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TITANIUM is one of the most abundant elements in the minerals that make up the earth's crust but its use in industry is only a generation old; yet probably no other important commercial mineral raw material (except possibly magnesium) has undergone more changes and developments in sources of supply, in processing techniques, in uses and applications, in the past 10 years, or stands on' such a threshold of still more advances. Its outstanding use today is as the oxide, and because of its extreme whiteness, high refractive index, chemical stability, and relative cheapness, it has become the white pigment used in the largest volume. New developments in the uses of titanium metal, potential and actual, may surpass the pigment use of the oxide before many years. TITANIUM-BEARING MINERALS Although a number of minerals contain titanium as the principal metal, only a few are of commercial importance. These are arizonite, ilmenite, and rutile. The other oxides, brookite, pseudobrookite, and anatase, occur in a few deposits, one at least of minor importance. The silicate titanite, and the double oxide of calcium and titanium, perovskite, occur in a few deposits in quantities sufficient to be considered as potential ores were not richer deposits of the oxides available elsewhere. Arizonite is a name given by Palmer46a to a mineral found some years ago in minute quantities in Arizona, which has the formula Fe203.3Ti02. Unexpectedly, it was found that the black titaniferous iron oxide found in large quantities on the beaches of many continental land masses corresponds in chemical composition to this formula (although ferrous oxide is always present). No one has yet been able to prove that the commercial mineral on the beaches is truly arizonite, or an allotropic modification of it, since X-ray investigations by Howard Carl and A. F. Gabriel, of the U. S. Bureau of Mines, and by the X-ray laboratory of the Chemical Department at the Experimental Station of the du Pont company, have shown only that the sand mineral gives just a jumble of lines, rather than an identifiable pattern. Lack of a better name,

Jan 1, 1949

By George C. Branner

STATE geological surveys have had an interesting development in this country. They first appeared more than a hundred years ago. The fact that they have persisted and are now an important part of most state governments indicates the basic need for state departments con-cerned with mineral problems. The number of state surveys in 1941 (43) is at an all-time high, as is the aggre¬gate appropriation for their support for the fiscal year 1940-'41 ($1,600,708). The first surveys, those of North and South Carolina (see Fig. 1), made their appearance in 1820-'30, but neither survived that period. During the next two decades surveys were created in twenty states, but only three survived. In fact, it was not until the decade 1900-'10, when eighteen surveys were created and only five abolished, that these agencies became firmly established.

Jan 1, 1941

By Ray W. Arms

DRY cleaning, or pneumatic separation, is not, strictly speaking, a recent discovery. Among the archives of the Patent Office may be found many patents dating back as far as 1850 which cover early attempts to separate materials of varying specific gravity or of different shape by means of air. Hundreds of patents covering this art have been issued, which may be roughly classified into four general groups, as follows: 1. Stationary devices with pulsating air currents. The separating surface is usually riffled and air is supplied by bellows or compressors. This group also includes air jigs, which have been used rather extensively. 2. Stationary devices with continuous air currents. These submitted the material to a continuous current of air, either horizontal or vertical. Chaff is blown from wheat by such a device. 3. Reciprocating or vibrating devices with pulsating air. A small group in which the pulsating air is supplied by bellows and some motion provided in the separating surface to move the stratified material to various discharge points. 4. Reciprocating or vibrating devices with continuous air supply. This is by far the most important group and all recent developments have been along this line. All of the above groups involve the stratification of material by air and include none of the dry methods that use other principles, such as coefficient of friction, magnetism, etc. Air Stratification In all of the above groups of air separating devices, the same phenomena are found as exist in water concentrators; that is, free settling will be found in some and hindered settling in others, with a complex action on the reciprocating tables similar to the wet tables. The experimental value of the settling ratios of particles in air has never been determined but, following the formulas given in Richards'

Jan 1, 1924

By E. G. Williams

Manganese-ore has been found upon the Isthmus of Panama throughout' a region of nearly three hundred square miles, over the greater part of which, however, it is known only in small bodies without commercial value. Only six mines, controlled by two companies, have actually shipped ore, although a large area has been taken up in miningelaims. The ore-bearing region extends along the coast of the Carib. bean Sea, beginning on the west near Puerto Bello and extending easterly about 35 miles toward Point San Blas. Ore has been discovered in the interior, at a maximum distance of about 10 m. from the coast. Fig. 1 is a map of a portion of the Isthmus

Jan 1, 1903

P. H. ARGALL, Magdalena, N. Mex. (written discussion *).-The Chilean mill has generally been considered a fine-crushing machine and as such has had many advocates; it has also. had quite a number of denouncers; hence, the action of the Portland engineers in using the Chilean mill for the preparatory work usually accomplished in, rolls or rock breakers and adding a ball mill to do the fine grinding is novel, though of doubtful utility in the long run, even though a fair efficiency is obtained for the combination machines, as measured by Chilean mill practice. In order to follow the development of Chilean mill practice on Cripple Creek ores, I might say that two 6-ft., Chilean mills were placed in operation in Stratton's Independence mill in April, 1908, treating ore crushed by rolls to pass Y4 in. screen aperture. Screening was, however, found to be an unnecessary refinement, as was also the use of plows in the mills; both screening and plowing were abandoned before the Portland engineers finished the experiments in stamp milling upon which they were then engaged. Two additional 6-ft. Chilean mills were added in the spring of 1911, three of them giving the required 10,000 tons per month capacity, one being always in reserve. The Portland company began using Chilean mills in June, 1910, at its Victor mill, and the same company purchased the Stratton's Independence mill in June, 1915, and remodeled it; it is now known as the Independence mill. A description of Stratton's Independence milling practice, is given in the November, 191.1, issue of Mining Majazine (London). These Chilean mills were used as fine grinders and that they accomplished their purpose is shown by the screen analyses, in which 62 per cent. of the pulp passed 150-mesh screens. To make coarse crushers of these Chilean mills, the Portland engineers have increased the speed, substituted steel in various parts for cast iron, provided new and enlarged thrust bearings to take care of the centrifugal force incident to higher speed, and have, thereby, greatly increased the cost of the machines. They have also reduced the width of the tires and dies from 8 in., as used in the original mill, to 7 in., a reduction of 12 ½ per cent. in the crushing surfaces, to say nothing of the loss of abrasion or attrition incident to the larger surface. At the same time, they have apparently increased the weight of the rollers by using tires 5 7/8 in. thick as against tires varying between 3 and 4 in. on the original mills, thereby increasing

Jan 4, 1920

By T. E. Godson

AS this is the age of reform, a uniform mining law for North America is a moot subject for discussion at this meeting of the Institute. The question is one of peculiarly technical and, in many respects, local character. We all appreciate the value of the metal-producing industries and recognize the necessity and importance of a well-considered and evenly balanced mining law as a branch of our jurisprudence either for the Provinces or the Dominion as a whole. Mining has taken its place as a forempst industry and legislation that seeks to control and govern it is the concern of not only the active miner but the citizens of the state. A law that, through its charitable measures brings into being the prospector, the pathfinder and superstructure of all mining activity and industry! protects his interests, safeguards invested capital, and encourages and enforces development, possesses at least the salient requirements of a businesslike Act. The manner of doing so is, I think, one of local and internal concern. May I be permitted to say without presumption that of the five mining codes, or Acts, that we have in the Dominion of Canada born and bred within the Provinces of British Columbia, Ontario, Quebec, New Brunswick, and Nova Scotia, some of them could be materially improved. In many respects they do not measure up to the times; they were no -doubt creations of merit at the date of their .birth but they have not been clothed in seasonable raiment as the years passed by. It is a stern fundamental principle that all natural resources are the inalienable property of the crown. If it is mineral land, then it follows for the protection of the state and the direct advancement of the occupant that the land should be developed as such. The method or machincry by which this must be accomplished is a matter of detail, not of principle. If the right to possession as a licensee depends on discovery, it is not inconsistent with the duty the crown owes to the state that a grant in fee should pass to the discoverer if there is imposed, after patent issues, a requirement of continuous work or the alternative of an acreage tax sufficiently burdensome to make it unprofitable that the land should be held in an undeveloped state. If this requirement is recognized, the mental distinction between a grant and lease ceases to exist. A

Jan 1, 1920

By J. P. Carson

THE Croton water-shed furnishes the source and storage of watersupply to both the old and the new aqueduct. The Croton river rises in the southern part of Dutchess county, about 68 miles from the lower end of New York city. Its three main branches, called the East, Middle and West branches, flow southward across Putnam county, joining, near its southern boundary, to form the Croton, which continues thence in a general southwest direction across Westchester county to the Hudson river at Croton Point, about 35 miles north of the city. The water-shed above the proposed site of the Quaker Bridge dam extends about 33 miles north and south, with an average width of 11 miles, making in all about 362 square miles, from which, by complete storage, an average daily supply of 250,000,000 gallons may be collected—sufficient for the needs of the city, probably, for the next fifteen years. The water-shed above the Croton dam is 23 square miles smaller, and furnishes the present daily supply of 100,000,000 gallons. By referring to the map it will be seen that the shortest approximately straight line between the proposed site of Quaker Bridge

Jan 1, 1891

By Moshe Sheinkin, Douglas E. Julin

Large tonnage operations face many problems in adequately planning ahead for future years production. In order to maintain desired levels of production, such problems as source of tonnage, man- power and equipment requirements, tailings disposal and water requirements must be anticipated. Of course, before any of these problems can be analyzed, daily tonnage requirements and its source must be determined. Looking ahead for one year or even two or three is usually not sufficient time to adequately prepare an area for production. Because of the sequence of mining and the multilevel nature of the 42,000 tpd Climax mine in Colorado long-range planning must be on a ten-year basis. By using a ten-year base, adequate time is allowed to gain access and prepare a new level for production. Usually eight years will be required for this phase of the initial mine preparation. Once production has been started on a level and access to the area is available, three years is usually sufficient to prepare a new block for production as long as it follows in the normal sequence of mining.

Jan 4, 1967

By H. A. Wheeler

That lead and zinc deposits are the result of prolonged,, slow deposition is the idea of most students of ore deposits, and in many cases, where the ore-bearing solutions have been very weak or the precipitating conditions have been very feeble, the ore accumulations have undoubtedly taken a long period of time. As these two vital conditions have been subject to great variations in the different mining camps, the following example is highly interesting in showing that deposition can be very rapid under favorable conditions, geologically speaking, and also extremely recent. In fact, the writer is inclined to regard most, if not all, of the Mississippi Valley deposits of lead and zinc as probably being very young, at least not older than Tertiary, if not Quarternary, in age. The extensive Joplin lead and zinc district, in southwestern Missouri, which is about 60 years old and has numerous mines that were abandoned from 1 to 50 years ago, shows that the lead and zinc today are in an active condition of solution and redeposition, although these two metals occur in the predominant form of sulfides. The mine waters from the older and more or less abandoned portions of the district are frequently so acid, mainly from the oxidation of associated pyrite, as to necessitate the use of wooden pipes and pumps. The first boom in the Oklahoma zinc fields, which is the southwestern extension of the Joplin district, occurred when ore was accidentally struck in drilling a water well. Among the mines then opened up was the Mission mine, at Lincolnville, Ottawa County, Okla. This mine was opened in 1903 in lean "sheet ground," or a flat blanket formation of chert carrying disseminated zinc blende, or "jack," and galena. Theore-body was very free from iron pyrites and the concentrates were very high grade, the "mineral," or lead concentrates, assayed 80 to 85 per cent. lead and the jack, or sphalerite, assayed 60 to 65 per cent. zinc. The orebody was very shallow, occurring at a depth of 76 to 95 ft. (22 to 28 m.) and very wet, requiring three or four pumps to handle the water. The mine was operated until 1914, when it was closed by litigation and immediately filled with water. The second Oklahoma boom, five years ago, opened up the large, active camps of Picher, Tar River, and Century, which are located 2 to 5 mi. west of Lincolnville. They are considerably deeper, being farther down on the westwardly dipping monocline that emanates from the Ozark

Jan 1, 1920

By James Douglas

The Copper Queen mine was opened in 1880 by Messrs. Martin, Ballard & Reilly, and the first copper-furnace was blown-in on August 20th of that year. Prior to that summer nothing but prospect-work had been done on the copper Queen and on a number of adjacent claims. In fact, it was a small deposit, not of copper-ore, but of cerussite, which still remains undeveloped, on the western slope of the Queen hill, which

Jan 1, 1900

By Robert F. Mehi

The mechanical behavior of metals and alloys is presumably conditioned by two factors; namely, the crystallinc symmetry and the interatomic forces. Considerable attention has been given to the first of these factors through the recent advances in X-ray technique. It is the purpose of the present paper to call attention to the importance of the second of these factors, to point out promising methods of investigation, and to present some pertinent data. Plastic deformation takes place by slip along atomic planes.' This slip may be inhibited in a number of ways: by the interatomic forces of, cohesion which bind the atoms rigidly in a lattice structure, which in pure metals is usually of high symmetry; by latticc distortion caused by solid solution formation or by mechanical strain; by the intercrystalline boundaries whcrc slip is restrained, probably by the non-registration of the atom planes in adjacent crystal1ites;2 and by the presence of small hard particles which serve to "key" the slip along the atom planes.5 In pure metals, and perhaps also in solid solutions, the atom planes of easiest slip are those exhibhing the greatest density of atomic population and the greatest interplanar distance4 and apparently can now be pre-dict,ed from the analysis of the lattices. Concerning the interatomic forccs, which resist this slip by holding the atoms firmly together, little is known. Most textbooks on physical metallurgy, following the work of Bot-tone,5 correlate the hardness of the pure metals with the atomic volume,

By W. B. Wise, H. D. Attra, W. M. Black

The purpose of this paper is to illustrate a comparatively new approach for solving a problem that has plagued oil producers for many years—how to make the most money with available field production capacity. In a very basic operation such as a top-allowable one-well field, a computer and staff of engineers are not required to determine that the best operation is to produce that well at its maximum for as long a time as it will produce. However, as the problem becomes more complex and the number of wells and number of reservoirs increase, it probably will be a wise choice to devote some engineering thought and calculation time to determine the best way to operate that field on both an ultimate and day-to-day basis. Continued developments in the field broadly referred to as "operations research" have led to a number of useful engineering analyses for optimizing field operational problems. One of these techniques, termed linear programing, is parlicularly interesting because of its potential applications to the study of complex oilfield operating problems. Linear programing is concerned with the problem of planning a complex set of interde~endenl activities in the best possible (optimal) fashion. A field application of linear programing is being used to maximize daily income from a multi-reservoir producing operation. The initial results of this study indicate that the linear programing technique (I) can be applied effectively to field problems, (2) can be used to detect unsuspected avenues for improving operations and (3) can effect a significantly improved means of controlling field operations through the use of the highspeed computer. INTRODUCTION The usual approach for studying complex field operational problems has been to look in detail at several basic plans suggested by judgement and experience and, then, to choose the best plan from those investigated. This approach is entirely satisfactory provided: (1) that judgment and experience alone will reliably pick the best or near the best program as one of the plans to be investigated; and (2), and most important, that the factors which control field production will not change. This paper deals with the large group of field operations which are at least one-step removed from a satisfactory solution using the conventional method of analysis. Problems such as pipeline- and gathering-system design, transportation studies, large field development projects and multi-reservoir producing operations fall in this latter category. To find the best program for handling these problems when the best program is not obvious, a complete optimization study is required, and high-speed computers are required to continually update the program once it is selected. Operations of this type have an extremely large number of possible solutions. However, only one will result in maximum economic return and, more important, this one program must be re-evaluated and adjusted constantly to accomodate such changing field factors as the number of producing days, the price of crude, the discovery of new reserves, declining reservoir pressure with subsequent decline in production and a host of other factors which characterize specific operations. One of the most widely used, direct methods of optimization is a numerical procedure termed "linear programing", which is designed to investigate systematically each of the possible solutions involved in a given problem, determining rapidly and uniquely the optimum answer. As implied by the name, linear programing requires that all field variables be either defined or expressed in a series of interdependent linear equalities or inequalities. These relationships are solved simultaneously, using a form of matrix solutions to determine the optimum values for each producing variable that will maximize net profits. The solution techniques used in a recent field case study is termed the "simplex method" and is discussed in full detail in Ref. 1.

By B. G. Klugh

In a paper before the Institute at Wilkes-Barre, Pa., June, 1911,' Mr. James Gayley discussed the application of this process to iron-bearing materials. The same author² described the results of operations at the plant at Birdsboro, Pa. The purpose of the present paper is to present further discussion of some techuical details involved in the operation of this plant, and of the theoretical and practical relations of this product to blast-furnace practice. Since Oct. 1, 1911, the Birdsboro plant has been in operation at the blast-furnace of the E. & G. Brooke Iron Co. The results have been highly satisfactory, although the material treated, being chiefly the flue-dust currently made by the furnace or taker] from the accumulated stock-pile, was excessively high, and yet not uniform, in carbon, so that the desirable control or regularity of the amount of fuel in the mixture treated could not be maintained. Nothing could more forcibly demonstrate the flexibility of the process than the fact that, under these conditions, the sinter produced was, in all cases, of excellent quality. The Dwight & Lloyd process, as such, slid its present highly-developed mechanical appliances were described by Mr. Gayley in the paper above mentioned. While the repetition of some particulars will be unavoidable in this paper, it will be confined to features bearing upon the metallurgical principles involved. According to the principle of the process, the finely-divided iron-bearing material to be sinterecl is intimately nlixed with

Jan 1, 1913

By Charles Fettke

IN 1914, the officials of the Brundred Oil Corpn., faced with the problem of introducing new methods to increase production in the old and nearly depleted pools of Venango County, became interested in the Smith-Dunn (Marietta) process which was at that time being tried out in southeastern Ohio and which was already yielding very encouraging results. A license to use the process in Pennsylvania was secured from the owners of the patents. These patents were later declared invalid. The method was first used in Pennsylvania on a property consisting of about 434 acres, of which 300 are productive, at Hamilton Corners, 15 miles northeast of Oil City, in Cherry Tree and Oakland Townships, Venango County. The producing horizon is the First Sand of the Venango Group. A small oil pool was opened up in this vicinity in 1904. By July, 1916, when the compressed air was first introduced to restore pressure, the production had dropped to a point where it was no longer possible to continue profitable operation. From that time until March, 1927, over 100,000 bbl. of oil have been recovered from the tract. The property is being operated at present by the Brundred Oil Corpn. and Lux. The 1926 production, amounting to 10,650 bbl., was only 400 bbl. short of the maximum reached during any year of the 10-year period that the process has been in operation. Inasmuch as the Hamilton Corners pool is the first one in Pennsylvania in which the Marietta process was tried out, and the one in which it has been longest in continuous operation, considerable interest attaches to the results obtained. Through the courtesy of H. D. Brown and W. J: Brundred, officials of the Brundred Oil Corpn., all their data on this operation were made available to the writer in connection with an investigation of rejuvenation methods in the State for the Pennsylvania Geological Survey.

Jan 1, 1928

By B. DE MARE

THE No. 6 open-hearth furnace at the plant of the Worth Steel Co., Claymont, Del., is the first to be rebuilt according to the Kuehn system. This as well as the other five furnaces at Claymont, has a nominal capacity of 75 tons, but the actual charge is about 242,000 lb. No hot metal being available, the pig-iron is charged cold. Oil of low grade with an asphalt base is used as fuel. These two items have to be kept in mind when discussing the actual fuel consumption. Careful records have been kept covering a five weeks run and the following is a brief summary of them The time required to heat the furnace preparatory to charging from the time a wood fire was started until charging commenced was 36 hours. This, I understand, is much less than with furnaces of standard design. The draft of the furnace, as shown by a gage in the stack-flue, is 1.25 in. The maximum draft with new checkers on former runs was 1.50 in., this draft gradu¬ally decreasing as the checkers closed up. Both of the first helpers claim the present draft is all they need for the proper working of the furnace, and, as with the Kuehn regenerators the draft remains practically the same from beginning to end of a run, this is satisfactory.

Jan 1, 1929

By E. A. Gulbransen, J. W. Hickman

ONE of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film A comprehensive program has been undertaken to study these phenomena This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C Before the introduction of the electron diffraction technique, it «as necessary to use either direct chemical analyses or X-ray diffraction analyses to determine the nature of the oxide film formed on the metal or alloy Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry In special cases the information obtained may be identical, but in general both view-points are necessary Much of, the early work was carried out on the oxidation of bulk samples where thick films were obtained The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses Although much useful information has been obtained in this manner, little could be learned about the character of the protective oxides during the period when the films were actually protective Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective LITERATURE The oxidation of iron has been extensively investigated by X-ray and electron diffraction Jackson and Quarrell1 found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe304, between 515° and 900°C the stable film was FeO Above the upper change point of iron the oxide was found to be Fe304 prom 400° to 515°C , FeO, Fe304 or a mixture of the two oxides was found Recrystallization of the air-formed film below 400° and above 900°C led to the formation of Fe304 In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described

Jan 1, 1946

By Russell A. Carter

Seven years of rising silver prices have effectively revived an historic Idaho mining district and given it a new lease on life. Initial production earlier last year from the DeLamar open-pit silver mine in southwestern Idaho ushered in a new era of mineral production in a region that has weathered boom-and-bust cycles reaching back the better part of a century.

Jan 1, 1978

J. H. HEGINBOTHAM, a, metallurgist of the General Engineering Co., talked on "Current Milling Practice at Kirkland Lake," at the December meeting of the Utah Section. The ore is enough alike through the whole district so that some generalizations and comparisons may be made. The question as to whether or not the flotation process should be used in the flowsheet for extracting gold by cyanide solutions is still being vigorously debated, and it will seemingly need some years for a definite answer to be given. Most of the gold is either free, though much of it is finely dispersed in quartz, or occurs with pyrite. At times there may be 2 per cent of telluride compounds in the ore, but the amount of gold telluride present is small and has not been definitely established. It has been shown by Dr. Haultain and others that though gold tellurides may be so finely disseminated that it is necessary to grind the ore exceedingly fine, the compounds themselves are not difficultly soluble. (An increase in temperature helps to dissolve tellurides, and also to settle pulps.) It is likely that if the ore were ground through 400 mesh, practically all of the gold would be soluble. As it is, with 96 to 98 per cent of the ore ground to minus 200 mesh, and some 70 per cent minus 325, the cost of

Jan 1, 1934

By N. N. Breyer

A specially built "hard" tensile machine with characteristics permitting the precise detertnination of the drop of the load at the yield point has been used to study the magnitude of the yield-point phenotnenon in prestrained martensitic 4340 steel. A new phenonzenon, the appearance of a secondary yield point, has been observed by holding the specimen at constant strain in the plastic region. Furthermore, it has been found that a series of yield-point drops could be introduced by successive constant strain holds in the plastic region. The isothermal kinetics of the development of the secondary yielding point lave been studied at four temperatures: 24° 0° -18°, and -79°C. From the results of the kinetic investigation, equations for the In a previous investigation1 it was shown that, contrary to generally held opinion, steels of medium carbon content, such as 4340, 4140, and 86B30, in the as-quenched martensitic condition, can be cold-drawn through a die with reductions in area of up to 10 pct without cracking. Tensile specimens of 4340 machined from bars quenched and prestrained in this manner exhibited tensile strengths of about 400,000 psi coupled with 30 pct reductions in area. In addition, it was found that each sample of such steels exhibited a yield point in the quenched, cold-drawn condition. Since these studies were conducted on a commercial hydraulic testing machine of a type which is not well-suited to detailed study of yield-point behavior, it was decided to study this phenomenon more thoroughly on a rigid straining machine. In this new investigation, use of such a "hard" machine not only allowed study of the magnitude of the yield-point drop but also revealed a new phenomenon—secondary yielding of the martensite introduced by stopping crosshead motion after plastic deformation of the sample had begun. The present paper is a report of these findings. MATERIALS AND PROCESSING The material used was a commercial 4340 steel of the composition shown below: 0.41 0.80 0.013 0.019 0.31 0.85 1.76 0.28 1 0.42 0.77 0.015 0.024 0.30 0.84 1.69 0.28 0.08 2 1 = Ladle analysis. 2 = Laboratory analysis. Bars of this steel were processed in the following way: 1) machined to predetermined diameters; 2) austenitized at 870°C for 1 1/2 hr; 3) oil-quenched; 4) cooled to -115°C for 1/2 hr; onset and increase in magnitude of the secondary yielding in this temperature region have been found to fit the relationship ?Ys = Atn where ?Ys is the magnitude of the secondary yield Point in psi, t is the time in seconds, and A and n are parameter characteris-tics of the material. Although the occurrence of the primary and secondary yield points could be rationalized qualitatively on the basis of stress-induced ordering of carbon atoms in the stress fields of dislocations, as postulated in an earlier paper, the kinetics of the secondary-yield-point development were interpreted to indicate that the ordering involves more than just single jumps of carbon atoms from high-energy to neighboring low-energy sites. 5) pickled and lime-coated; 6) drawn through a carbide die. The predetermined diameters were chosen so that drawing through the same die gave the various reductions desired. Tensile specimens of 0.252 in. diam with a 1 1/4 in. gage length were then prepared from the drawn bars and tested. In order to study the stress-strain behavior at the yield point in detail, a rigid tensile machine with a high spring constant was constructed. Columns of large cross section (relative to the specimen cross section) constituted the machine frame. A dc motor was used to drive a screw via a gear reducing train and a "crane" thrust bearing. In this relatively simple device small deformations could be observed un-blurred by the slow response and lower spring constant inherent in hydraulic machines.' A strain-gage dynamometer permitted load changes as small as 8 lb to be read. RESULTS Tensile test samples machined from bars in the as-quenched condition with no subsequent drawing and samples from bars with 3.8 pct reduction after quenching gave stress-strain curves typified by those shown in Figs. I and 2. The time lapse between predrawing and tensile testing varied but usually ranged between 3 to 6 days at room temperature. The strain rate during testing was 0.003 in. per in. per min. The as-quenched curve is seen to have a broad serrated maximum whereas the stress on the specimen prestrained 3.8 pct rose linearly to point A, Fig. 2, fell abruptly to B, and then gradually to C. The abrupt drop to B was accompanied by evidence of incipient necking. The drop of the stress at the yield point in the prestrained samples (A to B in Fig. 2) changed with the percent prestrain, as illustrated on Fig. 3. Although the tensile strength increased continuously with the amount of previous cold drawing, the magnitude of the yield point drop first increased—up to about 6 pct prior reduction—and then decreased. Specimens from bars predrawn more than 8 pct broke in a brittle fashion in the elastic portion of the stress-strain curve.

Jan 1, 1967

By J. W. Hickman, E. A. Gulbransen

One of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film. A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film. A comprehensive program has been undertaken to study these phenomena. This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C. Before the introduction of the electron diffraction technique, it was necessary to use either direct chemical analyses or X-rav diffraction analyses to determine the nature of the oxide film formed on the metal or alloy. Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry. In special cases the information obtained may be identical, but in general both viewpoints are necessary. Much of the early work was carried out on the oxidation of bulk samples where thick films were obtained. The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses. Although much useful information has been obtained in this manner. little could be learned about the character of the protective oxides during the period when the films were actually protective. Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique. In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective. Literature The oxidation of iron has been extensively investigated by X-ray and electron diffraction. Jackson and Quarrelll found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature. The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe³O4; between 515° and 900°C. the stable film was FeO. Above the upper change point of iron the oxide was found to be Fe³O4. From 400' to 515°C., FeO, Fe³O4 or a mixture of the two oxides was found. Recrystallization of the air-formed film below 400' and above 900°C. led to the formation of Fe3O4. In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described.

Jan 1, 1947