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By William Campbell

(Cleveland Meeting, October, 1912.) [SECRETARY'S NOTE.-To avoid repetitions of foot-notes, references to authorities are made in the paper by means of figures, referring to a numbered list in the appendix.-J. S.] I. INTRODUCTION. IN the olden days the making of alloys was au art, and the secrets of the craft were jealously guarded. To-day it has become a science, though the old ideas in regard to the secrets and formula are dying hard. Modern progress may be attributed to scientific research and testing of materials, and the substitution of chemical analytical control for " cook-book " methods. We know to-day a great deal about the constitution of alloys, the reasons of the change in structure and physical properties by heat and mechanical treatment; and this new knowledge is due for the most part to the physical chemist and metallographist, who have shown us that alloys are simply solutions, and as such obey definite laws. The application of the theories of solutions and of the phase rule tells us what ought to happen when our alloys are in a state of equilibrium. The working-out of the temperature-composition diagram (thermal diagram) for numerous alloys has thrown a light on the structure and constitution which has dispelled most of the darkness in which we labored before the advent of metallography. The work began with the determination of the freezing-point curves, and here the research of Le Chatelier,1 Gautier,2 Roberts-Austen,3 and the other pioneers broke the ground. Next the physical chemists, Tammann,4 Rooseboom,5 Bancroft,6 and their colleagues, showed us the complete thermal diagram and its meaning. Then the researches of Heycock and Neville 7 on the Cu-Sn series and of Shepherd 8 on the * Associate Professor of Metallurgy, Columbia University in the City of New York.

Dec 1, 1912

By Oscar Weiss

An aerial magnetometer survey was carried out by the author's geophysical organization over the Vredefort dome, where Witwatersrand beds are wrapped around a granite plug 25 to 30 miles in diameter. The well- known magnetic shales of the Lower Witwatersrand system (to be referred to as LWW) give strong negative anomalies over the out-cropping portion of the dome. This is unusual as these same shales -cause positive anomalies over large areas near Johannesburg and along a strike of 130 miles between the East Rand and Klerksdorp. It is suggested that the negative polarization is caused by heat and stresses connected with the doming. This negative polarization of sedimentary beds, which usually cause positive anomalies, is a good example of how "magnetic lows" can be caused by "structural highs." Significant magnetic anomalies should be tested by gravity and seismic methods irrespective of the sign of the anomalies.

Jan 1, 1949

By C. R. Hayward

CARLE R. HAYWARD.-I do not want it understood that I think that the conclusion that the time of tempering temperature is immaterial has been definitely proven, but since these are the first definite figures put out, I thought before continuing on more work ourselves, it would be well to present them as progress and for information. J. A. MATHEWS, Syracuse, N. Y.-I think that if Prof. Hayward would consult the paper of Profs. Barus and Strouhal,1 1885, he would find about 250 pages, mostly figures, on this subject, in which they investigated the tempering effect by electrical and magnetic methods. There are so many figures in the paper that it is very difficult reading. One point particularly brought out was that even at a low temperature, such as the boiling point of alcohol, about 60° C., there is a tempering effect, increasing up to 4 hr. One reason they obtained those results, with which the present authors are at variance, was that they started with a high-carbon steel which hardens thoroughly, whereas the steel Prof. Hayward and his collaborator used was a comparatively mild steel which does not take a great deal of hardening. About 3 years ago Mr. Stagg and I published 2 a few figures bearing on the same subject, but we used .a low-carbon alloy steel of high tempering qualities and found a great deal of improvement, particularly in ductility, by continuing the drawing up to 4 hr. We used a chrome-vanadium steel showing after heat treatment 250,000 tensile strength. On short drawing, we got almost no ductility, but by continuing to 4 hr., we raised it to 12 per cent. I believe Prof. Hayward's results are due to using comparatively mild steel, whereas Prof. Barus used drill rod and carried out a, wonderfully exhaustive

Jan 4, 1917

By Lendall P. Warriner, Blandford C. Burgess

Jasper County lies just north of the geographical center of Georgia, bounded on the west and north by the Ocmulgee River. The county seat, Monticello, is approximately 65 miles east-southeast of Atlanta and 40 miles north of Macon. It is served by the Macon-Athens branch of the Central of Georgia Railway Co. and by five paved highways converging from adjoining county seats. Farming and lumbering are the principal local occupations. About half the county is covered with pine and mixed hardwoods; a large part of the forested land is owned by the Soil Conservation Service of the Department of Agriculture in its Piedmont Land Utilization Project. The topography is one of gently rolling field and forest with occasional hills rising 100 ft or: more above the creek beds. Though annual rainfall is in the neighborhood of 60 in., most of it falls in torrential downpours of short duration which tend rapidly to erode the red soil and convert the country roads to greasy tracks of red mud.

Jan 1, 1949

By James R. Holden, Frederick E. Wang

Through both single-crystal and powder X-ray diffraction methods, ten A6B23-type compounds have been confirmed to exist between lanthanides (A) (plus scandium and yttrium) and manganese (B); A = Y, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, and Lu. The formation of a compound of this type is shown to he extremely atomic size-sensitive; hence it can be classified as a "size-factorH compound. The "enveloping effect", a geometrical consideration observed in its crystal structure, is proposed as the reason for the A6B23-type compound being size-sensitive. The approximate ideal geometrical ratio of the radii R/r is 1.31 while experimentally A6B23-type compounds have a radius ratio lying within the range 1.2 to 1.4. FLORIO t al.' characterized the structure of Th6MnZ3 as fcc, space group Fm3m, with 116 atoms in the unit cell. Since then, a number of isotypic binary compounds, and recently Gd n,,' have been confirmed to exist. The fact that strontium and barium form A6Bz3-type compounds with magnesium strongly suggested the possible existence of Ba6Liz3. However, investigation3 showed the compound Ba6LiZ3 to be absent. Since both strontium and barium are group 11-a elements and are therefore "open metals",6 the nonexistence of Ba6LiZ3 can hardly be explained satisfactorily by valence-electron considerations. On the other hand, the consistent atomic-radius ratio, (R/r),* observed for the known A6Bz3-type compounds,3 strongly suggests that the formation of compounds of this type is atomic size-sensitive. Therefore, one is tempted to explain the nonexistence of Ba6LiZ3 entirely on the basis of the atomic-size difference between strontium and barium. However, this approach is not entirely without objection. Atoms are not rigid spheres and are known to vary in size within certain limits.7 Since the atomic-radius difference between strontium and barium (0.07 to 0.09A) is within these limits, it is reasonable to assume that the size difference would have a negligible effect on the formation of Ba6LiZ3. This view is further supported by the fact that the radius ratio, R/r, in other known "size-factor" compounds is observed to range widely—for example, from 1.08 to 1.45 for ABz-type compounds (C15, MgCuz type)' and from 1.37 to 1.58 for AB5-type compounds (D2d, CaZn5 type).g The present investigation was undertaken in order to find a more satisfactory explanation for the non-existence of Ba6LiZ3 and, consequently, a better understanding of the nature of the A6Bz3-type compound. The primary objectives are to confirm the previous conclusion3 that the A6B23-type compound is indeed a "size-factor" compound and subsequently to determine the atomic-radius ratio range in which the A6Bz3-type compound can exist. In order to achieve these objectives, stoichiometric A6Bz3 alloys, where manganese (B) was alloyed with various lanthanide elements (A), were selected for investigation. The atomic-radius ratios of lanthanide elements with manganese range from 1.26 for Lu/~n to 1.46 for Eu/Mn. This radius ratio range includes and exceeds the range of all previously reported A6Bz3-type compounds—1.32 for Th/Mn' through 1.38 for Sr/Li. Furthermore, the atomic-size difference between successive elements of the lanthanide series in order of atomic number) is of the order of 0.01A (europium and ytterbium are exceptions). The series of lanthanon-manganese alloy systems is ideally suited to a precise determination of the limits of allowable atomic-radius ratio for A6Bz3-type compound formation. EXPERIMENTAL PROCEDURE The lanthanide metals, in ingot form, supplied by Michigan Chemical Corp. (St. Louis, Mich.) and Nuclear Corp. of America (Burbank, Calif.), were guaranteed by the suppliers to be at least 99.9 wt pct pure (traces of silicon, calcium, and other minor constituents present on occasion, not to be more than 0.05 wt pct) as shown by spectrographic analysis. Manganese metal, in polycrystalline form, was redistilled from the commercial, chemically pure grade and was analyzed to be at least 99.95 wt pct pure. In all cases, the atom ratio between the two elements in each charge was A (rare-earth meta1):B (manganese) = 6:23 and a constant weight, 3 g, of

Jan 1, 1965

The following is an incomplete list of members and guests who called at Institute headquarters during the period Sept. 10, 1919, to Oct. 10, 1919. L. D. Anderson, Salt Lake City, Utah. P. S. Matthews, Newark, N. J. Ray J. Barber, New York City. A. Poole Maynard, Atlanta, Georgia. L. A. Barton, Major U. S. Engineers. L. J. Mayreis, Jamshedpur, India. J. A. Battle, Chicago, 111. Benj. L. Miller, Bethlehem, Pa. R. W. Bissell, New York City. Geo. D. Morgan, Bartlesville, Okla. Gilman E. Brown, Shanghai, China. A. C. Munroe, El Paso, Texas. Stanley Brown, Chuquicamata, Chile, Paul I. Norton, Jr., Columbus, Ohio. S. A. Walter G. Perkins, Stanford University, Norman Carmichael, Clifton, Arizona. Cal. Richard H. Catlett, Newark, N. J. Fred S. Porter, Seattle, Wash. Roderic Crandall Charles E. Prior, Cherry Creek, Nevada John J. Croston, Atlanta, Georgia. G. M. Richards I. N. Dally, Seattle, Wash. Gilbert Rigg, Melbourne, Australia. A. Faison Dixon, New York City. Pierre H. Sauvajol, Paris, France. Walter Dobbins, Springfield, Ill. Carl Scholz, Chicago, Ill. Foss E. Douglass, Rancagua, Chile. Ellsworth H. Shriver, Marysville, Ohio. H. S. Emlaw, Grand Haven, Mich. Harvey B. Small, Magangue, Colombia. R. S. Everet, Barre, Mass. Henry B. Smith, New Britain, Coma. H. W. Gipp, Melbourne, Australia. J. T. Smoody, Cornwall, Pa. F. A. Glass, Brainerd, Minn. S.. J. Speak, London, England. C. D. Grier, New York City. D. R. Thomas, New York City. James L. Head, Rancagua, Chile. Kirby Thomas, New York City. Geo. B. Holderer, New York City. R. M. F. Townsend, Washington, D. C. W. Spencer Hutchinson, Boston, Mass. Carl J. Trauerman, Helena, Mont. Henry Jequier, Paris, France. A. C. Veatch, London, Eng. L. W. Kemp, Chuquicamata, Chile. Myron R. Walker, Pittsburg, Pa. Herbert S. Kohlberg, El Paso, Texas. Curtis C. Webb, New York City. H. M. LaFollette, La Follette, Tenn. James Wilding, San Francisco, Cal. Richard Lamb, New York City. S. H. Zimmerman, New York City.

Jan 11, 1919

By Bjorge, Guy N.

MINING method improve through the gradual process of evolution and in 1340 there were no marked outstanding innovations. On the other hand refinements of detail and betterment: in equipment design continued to progress. Among the most important changes have been the increased application of trucks and highway equipment, including tractors and bull- dozers, to open-pit mining as exemplified by Phelps Dodge's Morenci operations; the Mesabi iron range; and the Tri-State district. Mass or bulk handling contributed its part underground with slurhers and conveyors at Consolidated Coppermines and slushers at Climax; and in open-pit mining. conveyors found increased use on the Mesabi range.

Jan 1, 1941

Jan 1, 1886

By R. E. Heithecker

Almost every oil well drilled into limestone formations in Kansas is treated with hydrochloric (muriatic) acid upon completion: to increase potential capacity of well and thereby increase its "daily allowable" production; to shorten time required to produce recoverable oil; and to increase quantity of oil recovered ultimately from reservoir. Acid treating marked a forward step in the producing fields of Kansas; in fact, many old limestone fields that almost had reached their economic producing limit were "rejuvenated" with acid and their capacities to produce increased several times. It also caused a marked increase in the ultimate oil recovery of some old and nearly depleted fields of Kansas. The effect of the acid was due to the cleaning-out action by the acid at the face of the limestone, the enlargement of the small drainage channels, and the apparent penetration of the acid to previously undrained porous and saturated strata. Studies of the effects of acid were made in the Fairport field, three groups of wells in the El Dorado field and the Shutts field. Estimation of increased recoveries resulting from acid in these fields and groups of wells ranged from 1000 to 2400 bbI. per acre. Limestone structures that had been tested by drilling and found noncommercial were later completed as commerical oil-producing formations through the use of acid. The Kansas City formation, Valley Center field of Kansas, is an example. Increased oil production and revenue from the old fields justified the reconditioning of equipment, which in most cases had become in poor mechanical condition. The first treatment with hydrochloric acid of an oil well in Kansas was in October 1932, and by the end of 1937 almost 6000 wells had been treated. Many wells were treated more than once and the total number of treatments exceeded 8000 by the end of 1937. Approximately 12 3/4 million gallons of acid was required for these treatments. The report includes 15 illustrations and 16 tables.

Jan 1, 1939

By R. E. Heithecker

Almost every oil well drilled into limestone formations in Kansas is treated with hydrochloric (muriatic) acid upon completion: to increase potential capacity of well and thereby increase its "daily allowable" production; to shorten time required to produce recoverable oil; and to increase quantity of oil recovered ultimately from reservoir. Acid treating marked a forward step in the producing fields of Kansas; in fact, many old limestone fields that almost had reached their economic producing limit were "rejuvenated" with acid and their capacities to produce increased several times. It also caused a marked increase in the ultimate oil recovery of some old and nearly depleted fields of Kansas. The effect of the acid was due to the cleaning-out action by the acid at the face of the limestone, the enlargement of the small drainage channels, and the apparent penetration of the acid to previously undrained porous and saturated strata. Studies of the effects of acid were made in the Fairport field, three groups of wells in the El Dorado field and the Shutts field. Estimation of increased recoveries resulting from acid in these fields and groups of wells ranged from 1000 to 2400 bbI. per acre. Limestone structures that had been tested by drilling and found noncommercial were later completed as commerical oil-producing formations through the use of acid. The Kansas City formation, Valley Center field of Kansas, is an example. Increased oil production and revenue from the old fields justified the reconditioning of equipment, which in most cases had become in poor mechanical condition. The first treatment with hydrochloric acid of an oil well in Kansas was in October 1932, and by the end of 1937 almost 6000 wells had been treated. Many wells were treated more than once and the total number of treatments exceeded 8000 by the end of 1937. Approximately 12 3/4 million gallons of acid was required for these treatments. The report includes 15 illustrations and 16 tables.

Jan 1, 1939

By D. K. Crampton

ON giving thought to the subject of this paper, my first reaction was that many and striking changes have come about as a direct result of the war. However, more careful analysis indicates that few, if any, of these changes can be wholly attributed to it. The actual situation is that all these changes were conceived and most of them at least partially executed in re- cent prewar years, it remaining the role of war to achieve results in a fraction of the time that might normally have been taken, lacking its driving impulse. The further discussion will therefore be with the premise that the individual changes have been greatly hastened rather than directly and primarily caused by any war conditions. Co-operation among copper alloy producers on production problems is agreed to be much worth while. The industry was too long noted for jealousy and secrecy as to equipment, methods, and even materials produced. Gradually, a more open and co-operative policy evolved but even just prior to the war the interchange of ideas was relatively cautious and limited. The need for a great increase in production in record time fostered a more co- operative attitude; exchange of ideas and experience concerning all phases of production increased tremendously to the benefit of the individual participants and thus the war effort, too. This more united effort has undoubtedly led to many specific improvements in process or equipment and these in turn to more rapid and economical operation than could have taken place on an each-for-himself basis.

Jan 1, 1944

By J. W. Buch

IN THE FIELD of track haulage, interest has seemed to center on the question of larger mine cars both for handling material from loading point to shaft bottom or surface, and for shuttle service. Saving of time in car changing is obvious if larger cars are used. In addition, shorter trips result where car transportation is from face to opening without transfer. This also brings about side-track and equipment savings. Track shuttle service, using large automatic-dump cars (10 tons) between loading machines and trip loading point, has been a satisfactory solution for the operator who mechanizes a working mine regularly equipped with a large number of small mine cars. This development in track shuttle haulage, has made track installation and maintenance increasingly important, requiring closer supervision.

Jan 1, 1942

By DOOLITTLE E. M.

(Canal Zone Meeting, November, 1910.) The following notes are contributed, not with the idea of offering a complete history of the development of this very important process as applied to the Leadville district, but with the hope that the practice, as it was carried out in the Bi-Metallic Smelter, may still be of interest to others. The Bi-Metallic Smelter, at Leadville, Colo., was the first to make a commercial success of the process described in the following pages, which consisted essentially of smelting raw silver- and copper-bearing sulphide ores in blast-furnaces to form a matte, which was generally re-smelted with siliceous ores for a second high-grade matte. Robert Sticht, in his excellent monograph on the subject,1 has outlined briefly the plant belonging to this company. He says, in effect: The Boulder, Mont., enterprise set the example for others with whom the patentee (w. L. Austin) had been negotiating, and the old La Plata lead-smelter at Leadville, Colo., was fashioned into a crude, temporary experimental plant for the Bi-Metallic Company, and the feasibility of the process demonstrated by a trial run. Subsequently, the plant was considerably improved, and, being supplied with very favorable ores, continued to run without interruption from August, 1892, to June, 1893. In September, 1893, smelting was resumed in a completely remodeled establishment, some $200,000 having been expended upon the new work. Thus, aside from the Montana experiments, which, under the direction of W. L. Austin, began as early as- 1885 2 at Toston, and continued with indifferent success for six or seven years, the Bi-Metallic plant at Leadville may be said to have * Formerly Superintendent, Bi-Metallic Smelting Co. + Formerly Chief Assayer and Chemist, Bi-Metallic Smelting Co. 1 Modern Copper Smelting, E. D. Peters, 7th ed., p. 415 (1895). 2 Trans., xvi., p. 259 (1887-88).

Dec 1, 1910

By William J. Priestley

Much time has been devoted, by metallurgists, to the study of steel after solidification and remarkable strides have been made in the heat treatment of steel, but less knowledge is available of the thermophysical activity of the constituents of steel prior to solidification in the mold. It is known that certain elements added to steel produce marked changes in physical properties, also that other elements added to steel produce similar changes, but we have only meager knowledge as 'to. how these elements combine in steel under different conditions of solidification. It is not sufficient to know, from chemical analysis, that a certain element is present in steel. We should know how this element is in combination with the other elements and whether the combination is such as will give the greatest physical properties. Certain elements go into solid solution with the iron, while others segregate to the grain boundaries and combine with the impurities collected there. Until it is known where an alloy produces the most beneficial effect and a means is determined for controlling its physical location by altering solidification conditions, or otherwise, we will not obtain the maximum value from our alloys. When molten steel freezes, it forms a heterogeneous mass of various crystalline constituents; and as the transformation of steel from a liquid state to the solid crystallized state is a critical step, involving as great a transfer of heat as any other operation in the making of finished steel, a variation in the rate of this heat transfer will have much to do with the arrangement of the various constituents in the solid state. The object of this paper is to show some of the effects on steel caused by variations in the rate of cooling in the ingot mold, particularly as to ingotism, segregation, dendrites, and intergranular material.

Jan 1, 1924

By J. Burns Read

IT IS the purpose of this paper to summarize, as far as possible, the metallurgical information and experience gained by the Ordnance Department, during the War, in the manufacture of artillery cartridge cases, to describe the tests to which artillery cartridge cases were put, and to summarize the knowledge and experience gained in this testing. The authors wish to acknowledge the aid given by manufacturers, army officers, and civilian employees of the Ordnance Department in obtaining these data. Artillery cartridge cases are cold drawn from circular disks punched from strips of rolled brass. The manufacture involves from 25 to 30 main operations, which are done almost entirely on a punch press. Descriptions of the operations have appeared in various periodicals and, therefore, will not be given here. After each cupping, or drawing, operation, except the last, the cases are annealed at from 540° to 650° C. (1000° to 1200°F.), to remove all the hardening stresses set up in the metal and to allow complete recrystallization. After each annealing, the cases are pickled in niter cake or sulfuric-acid solution and then washed in water to remove all traces of acid. In some instances, the cases are then immersed in a cyanide-salt solution, and afterwards rinsed in water, to remove the thin layer of copper that forms on the surface of the cases during the acid pickle. The last cold-drawing operation is followed, by the heading operation which, by flattening the head of the case on the outside, causes the metal to flow on the inside to approximately the proper finished dimensions. The mouth, or open end, is then annealed at 430° to 480° C. (800° to 900° F.) by immersion in a salt bath or by gas flames. After being washed, the cases are tapered, when they are ready for machining, inspection, and testing.

Jan 4, 1922

By Robert D. Longyear

IN MOST diamond core drilling the primary objective is the recovery of samples to be used for chemical analysis, physical tests, or visual inspection. Unless these samples are reliable and the information systematically recorded, the time and money spent in securing them are largely wasted. A properly taken diamond-drill sample is similar to a properly moiled channel sample but more accurate. No channel sample can be moiled in as even a groove as the smooth cylinder of material normally removed in diamond drilling. More important still, sampling by the diamond drill practically eliminates that personal equation which Jora1emon4 reference numbers apply to publications listed in the bibliography at the end of this article) has aptly termed "the almost magnetic attraction of the most conscientious hand toward rich pieces of ore."

Jan 1, 1937

Truman H. Aldrich '78 Andrew S. McCreath '75 W. S. Ayres '73 Walter McDermott '74 A. A. Blair '75 Philip N. Moore '74 Walter M. Brodie '72 Henry S. Munroe '72 H. M. Chance '74 James Wilson Neill '79 Frederick G. Corning '77 I. P. Pardee '73 Henry S. Drinker Founder Edward C. Potter '79 Ernest F. Eurich '74 Alexandre Pourcel '77 W. E. C. Eustis '76 William H. Radford '76 A. Heckscher '79 Robert H. Richards '75 Henry D. Hibbard '79 Albert F. Schneider '74 Julian Kennedy '79 Porter W. Shimer '79 William St. George Kent '72 John Stevenson, Jr '76 Frank Lyman '77 Arthur Thacher '76 John Markle '79 Edward H. Williams '76 Samuel Mather '79 Thomas D. Wood '79

Jan 1, 1929

By H. P. Greenwald

THE Committee on Rock-Dusting was formed after the fall meeting of the Coal Division in Chicago in 1938. Its primary task was to study the recommended American practice for rock- dusting coal mines to prevent coal-dust explosions as approved by the American Engineering Standards Committee. After approximately two years' work he committee concluded that although certain portions of the recommended practice could well be revised, information needed for a logical revision was not at hand, and it was inadvisable, therefore, to make revisions

Jan 1, 1943

Professional Divisions I-Institute of Metals Division* GEORGE K ELLIOTT, Chairman GEORGE C STONE, Vice-chairman WILLIAM M CORSE, Secretary-treasurer Executive Committee D K CRAMPTON SAMUEL L HOYT R I, SUHL W K FRANK ZAY JEFFRIES A E WHITE H W GILLETT H C JENNISON R F WOOD STANISLAUS SKOWRONSKI II-Petroleum Division F JULIUS FOHS, Chairman EDWARD L ESTABROOK, Vice-chairman C P WATSON, Secretary-treasurer

Jan 1, 1923

By J. C. Swartz

Measurements of the effect of precipitation stresses on the solubility of cementite (Fe3C) precipitates in a iron are reported. Solubilities were determined from measurements of the Snoek relaxation due to interstitial carbon after quenching from various equilibrium treatments. Stress-free precipitates were obtained by a spheroidizing treatment of vacuum-melted Fe 0.06 wt pet C. Subsequent equilibration treatments were designed to suppress nucleation of other precipitates. The results for stress-free cementite give a heat of solution of 14.8 i 0.2 keal per mole and an entropy change of 1.1 i 0.2 eu in the temperature range 400" to 715°C. Comparison with previous data indicates that the heat of solution increases about 6 keal per mole as temperature increases from 700" to 1000°C. Data on self-stressed cementite in quench-aged specimens of Fe 0.013 wt pet C indicate 1) an apparent heat of solution of 12.1 i 0.4 keal per mole in the range 280" to 690°C, 2) a strain energy of- 1.1 keal per mole Fe3C accompanying precipitation at 280°C, and 3') a gradual decrease in the strain energy of precipitation with increasing equilibration temperature. In com-parison with 2 and 3 the strain energy calculated for an isotropic model is 1.7 keal per mole Fe3C. The lower values obtained from the experiment indicated substantial stress velaxation by dislocation motion. WHEN a supersaturated solution of carbon in a iron is aged at temperatures in the range 200o to 700oC, the carbon clusters by interstitial diffusion and forms cementite (Fe3C) precipitate particles. Unstressed cementite has a volume per iron atom 9 pet higher than that of a iron;' hence, cementite precipitate particles are usually under pressure from the iron matrix. The pressure would tend to increase the solubility of cementite in iron.' This report describes anelastic measurements of the solubilities of self-stressed and stress-free cementite in a iron. Previous determinations of the cementite solubility are summarized in Table I. The method of cementite formation for each reference was studied to ascertain the state of stress of the cementite. The results judged to be for stress-free and stressed cementite are distinguished in the table. In the next section an estimate of the stress effect is obtained which is clearly too small to account for the large difference between the previous results in parts A and B of the table. THEORETICAL Let AGO be the standard free-energy change of the reaction Fe3C (eem.) = 3Fe (a) + C (in a) [1] in the absence of stresses. Since cementite precipitates appear to be rather pure10 and the carbon is so dilute in the iron,8 the cementite and iron of Eq. [ I] for the stress-free case have essentially unit activities and the activity of carbon equals its atom fraction xoC Then the stress-free equilibrium is expressed by RT In XoC = -?GO 121 To first approximation the change in the chemical potential of carbon due to the precipitation stresses equals the elastic strain energy W accompanying precipitation of a mole of cementite.2 Hence, in the presence of the precipitation stresses the equilibrium is described by RT In x sq = -?G° + W [3] where xsC is the mole fraction of dissolved carbon in the stressed case. An approximate value of W can be obtained from analysis of the inclusion problem in elasticity theory. The inclusion is a small portion of the matrix phase which has suffered a transformation while still imbedded in the matrix. In the absence of the constraint of the matrix the transformation would be equivalent to a uniform dilational strain eT. Both the matrix (a) phase and inclusion (0) phase are assumed to be homogeneous, isotropic materials. When the a and 0 phases have the same elastic moduli, which is approximately true for iron and cementite,11 the total strain energy per mole ß is12 2µVß(eT)2(3 +4 µx)-I [4]

Jan 1, 1968