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By Norman P. Goss

It is generally agreed that cold-working mechanically refines the grains into smaller fragments and with continued working these are oriented with certain crystallographic directions bearing a relation to the direction in which the metal is worked. Some of the energy expended on the metal during plastic deformation appears in the form of heat, but a very small portion remains in the metal as stored energy. The entropy, specific heat capacity, temperature at which recrystallization will just begin, density, ductility, elasticity, tensile strength, and resistance to corrosion are affected. These properties have been studied extensively and some of the changes in the physical properties due to cold-working were attributed to lattice distortion.l-8 The broadening of the Ka lines on the X-ray diffraction diagrams of plastically deformed metals is believed to indicate lattice distortion, and consequently the existence of internal stresses. The evidence supporting this theory rests solely upon the observed experimental fact that the diffraction lines are broadened and the Ka doublets are completely diffused. Elam9 has reviewed the matter of lattice distortion in relationship to the hardening of metals by plastic deformation. The X-ray diagrams of plastically deformed metals differ in general from annealed metals. The hardening of a metal was believed due to lattice distortion.9 The resolution of the doublet is lost when a metal is cold-worked and the Laue spots are elongated. At one time this elongation was thought to indicate the elastic bending of the crystal planes. However, more careful work showed that the asterism was due to new orientations developed within the fragmented grains during plastic deformation. Some theories attributed the hardening to fragmentation of the grains into smaller units. Jeffries and Archer,ll after carefully considering the problem of work-hardening from many angles, came to the conclusion that cold-working mechanically refines the grains into smaller crystal fragments, some of which at least differ in orientation from the parent grain. The increase in

Jan 1, 1940

By J. A. Ede

The property of the Spring Valley Coal Company, situated in Bureau county, Ill., comprises something more than 30,000 acres of coal-lands, on which have been opened four mines, designated as Nos. 1, 2, 3 and 4. Figs. 1, 2, 3 and 4 are plans of the first three; and Fig. 7 is a view of the surface-plant at No. 4, the workings of which it is not necessary to illustrate, as this mine has been practically merged in No. 2. No. 4 shaft is only 500 feet from No. 2, and both are ventilated by the same fan, and are in the same circle of air-supply. In speaking of No. 2, we now include No. 4. The system pursued in all the mines is " long-wall advancing," and the shafts are all vertical. The seam worked is locally and commercially known, in the Illinois series, as No. 3; but its position in the geological series is that of No. 2. It averages in thickness about 42 inches, arid has no partings, but mines in rectangular lumps, which stand a large amount of handling before breaking. An analysis made from Colliery No. 1 gave the following : Per cent. Moisture,.......... 1.45 Volatile combustible matter,.47.27 Fixed carbon,.........41.97 Sulphur,.........2.46 Ash,....... .. .. .. 6.85 Plate 6 shows a photographic view of this seam. The staff seen in the view is 37 inches long. The table on page 188, recorded in my office, which I presume to be correct, may be of interest. The bottom is fire-clay, varying in thickness from 6 to 24 inches. It affords what is considered good mining-ground. The roof immediately above the coal is a dark shale, lying in small bands, from 4 to 9 inches in thickness. Between the

Jan 1, 1900

By Lester C. Uren

Petroleum occurs, in nature, as a fluid saturating the pore spaces between the grains of porous rocks or aggregations of rock particles such as sand, sandstone, conglomerate, shale, limestone, etc. The oil, under the influence of gas pressure, hydrostatic pressure, gravity, earth pressure, and, perhaps, other natural forces, is caused to flow through the porous "reservoir rock1' into wells penetrating the stratum in which the oil occurs. The principal moving force is the pressure of dissolved or occluded natural gas within the oil, though this force is assisted by gravity and by the hydrostatic or buoyant pressure of ground water about the edges of the "pool." The wells, providing outlets to the surface, are centers of reduced pressure and the flow of rock fluids into a particular well is usually an expression of the difference in pressure existing between the space within the well and that of the stored oil within the reservoir rock. The greater this differential pressure, the more rapidly will oil flow from the source rock into the well. Opposing movement of the oil from the reservoir rock into the well are certain natural forces related to the rock structure, such as pore friction and capillarity, and certain others related to the physical properties of the oil, such as viscosity and adhesion. The differential pressure between the well and the boundaries of the area drained by it must be sufficient to overcome the forces opposing flow if there is to be movement of oil into the well. If by any device the resistance to movement of the oil may be reduced, the oil will flow into the well at a more rapid rate and the effective area of drainage will be increased.

Jan 1, 1925

By M. Van Weyenbergh, G. Van Esbroeck

THE copper mines of the Katanga region in the Belgian Congo lie along the same mineralized belt as those of Northern Rhodesia. There are two distinct types of deposits in that belt, the dolomitic and the quartzitic. In the dolomitic type the metallic minerals are found in a dolomitic limestone country rock. Through oxidation and enrichment,, large deposits of high-grade oxidized copper ores were formed, some of which are being worked by the Union Miniére du Haut Katanga. Such deposits are all in Katanga. The quartzitic deposits are found in Katanga and Northern Rhodesia. Here the primary mineralization occurred in sandstones and quartzites, in horizons stratigraphically lower than the dolomites. These rocks are not favorable to secondary enrichment and the oxidized zone is poorer than the sulphide zone, which alone contains the ore. There are also in Katanga a few ore-bearing veins. One of them is being worked in the Prince Leopold mine at Kipushi. PRINCE LEOPOLD MINE The Kipushi ore body fills a fault vein and invades the wall rocks more or less extensively by metasomatic replacement. The vein strikes north-northeast and south-southwest and dips to the west. The variable dip averages 60ºto a depth of 300 ft., and more uniformly 80º below 400 ft. In the upper section the average width is 200 ft. and below the width is about 150 ft. The length of the ore body is 2300 feet. The eastern side of the vein-the footwall-is dolomitic and contains irregular masses of ore sometimes extending 100 ft. or more from the main

Jan 1, 1939

By O. A. E. Jackson

In all three principal dunite dikes, minute disseminated grains of pyrrhotite are to be seen in the fresh rock in amounts less than 1 pct. Traces of nickel have been reported from many such specimens. Nickeliferous pyrrhotite is the principal nickel-bearing mineral, although olivine contains very minor amounts of nickel in solid solution, substituting for magnesium and iron. Such occurences are of no economic significance. Nickel analyses of possible economic significance (up to 3 pct Ni) have been returned from samples taken near the margins of the two large western dunite dikes. These samples were from schistose zones along and within the dike walls. The mineralized shear zones, up to 30 ft wide, strike N 30 W and dip from 65" to 90" west. They consist of layers of hard, fresh, green-gray dunite, mineralized with finely disseminated pyrrhotite. These layers alternate with layers of soft, black, oxidized schistose dunite up to 1 ft wide, well mineralized with pyrrhotite and tabular-fractured pentlandite in crystals up to 1/4-in. diam. Sulfides identified in polished sections were chiefly pyrrhotite and pentlandite, with much smaller amounts of chalcopyrite. There are two varieties of pyrrhotite. One develops a fine polish and conforms to published descriptions. The other is slightly darker and browner, does not polish as well, and displays flamelike growth or intergrowth structure when etched with nitric acid fumes. Pyrrhotite and pentlandite crystallized contemporaneously in the form of veins in the olivine and as fillings of the interstices of euhedral olivine crystals. Chalcopyrite replaces the other sulfides. The most striking feature of the deposits is their occurrence in intimately fractured and schistose zones in the dunite where faulting has been localized along the contacts of the sediments and the dunite dikes. Though far too little detailed work has been done to be certain, there appears to be a higher concentration of sulfides in the shear zones along the margins of dike apophyses, sediment reentrants, and strike and dip irregularities. Much more study would be required in order to submit a plausible theory of formation of the nickel deposits, supported by laboratory and field evidence. Results of the present study, especially localization of the metals by fracturing, certainly indicate that the nickel concentrations were brought about by precipitation of nickel sulfides from fluids that used the fractures as a means of ingress. Studies of nickel sulfide deposits throughout the world have demonstrated that such sulfides were deposited at considerable depths and at temperatures of several hundred degrees. This would rule out the possibility of groundwater as the transporting medium. The two possible sources of hot nickel-bearing fluids are quartz diorite and gabbro. The first possibility is that large volumes of fluids, expelled from the quartz diorite magma during its crystallization, obtained a supply of nickel by altering the nickeliferous olivine of the dunites. The likelihood of this process is lessened by the recognition that, although the dunites show some alteration to serpentine, talc, and trem-olite, they are for the most part remarkably fresh outside the schistose zones. The worldwide association of nickel with basic rocks, together with the presence of pyrrhotite in thin films on joint planes of the gabbro on Jumbro Mountain, favors the gabbro source. The writer extends thanks to C. Phillips Purdy, Jr., project chief of American Metal Climax Inc., for giving him the opportunity to study these deposits. He is also indebted to the officers of American Metal Climax Inc. and Discovery Mines Inc. for permission to publish this article.

Jan 1, 1961

By AIME AIME

MATTERS pertaining to mine ventilation were, taken up at the annual meeting Wednesday morning with E. A. Holbrook in the chair. In the absence' of its author, G. E. McElroy, the first paper, entitled "Economic Size. of Metal Mine %Airways," was read by title by the chairman. The second paper, "Intermittent Mine Ventilation," by Oscar A. Glaeser, was 'abstracted by Dan Harrington. It related to metal-mining practice, being inapplicable to coal mining, of course. B. F. Tillson asked how the ,quantity of air was measured and con- trolled in the different splits and Mr. Harrington stated that an anemometer presumably was used and that split- ting was controlled by adjusting the steel doors to the desired position by means of screws. George 'S. Rice asked if the fan were underground, and Mr. Harrington replied that it was. Although he had at, one time recommended that it be placed' on the surface, certain factors led the management to keep it underground, a. location that has several advantages in this particular case.

Jan 1, 1932

By F. G. McCutcheon

UNTIL about 1930, the universal practice of horizontal-retort zinc smelters in the United States, as far as the writers are aware, was to operate the retort furnaces on a 24-hr cycle; that is, the retorts were charged in the early morning of one day, and in the early morning of the following day the residues were cleaned out, the retorts recharged, and a new cycle started. During the business depression of the early thirties, zinc production fell off to the extent that zinc smelters had idle retort capacity. Rather than continue to run some of the retort furnaces on a 24-hr cycle and shut down the remainder, a few companies decided to try out a longer cycle. Although the output of zinc per retort per day is lower, the longer cycle permits a larger charge per retort and improved zinc recovery. Advantages of the longer cycle were soon evident, and the practice spread rapidly. Various lengths of cycle were used, typical examples being 28-hr, 32-hr, 36-hr, and 48-hr. The 48-hr cycle fits in best with the standard routine of smelter practice that was built up on the basis of the 24-hr cycle; that is, the retort furnace "maneuver" always comes at the same time of day, and can be performed in the cool hours of the early morning. Under some conditions, particularly in some of the older plants, where the retorts are smaller than in newer plants, a 48-hr cycle is longer than necessary, and some intermediate length of cycle may theoretically be most economical. Use of an intermediate cycle, however, means that the maneuver comes at different times on consecutive days, and that sometimes it comes during the hottest part of the day. The work on the retort furnaces is extremely hot and arduous at best, and it is much worse, of course, if it is done during the heat of a summer day. When labor was plentiful and tractable, many plants were able to operate on cycles of intermediate length, but the workmen did not like the working hours. Under present labor conditions, it is hardly practicable to operate with a cycle of intermediate length, so the choice has narrowed down to the alternatives of 24-hr or 48-hr cycles. In any discussion of economics, too comprehensive generalization is not warranted, because local conditions affecting economics vary greatly. The best economic practice at one plant at any given time may be uneconomical at another plant, or even at the same plant at another time. To determine the length of cycle that is the better practice at a given plant at a given time requires a weighing of the advantages and disadvantages of each cycle, taking into consideration all the local conditions. Some of the factors that must be considered in making the comparison are discussed briefly in the following paragraphs.

Jan 1, 1947

By H. A. Wheeler

The great depths attained by some of the older mines, and the milch greater depth at which they will have to he worked in the not distant future, strongly emphasize the imperfect and inadequate character of our present hoisting-practice. The depth of 3000 feet having been exceeded at several places, and 4000 feet almost reached

Jan 1, 1891

By Robert B. Bossler, Parke A. Dickey

The presence of connate water in oil sands is of far greater practical significance in secondary oil-recovery operations than it is in primary operations. The percentage saturations of oil, water, and gas in a depleted field determine whether it will be economically possible to recover oil by secondary methods, and whether water-flooding or gas-driving, or either, will be successful. It is suggested that economic recovery of oil by secondary water-flooding can occur only when a rich bank of oil is formed by the encroachingm water. If the sand has a greater effective permeability to water than it has to oil before flooding, a bank will not be formed, and water-flooding will not be successful, although gas-driving may be. Published results of laboratory work indicate that the effective permeability of a sand to oil and water depends primarily on the saturation of the sand by these phases. They also indicate that a small difference in relative saturation produces a large difference in effective permeability to the phase in question. There thus exists a critical range of saturations, wherein a small change in oil and water content of the sands will make water-flooding possible or impossible. In gas-drive operations the water saturation is less critical but no less important. The presence of connate water in a sand increases the proportion of the residual oil that may be recovered by gas drive. Sands containing oil saturations too low and water saturations too high to make water-flooding possible can often be subjected to gas drive with economic recovery of oil. The results of laboratory work on test samples that do not contain water cannot be applied to normal field operations. More tests on cores containing water as well as oil are desirable, and the improvement of coring technique is necessary. However, sufficient data are already available to enable an operator to use core data intelligently in estimating the chances of a secondary oil-recovery program. Introduction In recent years laboratory work has led to a much better understanding of the principles of oil-reservoir performance. The general principles of the expulsion of oil from sandstone by gas or water were developed by geologists of the Second Geological Survey of Pennsylvania in the 1870lsl but only recently has the mechanism of gas or water drive been intensively investigated. Most published articles have large the facts established in the labora tory to the primary production of oil from flush fields- This Paper is not based on any new observations, but is an attempt to apply some of the conclusions obtained in the laboratory and described in the literature to the recovery of oil from depleted pools by secondary methods. One of the most important factors that determine whether or not a secondary-recovery operation is economically successful is the ratio of injected fluid to oil recovered. This ratio may be expressed as the over-all or cumulative gas-oil ratio if gas is the driving medium, or water-oil ratio if water is the driving medium. Recent theoretical and experimental work has shown that the relative amounts of

Jan 1, 1944

By Parke A. Dickey, Robert B. Bossler

The presence of connate water in oil sands is of far greater practical significance in secondary oil-recovery operations than it is in primary operations. The percentage saturations of oil, water, and gas in a depleted field determine whether it will be economically possible to recover oil by secondary methods, and whether water-flooding or gas-driving, or either, will be successful. It is suggested that economic recovery of oil by secondary water-flooding can occur only when a rich bank of oil is formed by the encroachingm water. If the sand has a greater effective permeability to water than it has to oil before flooding, a bank will not be formed, and water-flooding will not be successful, although gas-driving may be. Published results of laboratory work indicate that the effective permeability of a sand to oil and water depends primarily on the saturation of the sand by these phases. They also indicate that a small difference in relative saturation produces a large difference in effective permeability to the phase in question. There thus exists a critical range of saturations, wherein a small change in oil and water content of the sands will make water-flooding possible or impossible. In gas-drive operations the water saturation is less critical but no less important. The presence of connate water in a sand increases the proportion of the residual oil that may be recovered by gas drive. Sands containing oil saturations too low and water saturations too high to make water-flooding possible can often be subjected to gas drive with economic recovery of oil. The results of laboratory work on test samples that do not contain water cannot be applied to normal field operations. More tests on cores containing water as well as oil are desirable, and the improvement of coring technique is necessary. However, sufficient data are already available to enable an operator to use core data intelligently in estimating the chances of a secondary oil-recovery program. Introduction In recent years laboratory work has led to a much better understanding of the principles of oil-reservoir performance. The general principles of the expulsion of oil from sandstone by gas or water were developed by geologists of the Second Geological Survey of Pennsylvania in the 1870lsl but only recently has the mechanism of gas or water drive been intensively investigated. Most published articles have large the facts established in the labora tory to the primary production of oil from flush fields- This Paper is not based on any new observations, but is an attempt to apply some of the conclusions obtained in the laboratory and described in the literature to the recovery of oil from depleted pools by secondary methods. One of the most important factors that determine whether or not a secondary-recovery operation is economically successful is the ratio of injected fluid to oil recovered. This ratio may be expressed as the over-all or cumulative gas-oil ratio if gas is the driving medium, or water-oil ratio if water is the driving medium. Recent theoretical and experimental work has shown that the relative amounts of

Jan 1, 1944

Six hundred miles inland from Australia's east coast Port of Townsville in Queensland's sea of rock and spinifex lies Mount Isa. The town, as in most mining towns, is dominated by its mine and the mine in turn is dominated by its 503 ft copper smelter stack. This candy and white painted stack is a striking introduction to one of the world's greatest copper producing mines and a town where people of over 40 different nationalities live remote but well. Mount Isa Mines Limited is surging into the ranks of' the world's great mines on the momentum of a relentless push begun in 1956. It is as if the time lost in the lean years of the past should be caught up in a hurry.

Jan 10, 1964

By H. Souder

The object of this paper is to bring to the notice of engineers a safety detonating fuse by the use of which misfires in blasting may be eliminated and safety in blasting operations promoted.

Jan 1, 1915

Jan 1, 1900

By G. Van Esbroeck

THE copper mines of the Katanga region in the Belgian Congo lie along the same mineralized belt as those of Northern Rhodesia. There are two distinct types of deposits in that belt, the dolomitic and the quartzitic. In the dolomitic type the metallic minerals are found in a dolomitic limestone country rock. Through oxidation and enrichment, large deposits of high-grade oxidized copper ores were formed, some of which are being worked by the Union Miniere du Haut Katanga. Such deposits are all in Katanga. The quartzitic deposits are found in Katanga and Northern Rhodesia. Here the primary mineralization occurred in sandstones and quartzites, in horizons stratigraphically lower than the dolomites. These rocks are not favorable to secondary enrichment and the oxidized zone is poorer than the sulphide zone, which alone contains the ore. There are also in Katanga a few ore-bearing veins. One of them is being worked in the Prince Leopold mine at Kipushi.

Jan 1, 1939

By A. B. Young

In the original design of the flue system, the flues from the roasters delivered their gases to a large brick dust chamber which discharged into another flue with stack connection, as shown in Fig. 1. The treater is so situated that the gases are taken by it directly from the chamber and discharged again into the flue. The complete installation comprises two treater units, only one of which has been installed at present. The treater is essentially a flue 1.0 ft. high, 12 ft. wide, and 61 ft. long. (3 by 3.6 by 18.5 m.). Suspended inside, vertically and running lengthwise, are four banks of No. 20 corrugated iron plates; each bank is 10 ft. long, making an effective treater length of 40 ft. The spacing from center to center of the rows of plat,es is 9 1/8 in. (23 cm.) giving six-

Jan 1, 1921

By Joseph W. Richards

This method of briquetting flue-dust, or flue-dust mixed with fine ores, or, in a few exceptional cases, coke-dust, has come into large commercial use in Europe, and a small plant is already in operation in the United States. It promisea to become of such great importance to the iron industry of the United States that the following description will certainly interest the majority of our pig-iron producers. Discovered in 1908, the process Tests upon the observation of Dr. Schumacher that blast-furnace flue-dust, while possessing of itself no binding or cementing properties, acquires strong cementing properties if mixed with a very small amount of certain salt solutions, the amount of which is so small that the resulting cementation appears to be rather by catalytic action of the salts added than by the mass-action of such chemicals. To be more specific, fresh blast-furnace flue-dust mixed with from 5 to 10 per cent. of its weight of magnesium chloride or calcium chloride solution—that is to say, with from 0.25 to 2 per cent. of its weight of magnesium chloride or calcium chloride—acquires the property of setting within a short time, from 15 to 60 min., and forming a hard cemented briquette. Alkaline solutions appear to have no action such as described, and they even interfere, if present, with the action of the magnesium and calcium solutions. When treated in this way the flue-dust briquette sets very hard, apparently from pure excess of cementing- and setting-power. It is, therefore, possible to mix with the flue-dust a considerable proportion of inert ore or like material, which has no setting-power by this process, and thus to make a compound briquette containing large quantities of ore mixed with flue-dust, but in which the flue-dust may be regarded as the cement or binding-material. A particularly strongly cementing flue-

Jan 1, 1913

By T. L. Joseph

Charcoal was the predominant blast-furnace fuel until 1838, when it was found, by the operation of a 2-ton experimental furnace, that anthracite could also be used. This information was a stimulus to the iron industry, particularly in eastern Pennsylvania where anthracite was available at low cost. The production of anthracite pig iron increased steadily and, in 1855, its tonnage exceeded that of charcoal iron. Of the 680 furnaces in operation in 1874, the 226 using anthracite produced nearly one-half the total tonnage. In 1869, the production of coke furnaces exceeded that of charcoal furnaces and, in 1875, coke surpassed anthracite as a metallurgical fuel. In 1907, the output of anthracite pig dropped well below a million tons and its present significance is largely historical. In recent years, the production of coke has gone hand in hand with the production of pig iron and it has gradually attained the position it now occupies as a universal blast-furnace fuel. Charcoal, however, has great merit as a blast-furnace fuel chief1y because of its freedom from ash and sulfur. The harmful effect of the latter and the necessity of keeping the percentage of this element in pig iron at a minimum are well recognized. Other contaminating elements can be reduced to specified limits in the steel-making process, but the control of sulfur belongs essentially to the blast furnace. The purpose of this paper is to point out the distribution of this impurity in blast-furnace materials and to indicate how its presence alters the composition, quantity, and free-running or critical temperature of the slag, and the relation between these factors, fuel economy, and the cost of iron. Sulfur Distribution in MateRials Table 1 shows the distribution of sulfur in charcoal practice. Similar figures taken from coke practice are given in Table 2. These data were

Jan 1, 1925

By Marion Rice

The copper-mining district of Jerome, Ariz., is of such economic importance that the following brief notes may be of interest. The ore deposits are said by Ransome1 to be pre-Cambrian, and are contained in the pre-Cambrian schists of the region. In the vicinity of the mine (the United Verde) the schist stands nearly vertical and strikes a little west of north. At least three varieties are distinguishable—(1) a green rock, schistose on its margins but grading into massive material, which is evidently an altered dioritic intrusive; (2) a rough gray schist with abundant pheno-crysts of quartz, apparently an altered rhyolite; and (3) a satiny, greenish gray, very fissile sericitic schist that may be a metamorphosed sediment. The ore occurs in varieties (2) and (3), the main belt of dioritic rock (1) lying just west of the orebodies. The ore is said to follow as a rule the layers of fine sericitic schist. T. A. Rickard2 Says that the ore at the United Verde Extension mine is found at the contact of diorite and schist, that both diorite and ore are earlier than the regional metamorphism, and that the quartz porphyry ("rhyolite" of Ransome) is of post-Cambrian age. The material considered here, a part of which was gathered by the writer, came from four of the mines of the district, and its study was undertaken at the suggestion of Dr. Berkey of Columbia University. The field relations and exact locations of the different specimens are not known, but a microscopic study of the thin sections gave some evidence as to the origin of the ore, which will be discussed below. The indications are that both ore and porphyry were introduced at the closing stages of the metamorphism, this being in accord with Ransome's view of the genetic relation of porphyry and ore rather than with the opinion that the ore is related to the diorite. Certain field occurrences mentioned in the literature also support this theory. Rickard, in the same article to which reference has been made, speaks of a vein of chalcocite several inches wide at the contact of one of the porphyry dikes, and Provot,3 although he regards the porphyry as subsequent to the ore, says: "Acid dikes encountered underground should be followed as they have been found in practice to lead to orebodies."

Jan 1, 1920

By Carl F. Dietz, Dyke V. Keedy

The problem of drying ores is one that most mill-engvineers are sooner or later called upon to meet, and it may be timely to point out some of the difficulties resulting from such operations from purely a metallurgical and economic standpoint. We mean, in the following pages, to discuss primarily the effect of such operations on the ore. itself, without particular reference to the mechanical or cost features of the subject. That an appreciable tonnage of the ore fed to the usual form of drier, either rotary or stack, is lost, is fairly well appreciated, but we believe that only a few mill-managers know just what their drier-losses amouilt to, and we have found that in most cases they console themselves with the fact that the drier-smoke is not very much discolored, and it is generally believed that the draft is not sufficient to carry away more than a negligible percentage of the values.

Jan 1, 1913

By Robert Baschwitz, John Chipman

The distribution of silicon between liquid silver and Fe-Si-C alloys has been studied at 1420oand 1530°C. The data are consistent with earlier studies. New data of Hager on the liquidus lines of the system Ag-Si and the distribution data are used to obtain the activity coefficient of silicon in both liquid phases. Data on the heat of mixing in iron permit accurate extension to 1600°C. Equilibrium data involving SiO2 and silicon in liquid iron together with revised data on the free energy of SiO2 are used to fix the activity of silicon in the infinitely dilute solution. The binary system exhibits strong negative deviation from ideality. At infinite dilution ? Si at 1600" is 1.25 x 10'3, and at concentrations up to NSi = 0.4 the slope d InySi/dNSi has a constant value of r; = 13. It is found that logysi in the ternary solutzon is approximately but not exactly the same function of Nsi + NC as of NSi in the binary. The results are consistent with currently available data on the free energy of Sic and its solubility in molten iron. LIQUID solutions of the system Fe-Si-C have acquired considerable importance as the laboratory prototypes of blast furnace hot metal. Equilibrium studies involving such solutions and slags approximating those of the blast furnace have yielded useful information concerning the thermodynamic properties of blast furnace slags. In studies of this kind great importance attaches to a knowledge of the thermodynamic activity of silicon in the solution as a function of temperature and composition. An attempt was made by Chipman, Fulton, Gokcen, and askey' to evaluate all of the pertinent data on this system and to deduce the desired relation between activity, composition, and temperature. These authors published data on the solubility of graphite and Sic in molten Fe-C-Si solutions and on the distribution of silicon between liquid iron and liquid silver. They showed further how the activity of silicon in very dilute solutions in liquid iron could be calculated from equilibrium data involving the molten alloy and solid SiO,. These calculations rested on the published thermodynamic properties of SiO, in- cluding its heat of formation which at that time was recorded as -209.8 kcal. This value has been under suspicion for some time and has recently been replaced by the concordant results from two independent laboratories2,3 which place the heat of formation of a-quartz at -217.6 kcal. This revision necessitates a re-evaluation not only of the activity of SiO2 in slag but also of silicon in molten iron. It is the purpose of this paper, therefore, to recalculate the activity of silicon, and in furtherance of this objective to present new data on its distribution between liquid Fe-Si-C alloys and liquid silver. HEAT OF SOLUTION OF SILICON IN IRON In order to determine the effect of temperature upon the activity coefficient it is necessary to know the heat of solution of silicon in iron as a function of composition. This is found in the data of Korber and Oelsen4 shown in Fig. 1. The curve corresponds to the following equation, which is of a form suggested by Wagner:5 Here AH is the heat absorbed in kilocalories in forming one gram atom of molten alloy from its molten elements and the N's are atom fractions. The relative partial molal enthalpies of the components, each referred to its pureliquid state and defined as zFe = aFe - PFe and zsi = HSi — -psi, are shown graphically. At low concentrations zSi = -28.5 kcal, in agreement with Kijrber and Oelsen's computation. This is in good agreement with the value of -29.3 kcal obtained by Chipman and Grant6 using an entirely different method. ACTIVITY AT INFINITE DILUTION From the known free energy of SiO, it is possible to obtain the activity of silicon in dilute solution in liquid iron from equilibrium studies. The heat of formation of a-quartz is —217.6 kcal and the heat capacity and entropy data are given by Kelley and ~ing.' The free energy of formation of ß-cristo-balite at temperatures above the melting point of silicon is expressed by the following equation: Si(Z) + O2(g) = SiO2 (crist); AF" =-226,500 + 47.50T [I] The value of the deoxidation product for silicon [%Si] x [%O]2 at 1600°C according to Gokcen and chipmans is 2.8 x 10"5, in agreement with results of Hilty and Crafts.9 More recent works of Matoba,

Jan 1, 1963