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By G. W. Brock

Experiments in the form of aging of overstrained tension specimens and elevated temperature tension testing, have been carried out on recrystallized arc-cast molybdenum. The aging behavior of molybdenum was found to be strongly dependent on the degree of plastic strain present in the lattice: the reason for this being the low solid solubility for the common interstitial elements in molybdenum. GEORGE W. BROCK, formerly Research Associate, Department of Theoretical and Applied Mechanics, University of Illinois, Urbana, III., is Research Associate, Department of Engineering Sciences, IBM Research Center, Yorktown Heights, N. Y. Manuscript submitted January 19, 1961. IMD THE term strain aging is familiar in connection with the recovery of the yield point in mild steel after tensile overstraining, and there are other instances where it is known to exert an appreciable effect on mechanical properties. For example, steel exhibits a greater tensile strength at mildly elevated temperatures than at room temperature and serrated stress-strain flow curves occur under certain conditions. It has been known for a number of years that the phenomenon of strain aging is directly connected with the presence of carbon and nitrogen in the lattice; and extremely small amounts of either element are sufficient to produce the effect. In this study, the aging behavior of overstrained tensile specimens of recrystallized molybdenum has

Jan 1, 1962

By C. A. Heiland W. E. Pugh

The principle underlying the majority of magnetic intensity variometers is a comparison of the force to be measured with another force of known magnitude. The known force may be (a) of a magnetic nature, such as magnetic fields produced by magnets or coils, or (b) of a mechanical nature, such as (1) the elastic forces of wires, or (2) the force of gravity, such as employed in bifilar magnetometers and magnetic balances. In instruments of such type, usually a magnetic system is employed, free to move about either a horizontal or vertical axis, on some sort of a suspension. If the earth's magnetic field alone were present, such a system would adjust itself into the direction of the field or that of its components. Owing to the simultaneous action of the comparison force, however, the magnetic needle assumes a position that differs from the direction of the magnetic force; for all such instruments, the angle of deflection is given by tan = FIX, where F is the known and X the unknown earth magnetic force component. In other words, the magnetic system merely serves as an "indicator" for the position of balance of the two forces. Considering the matter from this point of view, it is not immediately obvious why the temperature of such a magnetic system should modify the results. In magnetic instruments, we may distinguish two different effects of temperature: (1) a magnetic effect and (2) a mechanical effect. The first is due to the fact that the magnetic moment of a magnet drops with an increase in temperature. This drop is characterized by the temperature coefficient of the magnetic moment (see equation 1). The second effect is due to the change in the torsion of suspension wires with temperature or to the expansion of lever arms of masses acting on magnetic balances.

Jan 1, 1934

By A. H. Daane, R. L. Myklebust

The yttrium-manganese system has been investigated by thermal, metallographic, and X-ray diffraction methods. There are three intermetallic compounds present: YMn2 which melts congruently, YMn4, which undergoes syntectic decomposition, and YMn,, which undergoes peritectic decomposition. The compound YMn4 is ferromagnetic at room temperature with a Curie temperature of 214°C. There are eutectics at 25.2, 60.9, and 82.0 wt pct Mn which melt at 878°, 1100°, and 1075°C, respectively. Crys-tallographic data are given for YMn4, and YMn12 . The terminal solid solubilities are low. In a general program of study of yttrium metal in this laboratory some alloy systems of this metal with elements of the first transition period have been examined. This work was originally instigated by experiences in cladding yttrium with jackets of some protective metals such as Inconel for high-temperature service in air.' In some cases a low-melting phase was observed to form between the Inconel and the yttrium resulting in failure of the samples. In characterizing this reaction, a survey was made of the systems of yttrium with chromium, manganese, iron and nickel,, and it was found that a eutectic was formed between these metals and yttrium on the yttrium-rich side of the system. This present study of the Y-Mn system was carried out to examine in more detail the alloying nature of yttrium, and to correlate trends that have been observed in previous related studies. It was observed by Voge13 that in the systems of lanthanum, cerium, and praseodymium with each of the metals in the first transition series, the tendency to form compounds diminished in the order nickel, cobalt, and iron while no compounds were formed with manganese, chromium, or titanium. Beaudry and Daane4 observed a similar behavior in the systems of yttrium with some members of the first transition series except that the tendency for compound formation was greater. Both the Y-Ti5 and Y-Cra systems consist of simple eutectics, while in the Y-Fe,7 Y-CO, and Y-Ni4 systems, there are four, eight, and nine compounds, respectively. In addition to the above trends, the similar atomic radii and electronegativities of yttrium and thorium invite a comparison between their alloying behaviors with a common element such as manganese. In crys- tallographic studies, Florio et al.' have identified three intermediate phases in this system which are ThMn2, Th6Mn23, and ThMn,,. Gschneidner and Waber10 have examined published information on alloy systems of the rare-earth metals and have correlated this information with current alloying theory. From their study, they predicted that the Y-Mn system would contain one intermetallic compound. On the basis of this prediction, the trend in the alloying behavior of yttrium with the elements of the first transition series and the alloying behavior of thorium with manganese, one might expect from one to three intermetallic compounds to form in the Y-Mn system. A consideration of Hume-Rothery's rules of alloying based on size-factor, electronegativity, and valency suggested a small terminal solubility and possible compound formation. The present study was undertaken to confirm these predictions of low terminal solid solubility and compound formation and to establish the general alloying behavior of yttrium with manganese. EXPERIMENTAL Materials. The manganese used in this investigation was obtained from the Foote Mineral Co. as electrolytic plates of 99.9 pct stated purity; the yttrium metal was prepared in this laboratory. Table I gives the analyses of these materials. For the solubility studies at the yttrium-rich end of the alloy system, distilled yttrium, whose major impurity was 200 ppm Ti, was used. Preparation of Alloys. The alloys were formed by comelting the two metals in an are-melting furnace under an atmosphere of argon. The buttons thus formed were inverted and remelted three to five times to promote homogeneity. Due to the high vapor pressure of manganese, it was assumed that the weight lost during are-melting was all manganese. This assumption was based on the very good agreement observed between calculated compositions and chemical analyses of several alloys. The compositions of the dilute alloys used for solid solu-

Jan 1, 1962

By I. Lowthian Bell

THERE has been probably no improvement introduced into the manufacture of iron which created more surprise in the minds of practical smelters and of scientific men than Neilson's discovery of the hot blast. In 1829, Messrs. Dunlop & Co. consumed at the Clyde Works, near Glasgow, nearly 7 3/4 tons of coal to make a ton of pig iron, of which about 20 cwts. was employed under the boilers of the blowing engines, leaving nearly 7 tons for the consumption of the furnace itself. In the year 1833, by heating the air to 612° F. (322° C.), they reduced the 7 3/4 tons to 3 tons by the mere burning of 8 cwts. of coal in the apparatus for raising the blast to this temperature. The statement just given is strictly true in a commercial sense, but when we come to consider the question as one of physical science, it is necessary to eliminate some of the conditions which conduced to so extraordinary a result. Anterior to Neilson's time the fuel employed in smelting iron was coke, and it was supposed at that period, erroneously, however, that coal in its raw state, when burned with cold air, was totally unfit for the purpose in question. This mineral, as it was obtained from the Lanarkshire coal-field, contained about 35 per cent. of volatile matter, but the process of charring it was performed in so unskilful a manner that instead of receiving 88 cwts. of coke from 135 cwts. of coal, 60 cwts. only was the product of the operation. Again, the reduced consumption of carbon in the furnace itself was accompanied by a corresponding diminution of blast, and this was followed by an economy of half a ton in engine coal. After making a proper allowance, however, for all these collateral circumstances, we are within the mark when we admit that in actual coke, which is really the form the fuel has to assume before it is burnt in the blast-furnace, not less than 30 cwts. was saved by heating the blast to 615° F. (322° C.). This unexpected economy, be it remembered, was obtained by the combustion of the 8 cwts. of coal, somewhat wastefully applied in the hot-air apparatus. Numerous have been the opinions advanced by different authorities in the scientific world to account for the apparent anomaly, but none,

Jan 1, 1877

Jan 1, 1929

By J. R. Cain

In every process for making steel there are one or more stages where the metal is exposed to gas of one kind or another. Thus, in the open-hearth furnace, the carbon dioxide and water vapor in the products of combustion are oxidizing toward the ferrous and manganous oxides in the slag, tending to convert these to higher oxides; the higher oxides then , oxidize the steel, so that indirectly the products of combustion are oxidizing toward the steel. In the Bessemer process, there is direct contact of air and steel; also, the water vapor in the air blown into the converter is continually decomposed by the molten steel, yielding hydrogen and ferrous oxide, both of which are in part taken up by the metal. In the electric-furnace processes, there is always more or less air in contact with the slag covering the metal, and this air and the gaseous reaction products from it are dissolved in the slag to some extent and thus transmitted in part to the steel. In the crucible processes, there is always entrapped air in the charges and the crucibles are more or less permeable to the gaseous products of combustion from the furnace. In all the processes of manufacture, the molten metal is exposed to air while tapping into ladles and ingot molds and has an opportunity to saturate itself with air or with gaseous or solid products generated by chemical reactions between air and steel. Sievertsl has shown that molten metals requirc but a few seconds to saturate themselves with a surrounding gas. No one familiar with the operations at a steel plant needs to be reminded of the important role that gases play at all stages. The familiar "boil" of open-hearth furnaces, due to evolution of carbon monoxide when iron ore is added to the molten steel; the spectacular operation of the Bessemer converter brought about entirely by a gaseous reagent; the almost magic effect of small quantities of silicon, manganese, or aluminum added to the molten metal in ladle or furnace in quickly preventing bubbling and evolution of gases; the unwelcome phenomena of blowholes in ingots that have not been properly manufactured—these

Jan 1, 1920

By R. D. Pehlke, W. M. Small

The effect of added alloying elements on the solubility of nitrogen in a liquid alloy of 74 wt pct Fe. 18 wt pct Cr, and 8 wt pct Ni has been studied. At 1600°C and 1 atm nitrogen pressure, aluminum, chromium, columbium, manganese, molybdenum, tantalum, and vanadium increase the solubility of nitrogen in the liquid 18 Cr-8 Ni alloy, whereas additions of cobalt, copper, nickel, silicon, tin, and tungsten decrease the solubility. Interaction parameters based on a constant ratio of iron, chromium , and nickel have been used to quantitatively define the changes in nitrogen solubility. INVESTIGATIONS on the solubility of nitrogen in liquid iron have usually treated the pure metal, and often the influence of a single added element. Pehlke and Elliott1 carried out a comprehensive study on the influence of alloying elements on nitrogen solubility in liquid iron, and compared their results with previous studies. Turnock and pehlke2 have recently reported a study on the solubility of nitrogen in multicomponent liquid iron alloys. The original interaction parameter proposed by wagner3 was successfully employed in these studies. The need for obtaining information on the gas solubility in more complex alloys is indicated by the increasingly significant role played by dissolved gases in the processing of iron-based materials. The commercial stainless steels, for example, represent an area where data on nitrogen solubilities are required as a function of composition, temperature, and gas pressure. The nitrogen solubility in liquid Fe-Cr-Ni alloys has been studied by Humbert and Elliott.4 Their investigation covered the entire ternary system, and attempted to use data from binary alloys to predict nitrogen contents in liquid ternary alloys. Langenberg,5 using a method developed by Morris and buehl,6 calculated the nitrogen solubilities in multicomponent iron alloys from data available on binary iron alloys at 1600°C. Nelson,7 using a regular-solution model, extended this prediction to include the effect of temperature. Chipman and corrigan8 and Turnock and pehlke2 also employed empirical methods to calculate nitrogen solubilities in liquid multicomponent iron alloys. In order to provide a basis for predicting nitrogen solubility in liquid stainless steels, and to extend the data available for thermochemically modeling systems of this type, the following investigation was carried out. The study involved measupements of nitrogen solubility in a nondilute alloy and examination of the influence of a small addition of an alloying element on the nitrogen solubility. The study was focused on a very narrow range Of composition in the vicinity of 18 wt pct Cr-8 wt pct Ni (herein referred to as 18-8) with special emphasis on the change of.nitrogen solubility with the addition of a fourth metallic element. EXPERIMENTAL PROCEDURE A Sieverts' apparatus, described previously,1,2 was used in this investigation. The charge materials were contained in a recrystallized alumina crucible and inductively melted. Additions were dropped from a glass side-arm. All materials were hydrogen-refined and vacuum-treated to eliminate or minimize the oxygen content. The source and purity of materials is given in Table I. The initial metallic charge was heated to approximately 1000°C and held under vacuum for 30 to 45 min as a means for removing hydrogen and adsorbed gases. Argon was used as the calibrating gas to determine the "hot volume". The average hot volume of the system was approximately 50 cu cm STP and a few experimental runs were made using a reaction bulb with a hot volume of 80 cu cm. The temperature range studied was from 1550° to 1700°C and the temperature was measured optically. THEORETICAL PRINCIPLES General Discussion. Nitrogen dissolves in liquid iron alloys according to the reaction: 1/2N2(g) = N (wt pct in solution) [l] The equilibrium constant, K1, for this reaction is written as:

Jan 1, 1969

THE composition and quality of finished steel depend upon selection and proportioning of the raw materials of the charge as well as upon control of furnace practice. This chapter deals only with the raw materials of the basic open-hearth process that are important in determining the composition of the steel or slag. They are the metallic charge, oxygen-bearing materials, fluxes, alloying and deoxidizing additions, and certain refractory materials used for maintenance of bottoms. Other refractories, which may affect the slag composition, are discussed in Chapter 3. Wide variations are possible in the type and composition of charged materials but certain limiting relations among the elements of the charge must be observed. Since the process consists essentially of refining by the oxidation of undesired dements, a balance must be established between the sources of oxygen and the elements in the charge that are subject to oxidation (see Chapters 2 and 7). For example, if it is desired to use a high ratio of blast-furnace hot metal to scrap, it is necessary to add an oxygen-bearing material such as ore or mill scale to eliminate the excess carbon and silicon that are present in the hot metal. An example of the opposite extreme is the use of a metallic charge composed entirely of steel scrap. With this type of charge, it is common practice to substitute burnt lime for limestone as a flux and to charge some carbonaceous material such as coke to avoid an excess of oxygen in relation to the elements of the charge that are subject to oxidation. Elements such as copper and nickel, which are not oxidized or eliminated by, any other reaction, may be introduced into the charge only to the extent to which they are permissible in the finished steel. An example of adjustment of the charge for elements of this type is found in the use of steel scrap high in copper. In this case, metallic components of the charge other than the scrap should be low in copper, or a sufficiently high ratio of pig iron to scrap should be charged to dilute the copper from the

Jan 1, 1951

By R. R. McNaughton

The Consolidated Mining and Smelting Company of Canada, Ltd. at Trail, B. C., inaugurated a comprehensive program of investigation about 15 years ago to develop the most economical process of recovering the metal in the large accumulated stock of by-products of the lead smelter and the zinc plant. Two principal methods of recovery were followed to a successful conclusion—an electrothermic process to treat zinc-plant residues and cold slag and the fuming of hot slag from the lead blast furnaces. The latter was selected because it showed a saving over the former in its ability to handle hot blast-furnace slag, thus obviating the necessity of granulating, handling and eventually remelting the same slag for the electrothermic process. The design of a fuming plant was commenced in 1928, and construction, which was started immediately, was completed in July 1030. Operating intermittently for a general tuning up, the plant was officially blown in for regular operation in August. During this month the vagaries of a slag-fuming plant were studied and an operating crew was trained. A history of slag fuming at Trail and the development of plant design is given in a paper by G. E. Murray in the Transactions of the Canadian Institute of Mining and Metallurgy for 1933. Fuming Plant The fuming plant at Trail (Fig. 1) is a separate unit although of necessity interlocked closely with the lead smelter. The plant consists essentially of a fuming furnace with its accessories, a waste-heat boiler followed by an economizer, and a suction-type baghouse. The plant was built as the first of two 400-ton units with the intention of adding the second unit within a year, so that flues, fans and buildings were built to handle double the original load. Furnace.—The furnace as originally built (Fig. 2) was of water-jacket construction, 10 ft. wide, 20 ft. long and 6 to 10 ft. high. The roof height was made variable to check experimental work, which had indicated that this dimension affected the rate of reduction. Coal and air were supplied

Jan 1, 1937

By William Marsh Baldwin

THE ROLLING OPERATION proper is applied to metals and alloys not only in the production of flat products but also in the production of shapes, rods, wire and even in specialized forms in the production of tubes. The present discussion of rolling copper and copper alloys will be [ ] limited to a consideration of rolling flat products such as strip, sheet, foil, plate, and others. In this case (as in the others listed above), the rolling operation itself is only part of an integrated sequence of operations. In Fig I such a sequence going to make up a brass strip mill is sketched out. It is seen that the rolling opera-

Jan 1, 1948

Jan 1, 1969

By Grover R. Castle

INTRODUCTION "Project Financing" or "Project Loans" have become increasingly popular in recent years, and commercial banks are being asked to consider more and more of such financing. However, the analysis of this type of loan is quite different from the analysis of a loan to a financially sound corporation based on the company's balance sheet. For this reason Chemical Bank did a study of project loans in an attempt to be more sophisticated in our approach to them. As part of this study, we examined 29 project financings for which information was available. In this article I shall describe project loans and set forth the guidelines we developed, as an aid to credit officers who might have occasion to analyse this type of financing. DEFINITION OF "PROJECT FINANCING" OR "PROJECT LOAN" The terms "project financing" and "project loan" commonly describe the various methods that banks and institutional lenders use to finance the construction of new projects on a basis whereby payout is anticipated from the revenue stream generated by the project. A project financing often involves a loan to a new entity formed specifically to own the project. The analysis of a project loan proposal is quite different from the analysis of other term-loan proposals since it involves a credit decision based on the review of a projection or forecast rather than of historical earnings and/or it involves the reliance on contractual obligations of third parties. Lenders are asked to assume the added risks associated with project loans because: 1. Project financing may permit a company to obtain additional leverage. It is possible for companies to arrange financing on a project basis that could not be arranged as a direct borrowing. For example, a company may not be permitted to borrow more money directly, due to a limitation in a bond indenture. However, a project financing can sometimes be negotiated on a basis not prohibited by the indenture. 2. Often the sponsors of, or the stockholders in, the project are seeking an off-balance-sheet financing. For example, 11 of the 29 projects in our study were arranged on an off-balance-sheet basis and one showed on the balance sheet as a deferred income item. An off-balance-sheet financing, for the purpose of this article, is a financing which does not show as a direct liability on the balance sheet of the sponsors of or stockholders in a project. 3. Projects are often located in a foreign country. The financing is arranged so that the lenders assume the political risk on the loan because many companies rightly believe that this arrangement affords a degree of insulation from political risk not otherwise obtainable. 4. Many projects are jointly owned by several sponsors. This form of financing lends itself well to a situation where a new entity is formed to own a project and do the borrowing. Project loans can be used to finance a variety of activities including development of iron-ore deposits and associated pelletizing plants; development of coal reserves; construction of pipelines, alumina plants, fertilizer plants and refineries; etc. The specific areas of analysis can be quite different, depending upon the type of project being financed. It is important, therefore, to classify the proposal according to the type of project, and also by the nature of the financing - nonrecourse financing, financing covered by a guarantee of completion and financing supported by an undertaking lasting for the life of the financing. I will discuss each of these types in more detail later, but first, I should like to make some

Jan 1, 1985

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

THE. extraordinary volume of work done in this period, and the multiplicity of subject matter, make a year-by-year historical account undesirable, if the account is not to be an assembly of unrelated fragments. We shall, instead, undertake to narrate the development in this period of each of the branches of the subject separately, hoping that their interrelations will be self-evident. There is a certain arbitrariness in the selection of subject matter in the following sections. The development of important engineering alloys-for example, high-speed steel-is disregarded, for it is the primary purpose of this account to relate the advances in ideas, the growth of the science of metals; other historical accounts relate these parallel advances. Nor are advances in techniques stressed, though occasionally the most important are noted; nor is the progress described in allied fields such as welding, cutting, etc.; for though these developments have very frequently made possible the advances herein related, they are far too numerous to recount in anything short of a ponderous volume. There is a more serious arbitrariness, however; it is not an easy matter to draw the boundaries of physical metallurgy, and some contiguous subjects have been omitted that perhaps should have been included, such as, for example, corrosion, gases in metals, the magnetic behavior of metals and alloys, and certain other fields in the physics of metals. REACTIONS IN ALLOYS--DIFFUSION Many of the reactions occurring in alloys proceed by the operation of the process of diffusion in the solid state: the annealing of mixed powders to form alloys, the homogenization of castings or forgings, the freezing of alloys, the treatment of clad metals, the loss

Jan 1, 1948

By Galen G. Waddell

Several years of rock-burst research conducted by the U.S. Bureau of Mines in cooperation with the mining companies of the Coeur d'Alene mining district, Idaho, in addition to progress made by others throughout the world, have led to a good understanding of the rock-burst problem. This paper describes conditions which have caused specific bursts, present capabilities of detecting stress buildup and bursts, control methods, and a suggested approach to analyzing any individual mine-burst problem. A rock burst is the sudden, violent release of stored strain energy in rock by some mechanism of rock failure, generally accompanied by expulsion of rock with consequent damage to the mine. A burst may be audible for only a few hundred feet, or on the surface it may sound like a sonic boom miles away. A Dictionary of Mining, Mineral, and Related Terms, U.S. Bureau of Mines (USBM)* 1968yand defines a burst as Bureau "That phenomenon which occurs when a volume of rock is strained beyond the elastic limit and the accompanying failure is of such a nature that accumulated energy

Jan 1, 1971

THE problem of reaction rates in the open-hearth process is essentially that of trying to form a fairly clear picture of the "chemical mechanisms" in the bath. Quantitative data on reaction rates would perhaps not be of much practical importance even if they were available; however, what few approximate data there are can be used in combination with data given in Chapters 16 and 17 to sketch a picture of the "chemical mechanics" of the open-hearth process that is consistent with essentially all the present available evidence. The result may later be found incorrect in many details but even so it will illustrate certain useful methods for obtaining a clearer understanding of the process. Consistent with the treatment in Chapter 15, but in simpler terms, we may say that chemical reactions in general involve the following elements or steps : 1. The reacting molecules are mixed together in space in such fashion as to favor collisions among them. 2. Units of what is usually an intermediate molecular arrangement called an activated complex are formed at a certain rate, depending on temperature and concentrations. 3. .These activated complex units decompose into the reaction products (this step usually assumed to be so rapid as never to limit the over-all process). 4. In any of these steps, heat energy may have to flow into, or away from, the reaction zone to permit the reaction to proceed. 5. The products of reaction will usually have to move out of the way to permit further reaction. The temperature factor enters mainly through step 2, and its effect is very marked. (What is called temperature is really the mean energy content of all the molecules of the substance involved; at any one temperature a certain proportion of the molecules will have much higher energy content than the mean value.) Various reaction rates measured at around room tem-

Jan 1, 1964

By A. Goldberg, T. E. Tietz, J. E. Dorn

INTRODUCTION THE concept that the flow stress for plastic deformation of metals in the work hardening range is a function of the instantaneous values of the strain, strain rate and test temperature was promulgated by Ludwick1 many years ago. This thought has been more or less a guiding principle throughout the immediate period of development and growth of mechanical metallurgy. It has been tacitly assumed or knowingly applied to many investigations on the plastic behavior of metals. Spurred by the theoretical interest and practical importance of the plastic behavior of metals, many investigators have attempted to determine empirical, semi-empirical, and theoretical equations2-18 relating the flow stress with the strain, strain rate, and temperature. Although the applications of such equations have been extensive, the experimental verification of the existence of a mechanical equation of state is weak. Furthermore, some of the available evidence on plastic flow appears to suggest that no simple functional relation between stress, strain-rate, strain and temperature can exist. The mechanical equation of state demands that [a = a(e, E, T)[I]] Where o = true stress = load/instantaneous area e = true strain = In Instantaneous gauge lengths initial gauge length e = true strain rate T = temperature] This formulation implies that [da] is an exact differential. Therefore the flow stress (o) is a function of the instantaneous values of the strain (e) the strain rate (e) and the temperature (T), independent of the previous mechanical or thermal history. Having reached a certain strain, strain rate, and temperature, by any path whatsoever, a definite and fixed value of the flow stress should be obtained. One check on the validity of the mechanical equation of state is easily obtained. Consider the following three tests on the stress-strain curve at constant temperature: [A. Strain at rate [ei] B. Strain at rate i2 C. Strain at rate [Ei] to [ei] and continue test at i2] A graphical representation of possible results of such tests are shown in Fig I. If, for strains greater than [el], test (C) data coincide exactly with the data from test (B), as shown in Fig Ia, a limited verification of the mechanical equation of state is obtained for the range of strain rates from [ii] to [e2]. But if the data from test (C) differ from those of (B) beyond strain [el] where the strain rate is changed from [e,] to [€2i] the mechanical equation of state is not

Jan 1, 1948

By John Wulff, H. H. Uhlig

Since its first mention in the literature in the eighteenth century12 the phenomenon of passivity in metals has stimulated much speculation and attendant controversy as to its nature and cause. No one of the numerous theories so far proposed has been generally accepted. ‡ Faraday,' in 1836, associated the passivity of iron with a protective film over the surface of the metal, which materially prevents or slows down reaction with corrosive environments. His theory was that oxidizing acids like nitric acid form an unstable oxygen or oxide layer over the iron surface, which protects the underlying metal from further attack. This concept was simple yet plausible, and without alteration has frequently been assigned in present-day discussions as explanation of the passivity of many metals. With the advent in recent times of stainless steels, it is not surprising that this oxide film theory of passivity proposed by Faraday has been used to explain the phenomenal corrosion resistance of stainless steels and other passive alloys. The passive alloys, such as the chrome-iron alloys, are supposedly covered with a protective oxide film, which forms on exposure of the alloy to air, is extremely stable and self-healing, and accounts for the remarkable resistance of these alloys to corrosion. Within the past few years, several investigators, following the theory of film protection, have attempted to gauge the resistance of the supposed film on steels. Brennert8 and Donker and Dengg9 determined the potential at which a negative ion (e.g., C1-) moving in an electric field reacted with the metal anode, as detected by increased current flow or change in potential of the steel electrode in an electrolytic cell. The potential corresponding to reaction Brennert called the film break-through potential.

Jan 1, 1939

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

In a previous paper' the authors have investigated the structure of the oxide films formed on most of the metals that make up the alloys of this study. The metals were studied in order to provide basic information on the structures, both physical and chemical, of the oxide films and to determine how these structures are effected by the temperature, time of oxidation, and surface preparation. It was felt that an understanding of the physical and chemical structure as well as the stability of the oxide film might furnish clues as to the nature of the reaction process and the protective quality of the film. The oxidation of the metals was studied over the temperature range 300' to 7o0°C. except for copper, wherc the range selected was 100' to 500°C. The results of these studies were presented in graphical form as existence diagrams of the oxides on a time-temperature scale. For some of the metals the existence diagrams were simple and showed few chemical transitions, but there were numerous cases where the physical state of the oxide surface was a function of time and temperature. In general the physical state of the oxide surface changed with increasing temperature so as to increase the sharpness of the diffraction patterns and to cause orientation effects to be more pronounced. Deviatiois in lattice Darameters from X-ray values were noted. In general these deviations were of positive nature and may be due to solid solution of the metal in the oxide lattice. This effect might be expected in thin oxide films. In a study of the oxidation of alloys containing two or more metals, there may arise the complicating factor of identification of the oxides formed. A thorough understanding of the oxides formed on the pure metals, therefore, was, essential before investigation of the oxidation of alloys. In this paper it is our purpose to present a study of the following problems: 1. The existence diagrams of various alloys. 2. The effect of the structure of the alloying metal on the existence diagram of iron. 3. The effect of the percentage of chromium on the oxides formed on Fe-Cr alloys. 4. The relationships, if any, between the oxides formed and the protective quality of the oxides. The following alloys are included in this study: alloys of iron with body-centered cubic, face-centered cubic and other metals, 13 Cr-Fe, 18-8 stainless steel, K4²B, Nichrome V, Hipernik, Inconel, Stellite "²I," Refractaloy, Kovar, mild steel, a series of Cr-Fe alloys and a series of Co-Fe alloys. Since many of the commercial alloys in this list contain more than two metals, various complicating factors in the identification of the oxides formed may arise.

Jan 1, 1947

By W. P. Saunders, W. R. Hibbard, G. H. Eichelman

Interest in the various products of the austenite eutectoid transformation in iron-carbon alloys, particularly as produced by the isothermal sub-critical techniques introduced by Davenport and Bain,' has resulted in the application of similar heat treatments to other eutectoid transformations. Studies o f the beta copper-aluminum alloy eutectoid transformation revealed microstructures very similar to those found in iron-carbon alloys. Investigations5t6 of the kappa phase in the copper-silicon alloy system have established the eutectoid type transformation of this phase into terminal alpha and intermediate gamma phases. This transformation has been reported5 as forming a eutectoid type structure in a very sluggish manner by a long time isothermal treatment. The purpose of the present investigation is to study the products of the kappa eutectoid transformation as affected by transformation temperatures by means of microscopic and hardness methods. Preparation of Alloys The copper-silicon alloy equilibrium diagram is shown in Fig 1. The kappa field converges to a minimum silicon solubility at the eutectoid composition and all other completely kappa alloys are hypereutec-toid. Thus, kappa decomposition involves first the proeutectoid precipitation of gamma, followed by the eutectoid transformation of a lower silicon content kappa (5.2 pct) Smith6 has indicated that alloys containing between 5.4 and 5.7 pct silicon could be hot rolled, but that the latter composition was desirable in order to permit a wider kappa temperature range. The alloy was prepared by adding Baker's commercially pure silicon to an ingot of copper-silicon alloy containing 2.34 pct silicon remaining from the investigation of Brick, Martin and Angier.' Following the casting techniques of Krynitsky, Saunders and Stern,s the ingot was melted under a heavy layer of dried charcoal in a clay-graphite crucible in a gas-fired pot furnace. Small lumps of silicon were held under thc melt surface with a graphite rod. After the silicon had dissolved, the alloy was chill-cast and then remelted without a cover, stirred thoroughly, skimmed and poured into a preheated cast iron mold. The cast microstructure is shown in Fig 2. The casting, 10 X 4 X K in., was annealed at 750°C for 21 hr and furnace cooled, About }{& in. was milled from all surfaces. The plate was cut in half longitudinally and the bottom half analyzed by A.S.T.M. and The composition by weight was as follows: copper 94.24 pct, silicon 5.56 pct, iron 0.11 pct.

Jan 1, 1949