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By H. H. Kellogg

Equations representing the standard free energy of formation as a function of temperature, for thirty metallic chlorides, are presented and plotted on a free-energy vs. temperature diagram. The use of these data for calculations on reduction of metallic chlorides, refining of metals with chlorine, and chlorination of metallic oxides and sulphides is illustrated. CHLORINE metallurgy' has attracted metallur- gists for more than a century because the unusual properties of the metallic chlorides—low melting point, high volatility, and ease of formation from the oxides—make possible many useful extractive processes. Interest in chlorine processes is undergoing a renaissance due to present availability of chlorine at relatively low prices, and to recent advances in technology. During the present century there have accumulated a considerable number of reliable values of the thermodynamic constants for the metals and their chlorides. These data permit the calculation of free-energy equations for many metallurgically important reactions. Consideration of free-energy values makes possible certain predictions of the direction and extent of a given reaction, as well as the effect of temperature, pressure, and composition upon the result. Reaction rate, although not predictable from free-energy data, is usually sufficiently great at elevated temperatures that diffusion of the reactants and products to and from the zone of reaction determines the actual rate. Thus, if the free-energy indication is favorable, the chances are good that a high temperature metallurgical reaction will proceed at a reasonable rate, if adequate provision for rapid diffusion has been made. This paper presents standard free-energy equations for a number of metallic chlorides, based on data which are scattered throughout the literature. The equations are presented in a form that simplifies their use, and typical examples are given of the application of free-energy data to metallurgical processes. Free Energy of Reaction The free-energy change (AG) of a reaction is the true measure of the "driving force" of the reaction under a given set of conditions, and this is related to the standard free-energy change (AGO) of the reaction as follows: For the reaction: bB + cC = dD + eE ?G = ?G°+RTln ADd. AEA / ABb. ACc where A, = activity of constituent (i) T = absolute temperature, OK R = gas constant The criterion of a spontaneous reaction from left to right, at constant temperature and pressure, is a negative value for the free-energy change (?G). The standard free energy of the reaction is equal to the free energy of the reaction when all the reactants and products are at unit activity, since under these conditions the second term on the right-hand side of eq 1 is equal to zero. The concept of activity is treated fully in many textbooks on chemical thermodynamics1 and in a recent article by Chipman.2 Briefly, the activity (A,) of a constituent (i) is a measure of the reactivity of this constituent relative to its reactivity in some arbitrary standard state. For liquids and solids the standard state most often used is the pure liquid or solid constituent. Thus the activity of a pure liquid or solid in a metallurgical reaction is equal to unity. Gases under moderate pressure and at elevated temperatures behave very nearly as 'idea1 gases,' and the standard state is chosen as the gas at 1 atm pressure. The activity of an ideal gas is therefore equal to its partial pressure, and this relation is sufficiently exact for real gases in most metallurgical reactions. For a liquid or solid solution there is in general no simple way to express the activity of a constituent as a function of its concentration, and activity must be determined by experiment. A few solutions follow a so-called 'ideal' behavior, and if the pure constituent is chosen as the standard state, the activity of a constituent in an ideal solution becomes equal to its mol fraction. When a reaction reaches a state of thermodynamic equilibrium at constant temperature and pressure, AG becomes equal to zero and eq 1 reduces to: [ADd . AEe ?G°=RTln Abb ¦ Ac c equilibrium [2] The brackets surrounding the activity term are used to emphasize that each of the activities is an activity under equilibrium conditions—not just any arbitrarily assigned value. The bracketed term is the equilibrium constant (K) of the reaction. Eq 2 makes possible the calculation of equilibrium activities for a given reaction, if AGO is known at the desired temperature. The standard free-energy equations presented in this paper were calculated from the fundamental thermodynamic values of enthalpy of formation at 298°K (AH°,), standard entropy at 298°K (So298), heat capacity as a function of temperature (Cp), and enthalpies of transition, fusion, vaporization, and sublimation for the various constituents. Where possible the data reported in the recent "Selected Values of Chemical Thermodynamic Properties," published by the Bureau of Standards," were used. A large number of data came from the publications

Jan 1, 1951

By G. Sachs

X-RAY analysis and single-crystal study have been utilized in recent years as a new means of following constitutional changes in alloys. If such transformations can be suppressed by rapid cooling, they can be followed at room temperature in a particularly convenient manner. In the following we shall consider changes in solubility and polymorphic transformations with particular reference to phenomena of the age-hardening type. Finally a thermodynamic viewpoint is developed for examining such transformations.

Jan 1, 1931

Jan 1, 1928

By H. W. Bell

There was considerable prospecting for new supplies of oil in Arkansas during the past year, regardless of the overproduction affecting the industry throughout the country. Justification for this new work was not lacking, as the local markets more than threatened to absorb a declining production. There were, however, no important new discoveries in the state during 1929. The McDonald area in sec. 2515, S.-18 W., threatened to expand into a major producing area. Oil showings had been encountered here in wells drilled by the McDonald Oil Corpn. as early as the fall of 1928. In July, 1929, an initial production of 1000 bbl. of 32" oil was obtained in McDonald Bros. B-3 Wilson, from a sand at 2780 to 2786 ft., which is about 80 ft. higher than the sand previously tested in the neighboring wells. This production declined rapidly. At the end of the year there were six producers making about 200 bbl. per day total. Seven dry holes have temporarily stopped development in that area. The showing of B-3 was sufficient to cause considerable leasing activity. The area lies several miles west of the Louann portion of the Smackover field. The discovery well went to 2873 ft. and found Glen Rose lime in bottom. The age of the producing sand is in doubt; it seems closely related to the Tokio sand. During 1929, several paying wells were brought in, as a northeastern extension to the Smackover Heavy area, in sec. 34 and 35-15-15, from the Nacatoch sand. Over 20 new wells were drilled and resulted in at least 1500 bbl. production. The down-dip or off-structure territory contiguous to the Smackover uplift was further tested at various locations with the usual results; that is, a showing of "salt water gas," which soon blew off and in some cases a slight showing of oil. These gas showings, found further down the dip than oil, are the results of the ability of water to take gas into solution at the rate of about 3 per cent. by volume at atmospheric pressure and proportionally larger quantities, if available, at higher pressures (measured on the absolute scale). During the year no off-structure wrinkles sufficient to trap conlmercial quantities of oil have been found outside of the other known fields of

Jan 1, 1930

By A. H. Jones

(San Francisco Meeting, September, 1915). THE Belmont mill at Tonopah, Nev., was designed and constructed by the Belmont staff. Ground was broken in August, 1911, and milling operation started July 25, 1912. The metallurgical flow sheet, and the machinery adapted to carrying out operations in accordance with this plan, were decided upon from experience gained in the treatment of Belmont mine ores at the old Belmont mill at Millers, Nev. The detail drawings were made by the-engineering staff of the Tonopah-Belmont Development Co., under the supervision of Otto Wartenweiler, who also .had direct charge of the construction, consulting with the General Superintendent of the company, Frederick Bradshaw, and the writer.

Jan 8, 1915

By John Birkinbine

Forty years ago, when the first shipments of iron-ore were made from the Lake Superior region, the supply for the blastfurnaces active at that date was in most cases a local consideration ; the majority of the smelting-plants being close to the oremines. Of those which depended in whole or in part upon ores brought from distances greater than an economical wagonhaul, few obtained supplies by canal or railroad from points 50 miles removed. At the present time the ore-supply is a local consideration for but a small proportion of American blast-furnaces, and 700 miles or more separate a greater num-

Jan 1, 1898

Jan 1, 1929

By E. J. Dulis, A. Kasak, R. C. Westgren

The potential of uirought tungsten- and tantaluw-rich alloys of the W-Ta-Mo-Cb system was investigated for high-strength structural applications above 2500° F. Appreciable strengthening of tung-sten and tantalum—essentially attributable to solid-solzction effects—was obtained with binary, ternary, and quaternary alloys. Tensile strengths as high as 67,000 psi were achieved at 3000 OF. ThE quest for wrought structural materials which possess good strength properties at temperatures above 2000°F has led to a considerable research effort during the past decade. In addition to exploring the potential of various high-melting-point refractory metals (such as molybdenum, columbium, tantalum, and tungsten) for very high-temperature structural applications, alloy-development programs have been undertaken to achieve greater strengths than could be achieved with unalloyed refractory metals. The methods of strengthening refractory metal alloys have included both solid-solution and dispersion strengthening. General relationships among the relevant properties (melting point, recrystallization temperature, and high-temperature strength) of refractory metals indicate that the highest strengths at temperatures of 2500°F or higher would be obtained with tungsten-or tantalum-base alloys. Therefore, the present investigation was undertaken to determine the high-temperature strength potential of solid-solution strengthened alloys based on the binary system W-Ta; to effect further strengthening, minor additions of molybdenum and columbium (at the 6 and 12 pct levels) were made. The portion of the W-Ta-Mo-Cb quaternary alloy system of interest is shown schematically in Fig. 1. The component metals—W, Ta, Mo, and Cb—have a bcc structure at all temperatures, and their binary systems are mutually completely soluble.' Complete solid solubility in the W-Ta-Mo and W-Ta-Cb alloy systems has been demonstrated,' and, therefore, it was expected that the quarternary alloys of the system would also exhibit complete solid solubility at all temperatures. In the virtual absence of contamination by interstitial elements, all the alloys would be truly solid-solution strengthened. Twenty specific compositions of this investigation included binary, ternary, and quaternary alloys of the W-Ta-Mo-Cb system as well as unalloyed tungsten and tantalum. The compositions are shown in Table I. EXPERIMENTAL PROCEDURE Consumable-electrode vacuum-arc melting with ac power was used to produce small laboratory-sized, cylindrically shaped ingots (1-1/4 in. in diameter and 2 to 3-1/2 in. long) of the twenty compositions. A furnace was specially constructed to melt as many as four electrode rods simultaneously into molds lined with tungsten or tantalum sheet. High-purity rods of tungsten, tantalum, molybdenum, and columbium were used for consumable electrodes; the diameter of each rod was determined by the desired weight percentage of the component metal in a given alloy. The details of the construction and operation of the melting furnace will be discussed in another p~blication.

Jan 1, 1964

By L. Dudley Stamp

The years 1935 and 1936 have been momentous ones in the history of oil exploitation in Burma. While the possibilities of the discovery of an important new field in the country have become increasingly remote, there have been surprising and to some extent unexpected developments in and near the old established fields. Further, these developments have not only an important bearing on the future of the industry in Burma, but they point to conclusions of, world-wide significance in connection with the disposition of oil pools. BC'rma Independent of India According to the Government of India Act, passed by the British Parliament in 1935, Burma becomes independent of India, of which it was formerly a province. In future, therefore, statistics for Burma will be quoted separately from those of India. In 1934, 1935 and 1936 the oil production in India (including Burma) reached new high levels— though only a few per cent above the totals for 1919, 1920 or 1930. Part of the increase came from Assam, so that Burma's total is apparently below that of 1921. It must always be remembered, however, that Burma's largest potential producer—Singu—is used essentially by the Burmah Oil Co. as a reserve and its production is varied from year to year, and indeed from week to week, according to local market demand or the requirements of the Rangoon refinery. The figures of Table 1 must therefore be viewed in the light of these remarks.

Jan 1, 1937

By Thomas S. Blair

I FEEL a certain sense of responsibility in bringing before you the subject of the direct process in iron manufacture. I am aware that, in such a body as I have now the honor of addressing, there are few who are not already so well informed upon its past history that it would be a weariness to them to listen to anything else than an account of practical success. Yet, to claim that success involves so much that, if I do not make good my claim, I deservedly expose myself to severe criticism. The whole literature of the art, so far as it relates to the direct process, is, up to this time, but a history of failure. It is safe to say that more money, time, and talent have been fruitlessly spent in the pursuit of this object than in all the other unsuccessful efforts in the whole line of iron metallurgy. A distinguished authority in patent law has remarked that " the invention records of the United States and of foreign countries are filled with the waifs and abandoned relics of these abortive struggles." Dr. Percy, whose great work may be taken as an epitome of all that was worth mention, whether useful or curious, in pig-iron metallurgy, up to the date of its publication (1864), after giving elaborate accounts of various attempts at the direct process, condenses his own opinion of all that had been then effected, into a brief but summary comment upon a pamphlet of one of the sanguine inventors who had said: "It is evident that the present mode of working iron

Jan 1, 1874

By E. P. Klier, Taylor Lyman

THE structures formed when austenite is quenched to subcritical temperatures and allowed to transform isothermally have been the subject of intensive study since the work of Davenport and Bain.1 Isothermal transformation diagrams summarizing the results of many of these studies have become widely familiar to metallurgists. Of particular interest to metallographers are the dark-etching, acicular products of transformation formed by isothermal reaction below the temperature of maximum velocity of the austenite to pearlite reaction. These products, the bainite structures, can be formed in a wide variety of steels. However, the constitution of bainite is not well understood and divergent views have been expressed as to its mode of formation. In this investigation a combination of dilatometric, microscopic and X-ray methods has been brought to bear upon the problem in the hope of some elucidation of the bainite reaction as it occurs in hypoeutectoid steels. MECHANISM OF BAINITE FORMATION Davenport and Bain1 considered the mechanism of bainite formation to consist of two steps-an allotropic transformation followed by precipitation of carbide. The separation in time of the two processes was considered to be very slight in the upper temperature range and very marked at temperatures just above the martensite range. This concept has been restated by Vilella, Guellich and Bain2 in the form of a definition of the acicular mode of transformation as: The successive, abrupt formation of flat plates of supersaturated ferrite along certain crystallographic planes of the austenite grains; this supersaturated ferrite begins at once to reject carbide particles, (not lamellae), at a rate depending upon temperature. In effect, this is the acicular mode of transformation, even though the temperature be such as to limit the actual life of the quasi-martensite to millionths of a second. The investigation of isothermal decomposition of austenite in certain alloy steels (notably those containing chromium or molybdenum) has revealed that there may be a range of temperatures between the pearlite and bainite reactions in which the austenite decomposes at a relatively low rate.3-6 Further, it is characteristic that in the second region of fast reaction the decomposition of the austenite is incomplete by one reaction but goes to completion by a second reaction. These observations led Wever7 to a description of the bainite reaction as follows: I. The reaction takes place by initial precipitation of a martensitic intermediate structure. 2. In the upper temperature range this structure readily decomposes into ferrite and cementite. In the lower range carbon separates in an unknown form. 3. In the upper temperature range the precipitated carbide nucleates the precipitation

Jan 1, 1944

By Edwin Hopkins

THE year 1923 started a few days after the Venezuelan Oil Concessions, Ltd., discovered a 140,000-bbl. well at. La Rosa and a well of between 2500 and 5000 bbl. at La Paz, on the opposite side of Lake Maracaibo. These nearly simultaneous events changed, overnight, the general aspect of oil affairs in Venezuela. Up to that time, big things had been expected by the companies then in the district, but many major companies had shown little interest in the country. Within a few weeks the Pure Oil. Co. and the Gulf Oil Corpn. entered the field and acquired large properties. The Texas Co. purchased several concessions and the Standard of California, Atlantic Refining Co., and Mexican Petroleum Co. established offices. Representatives of many other companies visited the district during the first few months of the year. The sudden influx of buyers naturally caused a great rise in prices and this, together with overproduction in the United States, doubtless caused the slowing up of concession transfers in the latter part of the year. The following property transfers occurred: (1) The Gulf Oil Corpn. contract with the Maracaibo Oil Exploration Corpn., whereby the Gulf acquired the right to select 100,000 acres from the Maracaibo's zones. (2) The Gulf Co. purchase of one-quarter interest in seven concessions of the New England Oil Corpn., Ltd. (3) The Gulf Oil Corpn. purchase of several concessions of Kunhardt and others in the Perija district. (4) The Gulf Oil Corpn. purchase of certain portions of the one-kilometer Lake zone that were not covered by parcels or Government reserves (namely the "sobrantes"). (5) Pure Oil Co. purchase of all Government reserves turned back by Maracaibo Oil Exploration Corpn. in the districts of Mara and Miranda. (6) Standard Oil Co.: of New Jersey deal with the British Controlled Oilfields, Ltd., for control of approxi-mately the eastern third of the .district of Buchivacoa, state of Falcon. (7) Royal Dutch deal with the British Controlled Oilfields, Ltd., for the control of the central third of the district of Buchivacoa, Falcon. (8) The Texas Co. purchase of several concessions in Perija and one west of Mene Grande on the east side of Lake Maracaibo. (9) Purchase by the British Equatorial Oil Co., Ltd., of Goverment reserves corresponding to certain Creole Syndicate parcels under the margin of Lake Maracaibo near La Paz. (10) The Lago Petroleum Co. acquired a concession on all of Lake Maracaibo except a 1-Km. strip along the shore.

Jan 3, 1924

By C. A. Rowland, R. C. Nealey

Until recently there were very few dry grinding rod mills used. The early installations performed as anticipated. In the last seven years a number of dry grinding rod mills have been made, most of which have been used for grinding iron ore. The recent installations have not operated as anticipated in accordance with practices learned from wet rod milling. The paper does not establish any definite rules for the application of dry grinding rod mills but does attempt to establish some guidelines that can be followed. The paper reviews a number of flowsheets describing the problems encountered and some of the solutions found. Completely dried compared to partially dried feed is reviewed. Problems encountered in scaling up from pilot plant to production-size mills are described. Rod sizing, effect of rod length, rod bending, rod breakage, and rod tangling are discussed. While wet grinding rod mills have been used for 50 years to grind ores and make specifications sands, dry grinding rod mills have only recently come into significant use in the mineral industries. Among the materials now being processed in dry grinding rod mills are (1) lead sinter, lead slag, and limestone; (2) iron ore; (3) silica; (4) cement clinker; and (5) coke. Because the application of wet grinding rod mills was well understood at the time that dry grinding rod mills were introduced, the criteria and guidelines for selecting the former were carried over to the selection of the latter - in some cases with the anticipated results, but in many cases not. It is the purpose of this paper to describe, through a series of flowsheets, some of the recent problems encountered with dry grinding rod mills, to point out the solutions to these problems, and to set forth some guidelines for the selection and application of these mills. When dry grinding rod mills came into use, the following facts about their wet grinding counterparts were already well established: (1) The performance of large-sized mills can be accurately predicted from the performance of rod mills 5 or 6 ft in diameter. Wet grinding mills as large as 14 ft in diameter (inside shell) by 20 ft long with rods 19.5 ft long can operate satisfactorily.

Jan 1, 1970

By Jorge Munoz Reyes

There are three main oil areas in Bolivia (Fig. 1) although so far only one has yielded petroleum in commercial quantities. The Sub-Andean zone is along the easternmost ranges of the Andes, bordering the large eastern and northeastern lowlands. It extends from the Peruvian frontier, north of Lake Titicaca in a southeasterly direction towards the city of Santa Cruz and from there southward to the Argentine border. This zone forms a belt about 1200 km. long by 100 km. wide, and comprises a series of parallel, very rugged, low ranges. Oil has been known and utilized by the natives in these regions since colonial times, from the large number of seepages, which in modern times have led to the discovery of many fields. The second oil zone of Bolivia lies along the eastern and southern borders of Lake Titicaca, on the Andean high plateau, at an average altitude of 13,000 ft. above sea level. It comprises an area of approximately one million hectares (2,470,000 acres). Several seepages are known here, but little development has taken place, because of the difficulties encountered, as the greater part of the territory is covered by volcanic tuffs and ashes, which conceal the structure underneath. The third area is called the "Central zone," and is in the heart of the country, in the Department of Cochabamba, covering approximately five million hectares (12,350,000 acres). This area consists mainly of broad valleys flanked by low rolling ranges. Natural seepages are not known to exist, but there are secondary evidences of the presence of oil. The outcropping rocks are mainly Paleozoic (Silurian and Devonian sandstones and shales). Albertite and other forms of polymerized petroleum have been found in this region. Of these three main oil areas, only the first one is at present productive on a small commercial scale. This zone, developed almost exclusively by the Standard Oil Co. of Bolivia, a subsidiary of the Standard Oil Co. of New Jersey, is divided from south to north into the following local fields: 1. Bermejo (On the Argentine border) 3. Sanandita 5. Camatindi 2. San Telmo 4. Caigua 6. Machareti

Jan 1, 1935

By R. L. Fullman, J. W. Cahn

A method is derived for obtaining the distribution of sphere diameters and plate thicknesses (or pearlite spacings) from size distribution functions obtained along randomly oriented lines. The method described offers several advantages over existing methods. IT is often of interest to measure not only the average particle size but also the distribution in sizes of particles dispersed in an opaque material, such as an alloy. Particles of a single size will exhibit a range of apparent sizes on the plane of polish. If the sample contains a distribution of particle sizes, the distribution of observed sizes on the plane of polish is related to the distribution of actual particle sizes by an integral equation, For example, a distribution of sphere sizes, N(r),

Jan 1, 1957

By D. W. Jessup

ONLY during the past few years, have the old-fashioned methods for treating ores and byproducts progressed to any marked degree. The advent of multiple-hearth roasting, blast roasting, the baghouse, and the Cottrell plant indicate this change. It is the ability to roast and smelt sulfide ores and concentrates that gave this later advance. Further investigations that will solve the problem of efficient handling of flotation concentrates and their attendant ills are of the utmost importance. With future developments, the metallurgist will be able to smelt more economically and to treat still more refractory ores, making the early methods appear small by comparison. GROWTH OF SMELTING Well within the memory of pioneer smeltermen, the ore was charged directly into the blast furnace as it came from the mine;, only the richer, ores were smelted, the lower grade and sulfide ores were undesirable. Matte was, at first, thrown away and only two products) were desired-slag and lead bullion. Scores of the early smelting companies failed because of improper reduction of ores, high costs, short- furnace campaigns, inability to treat sulfide ores, and ores containing-zinc. With the failure of weaker companies, consolidation eliminated many others, until today the field is dominated by a comparatively few organizations, each strong financially. Formerly, a few thousand dollars would erect a small plant, whereas the modern smelter costs over a million dollars. Ore and products to which formerly no attention was paid are now treated with comparative ease and at a good profit. Mechanical improvements have modernized smelting, furnace tonnages show an increase, and metal recoveries have made enormous strides. Even though costs have decreased, they have not dropped in proportion to the improvements, because of the higher wages, greater costs of fluxes and coke, more undesirable ores smelted, etc.

Jan 8, 1925

By AIME AIME

This volume, an octavo of 626 pages, is now ready for delivery. By its aid, any subject treated or alluded to in the Transactions can be instantly tracked. The names of persons, mines, works, towns, etc., have been included; and abundant cross-references and classified sub-headings have been added to facilitate rapid consultation. Thus, the student remembering the name but not the locality, or the locality but not the name, or neither the name nor the precise locality of a gold-mine, can find it under ?Gold-mines," or under either of the other heads. For a more extended statement of the nature and use of this Index, which is intended specially for the benefit of those who do not possess complete sets of the Transactions, and who consult the Library by correspondence, see the Bi-Monthly Bulletin for September, 1907. The price of the Index bound in cloth is $5, delivery charges prepaid. Half-morocco binding costs $1 extra. Buy at once a copy of this Index, and also as many back-volumes of the Transactions as you can afford. Every such purchase from the stock on hand is so much added to the income of the Institute. As far as possible, the money thus received will be devoted to maintaining and perfecting the Library, and making it useful to members in all parts of the world.

Jan 11, 1907

By E. C. Wright

FOR many years the cost of making pig iron and steel in the Birmingham district has been about the lowest in the United States. The close proximity of the important raw materials such as coal, iron ore, limestone, and the large available scrap supply made it possible to assemble all of the important ingredients necessary for steel- making with only nominal costs for transportation. Both iron ore and coal were being mined in this district at one time for about $1 per ton from underground operations. At that time mining wages were low everywhere and the labor rate in the South was considerably below that of other mining districts. This situation persisted until the emergence of labor unions as an economic and political force, emigation of southern labor to northern plants, and continued growth of industry in the South in the years following the depression of 1932. Since that time union organizing of miners and steel workers throughout the nation has increased labor costs in mining and steelmaking. This influence has been felt particularly in underground mining operations since the proportion of labor cost to total cost is still high. The previous advantage in basic labor rate in the South has been almost entirely eliminated by the equalization of labor rates in basic industries by national unions. Since 1945 these influences have been especially noticeable in increasing the cost of mining coal and iron ore in the South. The northern steel districts are still being largely supplied with iron ore from the Minnesota open-pit mines and the cost of this ore has not increased nearly as much as the cost of ore obtained from underground mines in Birmingham. A similar situation exists in coal mining; the thinner seams in Alabama are not so amenable to mechanization as the northern mines and, as a result, the output per man-day in southern mines is only about three tons of coal as compared to five or six tons per man-day in the large captive mines of West Vir-

Jan 1, 1950

By D. H. Newland

On the bulk basis New York's contribution to the production of oil is small, representing, as it does, a bare half of one per cent of the annual total for the United States. Yet it has more importance than is implied by such a statement. Petroleum includes a variety of organic compounds, some more and some less valuable. It would be a fairer estimate of the situation to say that New York in recent years has produced around 10 to 12 per cent on the average of all Pennsylvania grade oil, the supply of which is strictly limited and the demand steady even in times of overproduction of other grades. One may not infer from this that New York and other Appalachian states enjoy an independent position in the market with a price structure uninfluenced by that of the Mid-Continent, Gulf or California fields. On the other hand, the recent market demoralization in the South and West brought about by uncontrolled production caused prices to drop to a point where the life of the local industry was seriously threatened. The current cost of producing oil in New York under the methods of water-flooding, by which most of the output is now obtained, has been estimated by competent authority at not less than $2.50 a barrel. The

Jan 1, 1934

By J. W. Rutter, K. T. Aust

THE object of the experiments to be described in this report was to determine, first, which grains, out of a large number introduced into a sample in which their growth could proceed, were able to grow most successfully; and, second, the factors which control their growth selection. In an earlier study of grain boundary migration in high-purity lead,' it was found that, under some conditions, the most successful grain in an experiment of this type bears a special orientation relationship to the grain into which it is growing. The present work represents an extension of the previous study, directed at the determination of the orientation relationships which appear under a wider variety of conditions. Experiments of this general type have been done using commercial aluminum2 with somewhat conflicting results. In the present experiments, in contrast to the above,' the sample composition was a principal controlled variable, resulting in a considerable clarification of the phenomena observed. EXPERIMENTAL TECHNIQUE The experimental technique used in this investigation was essentially that employed previously in studies of grain boundary migration kinetics.1'3 The material used was zone-refined lead with various small amounts of tin or silver added to study the effect of varying the sample composition. The specimens were in the form of single crystals, about 1/4 in. 1/4 in cross section by 3 to 4 in. in length, grown from the melt in a horizontal graphite boat. A crystal grown in this way generally contained a lineage or "striation" substructure of the type shown in Fig. 1 of Ref. 1. This substructure consists of an array of low-angle boundaries which partition the crystal into regions misoriented from each other by a few degrees. The substructure constitutes a source of driving energy, estimated to be about 4000 ergs per cc, for the migration of a large-angle grain boundary into the striated crystal. New grains were introduced by plastic deformation in compression of a localized reglon at one end of the sample. Re-crystallization occurs at room temperature in the deformed region, introducing a large number of new, striation-free grains into the specimen. These grains are able to grow into the melt-grown crystal on annealing at a suitable temperature. The stria-tions are removed by passage of the grain boundary, as the substructure energy is utilized to produce the boundary migration. Usually, only one or two of the recrystallized grains persist after growth has occurred for about 1 cm out of the deformed region. Laue back-reflection X-ray photographs were obtained to determine the orientation relationship between the melt-grown crystal and the recrystallized grain or grains which grew most successfully in each specimen. EXPERIMENTAL OBSERVATIONS Fig. 1 shows the results obtained for a series of specimens to which had been added tin in the range from 0 to 5 ppm by weight. In this figure is plotted, in the standard stereographic triangle, the single axis about which the most successful recrystallized grain or grains are related to the starting, melt-grown crystal by the smallest rotation. The range of angular rotations observed about such axes is indicated beside each stereographic triangle. The results shown in the stereographic triangle on the left, Fig. l(a), were obtained by localized deformation at one end of each specimen at room temperature, followed by annealing in a furnace which had been preheated to 300°C. The furnace atmosphere was argon. It will be seen that the orientation relationships observed between the melt-grown and recrystallized grains are quite random. On the right, Fig. l(b), are shown results for samples in which the de-

Jan 1, 1961