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By Robert Leach

THIS paper gives a brief summary of the process of manufacture of sterling silver, and some of its more important physical properties, as observed in commercial production of rolled sheet and wire. Although papers have been published by Turner and Smith,1 Rose,2 Sperry3 and Jordan,4 there are few technical data available, and unfortunately the time allowed for the preparation of this paper has not been sufficient to make it as comprehensive as the title might indicate. ANALYSIS OF STERLING SILVER Fine or pure silver is too soft for coinage and the manufacture of articles in which strength and resistance to wear are desired. From the earliest times of which we have record, copper has been the metal generally used to harden silver. Analyses of coins and silver articles from ancient tombs show varying amounts of copper, and old Roman silver objects in the British Museum have approximately the same analysis as our sterling. The first authentic record of the establishment of a standard alloy is during the reign of Henry II in England. During the twelfth and thirteenth centuries, the people in the Eastern Provinces of Germany had a reputation for the standard and purity of their silver coinage, and it is said that Henry II employed some of these Easterlings, as they were called, to improve and standardize the English coinage, which had become debased. The peculiar standard adopted is probably accounted for by the system of weights used. A troy pound contains

Jan 1, 1928

By Alfred H. Bell

Drilling activity increased in Illinois in 1935. There were 34 com-pletions as compared with 26 in 1934 and 18 wells were drilling at the end of 1935. Some large blocks of acreage were leased in Marion and Clay counties near the central part of the Illinois structural basin. Production of oil in the state totaled 4,305,000 bbl., a decrease of 4 per cent from that of 1934 There was some curtailment of production in the early part of 1935 but none after April 30 as shown in the following table. Percentage Pro-duced of Potential ProductioN (USING September 1934 Period as BaSis) Jan. .l-Feb. 20............................................ 79 Feb. 21-Feb. 25............................................ 85 Feb. 26-Feb. 38............................................ 79 Mar. 1-Mar. 11............................................ 85 Mar. 12-Mar. 31............................................ 100 Apr. 1-Apr. 9.......................................... 80 Apr. 10-Apr. 30............................................ 86 May 1-Dec. 31........................................... 100 This is equivalent to an average curtailment throughout the year of 5 per cent. The price of Illinois crude oil at the wells remained constant during 1935 at $1.13 per barrel. A small amount of oil was sold at a 1ower price, notably from the Dupo field, but to arrive at a value for the state's production there would be little error in assuming an average price of 81.13, giving a total value of $4,864,465. The following table shows production in Illinois by moths in 1935, according to the U.S. Bureau of Mines. Jan............. 332,000 May.......... 382,000 Sept ,............. 370,000 Feb............. 295,000 June. ........... 858,000 Oct.............. 391,000 Mar............ 370,000 July............ 377,000 Nov............. 369,000 April............ 338,000 Aug............. 379,000 Dec............ 344,000

Jan 1, 1936

By Alfred H. Bell

Drilling activity increased in Illinois in 1935. There were 34 com-pletions as compared with 26 in 1934 and 18 wells were drilling at the end of 1935. Some large blocks of acreage were leased in Marion and Clay counties near the central part of the Illinois structural basin. Production of oil in the state totaled 4,305,000 bbl., a decrease of 4 per cent from that of 1934 There was some curtailment of production in the early part of 1935 but none after April 30 as shown in the following table. Percentage Pro-duced of Potential ProductioN (USING September 1934 Period as BaSis) Jan. .l-Feb. 20............................................ 79 Feb. 21-Feb. 25............................................ 85 Feb. 26-Feb. 38............................................ 79 Mar. 1-Mar. 11............................................ 85 Mar. 12-Mar. 31............................................ 100 Apr. 1-Apr. 9.......................................... 80 Apr. 10-Apr. 30............................................ 86 May 1-Dec. 31........................................... 100 This is equivalent to an average curtailment throughout the year of 5 per cent. The price of Illinois crude oil at the wells remained constant during 1935 at $1.13 per barrel. A small amount of oil was sold at a 1ower price, notably from the Dupo field, but to arrive at a value for the state's production there would be little error in assuming an average price of 81.13, giving a total value of $4,864,465. The following table shows production in Illinois by moths in 1935, according to the U.S. Bureau of Mines. Jan............. 332,000 May.......... 382,000 Sept ,............. 370,000 Feb............. 295,000 June. ........... 858,000 Oct.............. 391,000 Mar............ 370,000 July............ 377,000 Nov............. 369,000 April............ 338,000 Aug............. 379,000 Dec............ 344,000

Jan 1, 1936

By J. C. Trantham, J. W. Marx

From 1955 to 1958 the Phillips Petroleum Co. conducted a series of small scale counterflow combustion field tests in a tar sand about 60-ft deep and 6 to 12-ft thick near Bellamy, Mo. A total of seven different well patterns, including conventional five-spots and seven-spots plus a 15-well line drive pattern and a 10-well radial pattern, were employed. Electric heaters, gas burners and wellbore fuel packs were tested as counterflow ignition devices. Direct drive ignition followed by reversal to counterflow operation was not possible in this case because of formation plugging by the semi-solid tar during the direct drive phase. Sustained counterflow burning was achieved with wellbore fuel packs under conirolled conditions which permitted close correlation of fire front velocity, air velocity, air-oil ratios and yields for a wide variation in process parameters. The tar in place was about 10' APl with a reservoir viscosity greater than 500,000 cp. The composite oil prodlcct was 26' API with a viscosity in the range of 5 to 15 cp. Vertical sweep efficiency in the line drive pattern was essentially 100 per cent, with no evidence of gravity segregation. Original tar in place ranged between 800 and 1,000 bbllacre-ft, specific rock permeability averaged about 800 md before burning and effective air pemeability with residual oil and water in place (at the time of ignition) averaged 250 md. The volume of oil recovered during stabilized line drive counterflow burning represented about 67 per cent of the volume of tar originally in place in the burned out zones. A minimum was found when air-oil ratios were plotted against formation air velocities, and a limiting air velocity existed below which the counterflow fire front reversed and burned back over its own trajectory, using the residual coke left behind. INTRODUCTION Early in 1955 the Phillips Petroleum Co. began preparations to field test counterflow underground combustion as a method for producing oil from high viscosity hydrocarbon deposits, such as bituminous (tar) sands. At that time all published information on the use of underground burning io increase oil recovery was based on the direct drive process, in which the fire front moved through the formatim in the same direction as the injected air stream. Such direct burning is not applicable to many heavy oil sands or to most tar sands because the heat-thinned native hydrocarbon congeals in the cold rock ahead of the fire front forming a gas permeability block which smothers the combustion. Laboratory experiments first demonstrated that this permeability blocking would not occur if the fire front and the air stream moved in opposite directions. In this counterflow (reverse) burning process the heated heavy oil or tar is driven back through the combustion zone. Here thermal cracking produces relatively light hydrocarbon products which pass through the heated rock behind the fire front (largely in the vapor phase) and are incapable of causing a gas permeability block.' Exploratory wring revealed that consolidated bituminous sandstones with a combination of tar saturation, permeability, thickness and depth favorable for experimental field testing existed at several points in western Missouri. By the fall of 1955, a test site for determining technical feasibility of the counterflow process under field conditions had been selected near Bellamy, Vernon County, Mo. — about fifty miles north of Joplin. The pay zone was too thin and too shallow to constitute a commercial prospect, but these same factors permitted controlled experimental operation with a small compressor installation and with a large number of monitor wells. These were needed for adequate observation of the underground phenomena at reasonable cost. RESERVOIR CHARACTERISTICS The reservoir chosen for the experimental field tests was a 124 thick section of tar sand extending from 49 to 61 ft subsurface, with shale and siltstone laminations sealing the top and bottom. This section was part of a larger 30-ft thick tar sand deposit which extended both above and below the test zone. Core analyses showed that the 12-ft sand was effectively subdivided into two approximately equal sections, with the lower zone being consistently more permeable than the upper zone. The most significant laboratory core data are summarized in Table 1. The line drive test which is the principal subject of this report utilized only the lower 6-ft thick zone, with the upper zone regarded as part of the 55-ft overburden. WELL PATTERNS The over-all field test program involved a total of seven different well patterns, including conventional five-spots and seven-spots plus a 15-well line drive pattern and a 10-well radial pattern. In some of the tests the full 12-ft zone was employed; in other cases only the more perme-

Jan 1, 1967

By John Griffen

HYDRAULIC classification as explained by Rittinger and others was largely restricted to conditions wherein the free-falling velocities of the particles were conceived as governing the separations effected (see chapter 9). The laws governing classification under free-falling conditions have been summarized by Chapman and Mott as follows:

Jan 1, 1943

By AIME AIME

HE State of Utah has an area of 84,990 sq. mi., and like other inland states in the West its population, although steadily increasing, is relatively small. The fact that it is a state possessing vast mineral resources is attested by a careful study of statistics which have been compiled by Federal and State investigators. Some idea of the extent of these resources and the degree of development of a particular state or region may be gained by such a study, but in the case of Utah statistics and other available information fail to portray completely the true extent and value of its existing metallic and non-metallic resources. The State is probably more widely known for its production of metallic ores which has placed it in an eminent position among the metal mining states of the Nation.

Jan 1, 1925

By Edward H. Robie

THE registration badges gave out, there were not enough programs, the Pioneer Hotel's rooms were insufficient, and some hundred applicants for banquet tickets had to be turned down at the Institute's Regional Meeting in Tucson, Nov. 1-5. Minor inconveniences these, however, occasioned by the fact that, optimistic as they are in Arizona, about half again as many partook of the week's activities as were expected. For this, the local program committee can be blamed-both the technical and social features were too attractive in quantity and quality. Seriously speaking, though, the Institute has probably never had a more successful Regional Meeting than this one. It being the first that has been held in Arizona in 22 years, no effort was spared to make it the distinctive gathering that it was.

Jan 1, 1938

By L. Weaver

THE Tennessee Copper Co.'s mines are in the southeast corner of the state of Tennessee. Polk Co., in the well-known Ducktown copper basin. Their new circular production shaft will eventually be the only ore hoisting shaft, and is located for handling ore from Boyd, Calloway, Mary, and Cherokee mines. A circular, rather than a rectangular, shaft was decided upon because: 1-The circular shaft section is stronger when lined with concrete. Reinforcing steel was not required, thus reducing lining cost by one- quarter. 2-Water sealing was desired; it was thought it could best be done with a concrete lining followed by pressure grouting to eliminate water seeps. 3-The shaft labor saving equipment could best be used in a large opening, so the round section was made for economy, sinking, mucking, concreting and water sealing. Less shaft steel is used than could have been possible with steel sets. There are no posts required; center beams and Tee plate assembly placed at 10 ft hold the 100 lb steel guide rails. The shaft is 12 ft 7 1/2 in. ID of the concrete walls. This is large enough for two 10-ton hoisting skips and a ladder compartment. One of the skip compartments is for hauling equipment. The grouting equipment was a 2%xlO-in. Gardner-Denver grout pump, air powered and developing 1000 lb pressure. A grout mixer, also air driven, fed the mixed solution into a tank coupled to the pump suction. Grout materials used were mostly water and Portland cement. Some Bentonite was used to seal porous ground near the surface.

Jan 11, 1950

By Frances Hurd

WHEN 60:40 brass is heated to 825° C., given a drastic quench to obtain the beta solid solution, and reheated, various changes take place in the structure. Reheating at 200' C. causes a fine, granular, sorbitic structure to appear which has been considered alpha solid solution. These particles coalesce at higher temperatures of reheating, and at 470° C., the alpha forms twins. A further study of these transformations was considered worth investigating.

Jan 1, 1927

By C. K. Leith

GENERAL GEOLOGY OF THE LAKE SUPERIOR IRON-BEARING AND COPPER-BEARING SERIES. THE geology of the Lake Superior region is of general interest, both from an economic and a scientific standpoint. The presence of large and rich iron- and copper-deposits has made a knowledge of the geology of the region necessary for purposes of exploitation and exploration. The ores of the region are contained in rocks of pre-Cambrian age, 'pith for most of the country up to recent years have usually been referred to as « crystalline schists " or " crystalline complex;" and regarded principally as metamorphosed basement-unit upon which the sedimentary rocks, beginning with the Paleozoic, were laid down. In the Lake Superior re¬gion this pre-Cambrian complex presents an unusual variety of rocks with determinable relations. It has been possible, with the large expenditures which-the magnitude of the iron-mining industry warrants, to work out their stratigraphy to a larger extent than has been possible in almost any other area of pre-Cambrian rocks. The real complexity of Lake Superior geology, the confusion of names and the multiplicity of reports covering small parts of the region, are such that interested persons, other than. geologists directly engaged in the work, may well hesitate to attempt to comprehend the geology of the region as a whole. The following paper is a somewhat elementary outline of the geology of the Lake Superior region with special reference to new developments not yet covered in published reports. Geological information concerning the region has been gath¬ered by mining companies, and by the geological surveys of Michigan, Wisconsin, Minnesota, Ontario, Canada, and the United States.. Perhaps in no other part of the country have the mining men themselves spent such large sums in purely geological work. This has made possible the publication of ,reports and maps by the State and Government surveys in much less time and at far less cost than would have been otherwise possible. The. U. S. Geological Survey is the only organization which has covered all of the region on the United 'States side of the boundary, and as its reports include the in¬formation gathered by the mining companies and State organi

Mar 1, 1905

By Nathan C. Rockwood

WHILE mining engineers have been searching in far corners of the country and of the world for hidden wealth there has grown up around us in nearly every city great wealth-producing mines calling for the investment of hundreds of millions of dollars and yielding products now sold for over half a billion dollars yearly-largely unknown and almost wholly neglected by mining engineers. But this neglect is explainable and excusable. They are industries of very recent origin-practically the growth of the last 25 years. They are in a very large measure the result of tremendous developments in engineering construction and the rapidly expanding use of portland cement concrete for structures of every description. Concrete as a material of construction is going through an evolution very much as did cast iron and other metals used in engineering; and this phase of the industry should appeal to the imagination of metallurgical engineers. At first iron was iron-a material of uncertain properties, owing both to small differences in chemical composition and in methods of manufacture. By successive steps iron was studied and knowledge of its properties developed-the striking effects of very small percentages of other minerals and of various heat-treatments.

Jan 1, 1924

By L. C. Graton, Joseph Murdoch

I. Introduction......................... 26 1. The Relations of Scale in Geologic Work........ 26 2. General Characteristics of Copper Sulphide Ores..... 29 3. Scope of Present Study................. 31 11. Description of the Important Minerals............ 36 1. Pyrite....................... 36 2. Pyrrhotite....................... 41 3. Chalcopyrite...................... 41 4. Bornite........................ 40 5. Covellite....................... 50 6. Chalcocite....................... 52 7. Enargite...................... 59 8. Tetrahedrite and Tennantite.............. 61 III. Conclusions.......................... 62 I. Introduction. The Relations of Scale in Geologic Work. Many features of human accomplishment rest upon the possibility of representing natural objects on a scale of different magnitude from the actual one. Most drawings, for example, are of very different scale from that of the object depicted, and indeed are useful mainly 011 this account. More important than the question of mere convenience, however, is that of meeting the physical limitations of vision.' Thus, a mural

Jan 1, 1914

By Gilbert Soler

PRODUCERS of alloy steels recognize the importance of chemical composition in rela-tion to the hot-working properties and the typical surface defects found in their prod-uct. Each analysis of steel has its own peculiar characteristics. Under conditions of standard mill practice each analysis is susceptible to certain types of defects. Mill practice must be varied to obtain the best combination of surface and internal quality in the product. Chemical composition influences the cast structure and crystallization character-istics of the ingot. It also determines the rate of heating and cooling, the plastic hot-working range, and the phase structure of the steel at various temperatures as well as the tendency toward scale formation and decarburization, This paper endeavors to emphasize the manner in which chemical composition affects the various properties of steel, and to indicate the relative impor-tance of these factors in relation to the hot-working properties and surface charac-teristics of killed steel. The influence of chemical composition may be outlined as follows: I. Effect on the cast structure of steel, including: A. State of deoxidation, and type of inclusions. B. Gas content of steel. C. Freezing point and melting point of steel.

Jan 1, 1940

By IRVING H. WENTIVORTII

(New York Meeting, February, 1912.) THE little town of San Nicolás, Tamaulipas, Mexico, lies approximately 60 miles east of Linares, situated in the State of Nuevo Leon, and 150 miles SE. of Monterey, as shown in the sketch-map. Fig. 1. The place is reached from Monterey by the Tampico train as far as Linares, a distance of 92 miles, and then by coach the rest of the way. It is situated in a narrow valley between low hills, the houses forming one main street and a plaza. It is peopled by about 500 inhabitants. The climate is temperate, the thermometer ranging from 90° in summer to a few degrees below freezing-point in winter; but this severe weather only lasts a day or two at a time, when the " northers " blow. There are no streams in the vicinity, but water sufficient for the use of the people is obtained from wells. The rainfall is about the same as that in the rest of NE. Mexico. The rainy months are July, August, and September. The rest of the year is practically dry, with an occasional showery day or two during the winter, when a " norther " is blowing. Timber is abundant in many localities. There are two varieties of oak, besides mesquite, ebony, "maguira," "patol," and a number of other kinds of trees indigenous to this region. I. HISTORY. On the discovery of the silver-lead hearing veins occurring in this district, the mining-camp of San Nicolás was founded in 1767 by the Spaniards, and numerous mines were opened and worked for a distance of abort 3 miles east and 5 miles west of the town. At the western extremity and near the Carrolena mine, a small town called San Pedro was built. The ruined walls of the houses form a single street, and all is over-

Aug 1, 1912

By CLAYTON C. BALL

In the year 1948, more than ever before, the coal industry established itself on the threshold of a new and exciting future expansion. While production did not equal the wartime and peacetime peaks of 1944 and 1947, it was, in review, a good coal year. During the latter part of the year a combination of mild weather, record stock piling, and general business slackening reduced coal demand to the extent that marginal mines suspended operations, while mines remaining active found it necessary to renew their attention to producing better products at lower operating costs.

Jan 1, 1949

By T. F. Witherbee

It is proposed to give, first, a description of the works; second, a report of the first six months of the present blast; and third, such improvements as have been suggested by the practical working. The site selected for this furnace was, at the time of commencing work, October, 1872, entirely covered by the navigable waters of Lake Champlain. A coffer-dam was first built of cribs of round timber filled with stone, forming three sides, while the shore answered for the fourth. Considerable excavating was done with a steam-dredge, a hole being left for it to pass out. The opening was then built up, and the cribbing banked up with blue clay from the bottom of the lake, to render it water-tight and the dam pumped out; the remainder of the excavating being done by hand. All of the foundations, with the exception of the elevator-tower, and fifteen feet of the east side of hot blast, rest on the Potsdam sandstone, which forms the shore line, dipping into the lake at an angle of fifteen degrees. Owing to jogs in the formation, a much greater depth was found necessary than was at first anticipated, the foundation under the stack

By T. F. Witherbee

IT is proposed to give, first, a description of the works ; second, a report of the first six months of the present blast; and third, such improvements as have been suggested by the practical working. The site selected for this furnace was, at the time of commencing work, October, 1872, entirely covered by the navigable waters of Lake Champlain. A coffer-dam was first built of cribs of round timber filled with stone, forming three sides, while the shore answered for the fourth. Considerable excavating was done with a steam-dredge, a hole being left for it to pass out. The opening was then built up, and the cribbing banked up with blue clay from the bottom of the lake, to render it water-tight and the dam pumped out; the remainder of the excavating being done by hand. All of the foundations, with the exception of the elevator-tower, and fifteen feet of the east side of hot blast, rest on the Potsdam sandstone, which forms the shore line, dipping into the lake at an angle of fifteen degrees. Owing to jogs in the formation, a much greater depth was found necessary than was at first anticipated, the foundation under the stack

Jan 1, 1876

By Steven Mitchell

BACKGROUND Homestake Mining Company began milling operations at the Bulldog Mountain Mine near Creede, Colorado in 1969. The Bulldog Mill, rated at 350 tpd, produces a bulk flotation condentrate assaying about 180 oz/T Ag and 20% Pb, from heads of about 16 oz/T Ag and 2% Pb. The circuit is straightforward with two-stage grinding to 1-5% plus 65 mesh, followed by rougher and cleaner flotation. Reagents used are Z-6, Z-11, Aerofloat 242 and Aero Promoter 404, with an Aerofroth 65-MIBC mixture for a frother. Additional information on the geology, mine and mill are available in references (1) and (2). A flow sheet for the mill and CIP plant together is attached as Figure 1. Final flotation tailings normally vary from 1.5 - 2.0 oz/T Ag. These tailings are cycloned to produce sand for underground backfill. After cycloning, the sands are repulped and given a final scavenger float. This sand scavenger recovers a small additional amount of silver which recycles back to the main flotation circuit. The tailings are recycloned and pumped to the mine or, if the mine cannot accept sand, to tailings. The majority of the silver in the flotation tailings exists in the fine fractions; cycloning upgrades the slimes and lowers the assay of the sand. The sand, after scavenging, typically assays 0.5 oz/T Ag, and the slimes assay about 3.0-3.5 oz/T Ag. From 1969 to 1976 all of the slime tailings and the sand tailings not used underground were impounded in a tailings pond located about

Jan 1, 1983

By AIME AIME

The following abstract of the minutes of the final Adjourned Annual Business Meeting, held Nov. 12, 1912, in the office of the Institute, 29 West 39th Street, New York City, is here presented for the information of the membership at large. On the announcement by the Secretary that there was a quorum present, President James F. Kemp called the meeting to order. The minutes of the Adjourned Annual Business Meeting of Oct. 7, 1912, were read and approved. (Sec p. xi,Bulletin No. 71, November). Prof. Jos. W. Richards, in behalf of the Special Committee of the Board of Directors and the Council (Messrs. Richards, Kirchhoff, and Rand), withdrew the two proposed amendments to the Constitution offered by the said Committee at the Adjourned Annual Business Meeting of Oct. 7, 1912. (See Bulletin. No. 70, October, 1912, p. vi., and Circular Announcement No. 8, Oct. 15, 1912, p. 15.) Professor Richards presented a syllabus of the proposed amendments to the Constitution and By-Laws prepared by the Special Committee. Several members present discussed various sections of the proposed Constitution, and the Committee advised that the suggestions would he duly considered before submitting the final document, which would be duly presented and sent to the membership at large at least 30 days before the next Annual Business Meeting, Feb. 18, 1913. Professor Richards presented a resolution, seconded by Mr. Kirchhoff, making a change in the present Certificate of Incorporation, so that it would conform to the proposed changes in the Constitution and By-Laws; said resolution was unanimously adopted. Professor Richards presented another amendment to the Constitution, which had been purposely omitted from the printed list, but had been requested by many members, namely, the creation of a " Class of Fellows." This question was freely discussed at the Cleveland meeting (see Bulletin No. 71, November, 1912, p. 1348), and in view of the diversity of opinion it was-decided to present it in separate form for separate action of the membership at large at the Annual Business Meeting, Feb. 18, 1913. In answer to question, the President announced that the proposed amendments to the Constitution and By-Laws presented by Messrs. Corning and Stone at the Adjourned Annual Business Meeting, Oct. 7, 1912, and published in Circular Announcement No. 8, Oct. 15, 1912, were still on record. Professor Richards presented a syllabus of the proposed amendments to the By-Laws, and several sections were discused by members present, but no action of record was taken. Mr. Charles F. Rand read a letter from Mr. L. K. Armstrong, Sec-retary of the Spokane Local Section of the Institute, referring to the proposed amendments to the Constitution, and he announced that many of Mr. Armstrong's suggestions were, in one form or another, already incorporated in the proposed amendments submitted by the Special Committee. A special vote of thanks was passed to Dr. Albert R. Ledoux for the valuable assistance rendered by him to the Special Committee in the preparation of the proposed amendments to the Constitution and By-Laws.

Dec 1, 1912

By H. I. Aaronson, H. A. Domian, G. M. Pound

The thernodyna,nics of I the Proeutectoid ferrite re-action ha1.e been investigated on the bases of three diifevent descviptions of the statistical thernzodynamics of interstitzal solid solutions. Especially at low ternperatures, substantial dijeretzces are found in the valltes of the extrapolated y/y + a and cr/a + y equilibriurn curls, and in the To- co7nposilion metastable eqliilibriunz curl-es thus co,npited. Although neither actiztity nor phase-diagram date are able to distingrish udeqiutely among the various descviptions, the statustics of Lacher, Fouller, and Guggenheinz provide the ?nost conplete epresentation az3ailable of the single carbon-ctrbon interaction energy (w) nzodel of an intevstitiril solid solution, and the relationships deduced frojrl then2 are accordingly pre.ferred. The findings tlzut w in austenite 'aries significu?ztly uith tenpevntrue and that phase-diagawr data arc not accurately con?palible usith eqcrctions deduced on the basis of actility infoation indicate, hou'e13er, that a wzore cornplex nlodel of the uustenite , und pvobably of the .feyrite, solirl solutions will have to forn the basis of f4tuve statistical t1.eat1nents. Some suggestions for such a ruodel arc advanced. Althoug11 w represents a vepltlsio energy in austozite, it was found to corvcsporzd in ferrite to a binding energy, in qualitatit.e accord zc,itlz the internal-friclion results of Keefer and wert. ThE transformation of austenite to proeutectoid fer-rite is becoming recognized as an exceptionally useful vehicle for quantitative studies of the kinetics of phase transformations.'" Reasons for this popularity include well-characterized microstructures which develop on a convenient scale with acceptable kinetics within a considerable temperature-composition region, the absence of great sensitivity to common impurities, and, especially. the availability of a unique wealth of the ancillary information indispensable for the quantitative interpretation of kinetic measurements, including phase diagram,3 crystallographies diffusivity,5 inter-facial energy,=17 elastiit," specific vlume, ''' and ativity'-' data. Development of considerable amounts of additional thermodynamic information from activity data is of particular importance with respect to kinetic studies, since much of this information is needed in temperature-composition regions not directly accessible to presently available techniques for the measurement of equilibrium properties. A generally useful approach to the thermodynamics of solid solutions, which is of especial value in this situation, is based upon the formulation of the free energy of such solutions as a function of temperature and composition. The free energy of solid solutions has been resolved into many components. Particularly in the case of interstitial solutions, with which we shall be concerned in the present study, however, only the positional entropy component has been intensively studied. The other components are conventionally taken into account by fitting equations for the activity of the interstitial species or the temperature-composition path of phase boundaries, derived principally from positional entropy considerations, to experimental information on these quantities through adjustment of one or more constants in the equations. A number of studies of the thermodynamics of interstitial solid solutions have been made primarily on this basis,'"25 but only Kaufman, Radcliffe, and cohenZ2 (hereafter KRC) and ener''% ave applied the results of such studies to develop relationships for the thermodynamic quantities of interest in the austenite —- proeutectoid ferrite transformation. KRC made use of a model developed by cheil'' (on the basis of a previous study by ohansson'), and subsequently rede-rived correctly by Speiser and retnak,' in which a carbon atom is considered to inhibit occupancy of a certain number of its nearest-neighboring interstitial sites. schei120 determined the number of sites in austenite thus excluded by matching calculated and experimentally measured curves for the variation of carbon activity with the mole fraction of carbon. zener17 used a different approach. He assumed that the positional entropy of carbon is ideal both in austenite and in ferrite (i.e., no excluded interstitial sites), and included all other contributions of carbon in a temperature-independent "free-energy change" accompanying the transfer of 1 mole of carbon between the two phases. This quantity was determined by "pinning" an equation derived for the boundaries of the a + y region to experimental data on the compositions of these boundaries at a single temperature. In the present investigation, three different approaches to the thermodynamics of the proeutectoid ferrite reaction are examined comparatively: I) the method of Zener; 2) the model employed by KRC and predecessors; and 3) the more detailed statistical thermodynamic treatment of the same model developed by acher and Fowler and uenheim, ' in which the problem of overlapping regions of influence of individual interstitial atoms is resolved. In order to make these comparisons, it is necessary to undertake an extension of one aspect of Zener's method; since the Lacher- Fowler -Guggenheim (LFG) treatment has not been previously used in the present context, the necessary thermodynamic "superstructure" for this treatment will be developed in parallel

Jan 1, 1967