide process in New Mexico (1900). Vol. 3. No 3, The oil situation in New Mexico (1920), 4, Geology of Sandia Mountains (1922); 5, Oil and gas m New Mexico in 1923.

Jan 1, 1933

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

It is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investi-: gators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by - experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from IIoo° to 17oo°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxida- tion of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous clays burned ' to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,= the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery0 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the clay, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid; i.e., the sulphur was in combination with the silica. orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

It is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investi-: gators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by - experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from IIoo° to 17oo°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxida- tion of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous clays burned ' to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,= the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery0 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the clay, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid; i.e., the sulphur was in combination with the silica. orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By J. Leja, N. Sheikh

The stability of lead ethyl xanthate precipitate in aqueous environment of different pH (4.5 to 10.5) and at temperatures 25°C-60°C was investigated. Dissolution leads to a wide variation of pH, xanthate, and lead ions concentration in solution and to a deposition of solid products of reactions. X-ray diffraction patterns of these solids enabled identification of Pb(OH)3, PbCO3, and PbS as constituents of the remaining undecomposed Pb(EtX)1, together with some unidentified compounds (which give rise to intensive peaks with d values of 2.82A and 1.71A, and numerous peaks of lesser intensity).

Jan 1, 1974

Earnings of engineers in the period 1956 to 1958 continued the upward trend observed in the previous survey interval, 1953 to 1956. The overall median (all graduates) was $6500 in 1953, $7750 in 1956 (a 19 pct upstep or about 6.5 pct annually), and $8750 in 1958 (up 13 pct from 1956 or 6.5 pct average yearly). The latter represents an increase from mid-1956 to mid-1958. For this same two-year span the Consumer Price Index rose 1.5 pct and the Average Gross Weekly Earnings for Production (Manufacturing) climbed close to 10 pct. Median earnings for the major classifications studied are presented in Table I. The increase in engineering earnings are not distributed equally among the various activity classifications or among the experience levels of the survey. Summary results of the changes of the median lines for the major divisions are presented in Table 11. Data in this table are approximations- dollars are rounded to the nearest $50 unit and percentages to the nearest full percentage.

Jan 1, 1959

By R. H. Widmyer, G. M. Wood

This investigation was prompted by the absence of a simple, accurate method to predict optimum second stage separation pressure in three stage separation operations. Three stage separation as used here includes two separators plus the stock tank. The first stage pressure is usually fixed by gas sales conditions and the third stage is at atmospheric pressure. Thus, the second stage pressure is the only one that may be varied in-discriminantly during production operations. No variations in temperature were considered in this study, even though it will vary among systems, for a change in temperature has little effect on the optimum pressure. Optimum pressures may be determined from flash calculations, but these are tedious unless a computer is available. An early attempt to develop a simpler method&apos; yielded an equation which gave the optimum pressure only as a function of initial and final pressure. Experience, however, confirms theoretical relationships which show that composition as well as pressure and temperature must be a factor. This indicates that the basic relationship should be an equation of the form, where P, is second stage pressure, P, is first stage pressure, A is a function of P. (stock-tank pressure) and the system composition, and n is a function of the number of stages and the system composition. Fig. 1 shows the basic variation of P2 with P for a fixed system composition. A series of such figures clearly showed the effect of composition. The peak of each curve reflects that second stage pressure at which the stock-tank recovery (gal/MMcf) residue gas is a maximum value. DEVELOPMENT OF NEW CORRELATION Wellstreams having 17 different analyses, ranging from low gravity crude to condensate, were used to determine the effect of composition. Each wellstream was flashed through three stages to determine the optimum second stage pressure for each first stage pressure. Equilibrium vaporization ratios proposed by Latham and Campbell were used throughout. The heptane plus fraction, for simplicity, was assumed to have the properties of octane. The results were subjected to an empirical analysis in an attempt to develop a correlation- that would be (1) simple, (2) accurate, and (3) eliminate the need for any flash vaporization calculations. This analysis yielded two equations, one for wellstreams having a specific gravity greater than one (air = 1.0) and one for those less than one. For crude streams (specific gravFor condensate (specific gravity < 1.0),

By Sir John Cadman

Since my previous review of the Persian fields, presented in 1929,&apos; considerable progress has been made. The main feature of drilling development has been the delimitation of the Haft Kel field and its extensions. Although the limits have not yet been reached, a productive area of about 40 square miles has already been proved and it is now certain that the field will be of the same order of importance as the Masjid-i-Sulaiman field. Production to main pipe line from Haft Kel was begun in November, 1929, and to date about 4,500,000 tons have been produced. Normal production has continued from the Masjid-i-Sulaiman and Naft Khaneh fields. The search for oil in horizons below the main producing limestone is perhaps the most interesting and important exploratory drilling work in progress. Promising results have been obtained in the first well deepened in the Masjid-i-Sulaiman field with this objective, and the exploration of these lower formations is being continued. In this connection an allied program of geochemical research work on the nature of the oils and oil-bearing rocks of different horizons is at, present being undertaken. Masjid-i-Sulaiman Field Since the Haft Kel field was brought into production in 1929, production from Masjid-i-Sulaiman has been reduced in order to equalize to some extent the producing lives of the two fields. The production for the last four years has been as follows: m Approximate Equivalent in TonB Barrels 1929 5,434,071 38,038,497 1930 4,925,869 34,481,083 1931 4,248,086 29,736,602 1932 Approximately 4,500,000 31,500,000

Jan 1, 1933

New York Meets first Wednesday after first Tuesday of each month. J. E. JOHNSON, JR., Chairman EDGAR RICHARD, Vice-Chairman D. M. LIDDELL, Secretary, 7 Wall St., New York, N. Y. C. A. BOHN, Treasurer JOHN V. N. DORR LEWIS W. FRANCIS Boston Meets first Monday of each winter month. R. L. AGASSIZ, Chairman JAMES G. CARLETON, Vice-Chairman E. E. BUGBEE Secretary-Treasurer, Mass. Inst. of. Technology, Cambridge, Mass. W. E. C. EUSTIS G. A. PACKARD Columbia Holds four sessions during year. Annual meeting in September or October. W. H. LINNEY, Chairman OSCAR LACHMUND, Vice-Chairman LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash. STANLY A. EASTON S. SHEDD Puget Sound Meets second Saturday of each month SIMON H. ASH, Chairman I. F. LAUCKS, Vice-Chairman PERCY E. WRIGHT, Secretary-Treasurer, 2012 L. C. Smith Bldg., Seattle. Wash. GLENVILLE A. COLLINS JOHN N. POTT

Jan 11, 1917

ALABAMA Anniston.-Carrington, F. G. Auburn.-Brown, R. L. Bessemer.-Abbott, C. E. Dobbs, G. G. Ferguson, V. Salmon, H. S. Schaber, C. F. Birmingham.-Aldrich, T. H. Aldrich, T. H., Jr. Allen, A. W, Ball, E. M. Bonnyman, J. Bowron, J. Bush, M. W. Crawford G. G. Crockard, F. H. Ellis, E. E. Fairbairn, C. T. Gallacher, J. Geisiner, H. S.

Jan 1, 1917

ALABAMA Anniston.-Carrington, F. G. Auburn.-Brown, R. L. Battelle.-Green, G. G. Bessemer.-Abbott, C. E. Dobbs, G. G. Ferguson, V. Birmingham.-Adams, J. H. Aldrich, T. H. Aldrich, T. H., Jr. Allen, A. W. Bonnyman, J. Bowron, J. Bush, M. W. Crawford, G. G. Crockard, F. H. Ellis, E. E. Fairbairn, C. T. Gallacher, J. Geismer, H. S.

Jan 1, 1917

By R. H. Marshall, J. Welchner, E. S. Rowland

THIS paper presents results on an exten¬sion into the realm of high-carbon steels of some work recently published&apos; on the effects -of time at temperature, quenching temperature and prior structure on the hardenability of one 0.20 and four 0.40 per cent carbon alloy steels. It was shown at that time that unless the conditions of time, temperature and prior structure are substantially the same in performing the hardenability test as in conducting harden¬ing of parts in production, the correlation of hardenability information with the [ ] hardness and properties of production parts is often not of satisfactory accuracy. The general effects of these variables on the austenitic grain size, distribution of excess carbides and critical cooling rate have been known for many years and one or more have been investigated by Shepherd ,2 3 Davenport and Bain,4 Digges,5,6 Digges and Jordan,7 Post and associates&apos; and Roberts and Mehl,9 to mention only a few. There has been no systematic investigation, however,&apos; into the quantitative variations produced on the hardenability of commercial high¬carbon steels by changes in these factors of time, temperature and prior structure. PROCEDURE A plain carbon hypereutectoid steel, S.A.E. 52100 and Graph-Mo, a molyb¬denum-bearing high-carbon steel contain¬ing some graphite, were chosen for this investigation. The chemical analyses of these electric-furnace steels are given in Table I. [ ] The procedure used was exactly that reported previously,&apos; hence the details will not be repeated here. Normalized (1650°F.) and spheroidized prior structures were utilized on all steels with hot-rolled and quenched (1600°F. oil) prior conditions added for the plain carbon steel. The end-quench test developed by Jominy10 was selected for use in this investigation and, with the noted exceptions, the American Society for Testing Materials standard. procedure was followed. The effect of time at temperature was examined at intervals of 0, 10 and 40 min. and 4 hr., and a few i6-hr. tests were run. Salt-bath heating of the specimens was employed to control and minimize the

Jan 1, 1944

By H. J. Rose

SIXTY-FIVE million net tons of coal were carbonized in the by-product and beehive coke ovens1 of the United States during 1924. This tonnage represented 13.4 per cent. of the bituminous coal which was mined in that year. Table 1 shows production and disposition.2 TABLE 1.-Production and Disposition of Oven Coke in 1924 BY-PRODUCT BEEHIVE TOTAL Coal charged into ovens, tons 49,061,339 15,914,310 64,975,649 Coke produced (exclusive of screenings and breeze), tons 33,983,568 10,286;037 44,269,605 Average yield of coke, per cent 69.3 61.6 68.1 Disposition of coke: PER PER PER CENT. CENT. CENT. Blast furnace 82.5 82.8 82.6 Foundry 4.6 13.3 6.6 Domestic 8.3 1.4 6.7 Water gas manufacture and all other uses 4.6 2.5 4.1 Cokes having somewhat different combinations of chemical and physical properties are desired for the various uses listed above, and these properties depend primarily upon the types of coal used. American coals have a wide range of purity and coking quality, and the chief subject of this paper will be the selection of coals for the manufacture of blast furnace, foundry, domestic, and water-gas coke, in by-product coke ovens. It will obviously be necessary to include a discussion of those physical and chemical characteristics that are generally considered essential or desirable for each type of coke.

Jan 7, 1926

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&apos; 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&apos;, at 0 pct Si as log K ,. The slope of each line gives the value

Jan 1, 1962