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By C. S. Barrett, P. Coheur

ANNEALING twins are common in the microstructure of copper that has been rolled and recrystallized. In such samples it follows that a twin relationship should exist between components of the recrystallization texture,1 and several examples of this have been reported. For example, twin relationships have been found in recrystallized electrolytic copper sheet, as indicated in Fig. I, from a paper by Coheur and Lejeune.2 In this pole figure the cube texture (100) [001] is indicated by the hollow squares in the lower half of the figure (the pole figure for 200 reflections) and in the upper, (111), part of the figure. The texture contains, in addition to this orientation, the first-order twins of it, shown in the figure by the filled triangles. This orientation relation has been suggested by others also, under certain annealing conditions,3,4 although pole figures have not been published to confirm it. Some orientations in recrystallized sheets are identical with their twins, because of the symmetry elements of the texture this is true, for example, with the (113) [211] texture so commonly reported for brass-hence it appears impossible in such samples to decide whether the twin relationships result from twinning or merely from the symmetry of the deformation process. The present investigation of a commercial copper strip seems to yield an example in which annealing twins account unambiguously for the principal orientations present. It proves to be a case, also, for which the recrystallization texture cannot be viewed as derived from the deformation texture by a first or second-order twinning mechanism . MATERIALS AND METHODS The samples investigated were of secondary copper (melted in Belgium) to which 0.19 per cent iron had been added to raise the recrystallization temperature. How much the orientation characteristics of this metal can be ascribed to the iron content and how much to other impurities or to melting and pouring practice has not been investigated.* The rolling was done in one direction only, on a mill with rolls of about 20-cm diameter. A strip 10 cm wide was reduced from 5 mm thickness to 0.05 mm by several cold passes at commercial speeds. The samples cut from this 99 per cent reduced strip were X-rayed throughout their entire thickness. A pole figure made soon after rolling and annealing was identical, within experimental error, with one that was made when a two-year interval occurred between rolling and annealing. X-ray patterns were made on a cameral that traversed

Jan 1, 1946

By Herbert H. Kellogg, Hugo Vasquez- Rosas

Recently the long-chain primary amines have been used extensively for the flotation of silicate minerals. The use of amines to float sulphide minerals has been investigated by several authorsl-5-l8 but most of this work has been done with the short-chain (less than six carbon atoms) primary amine compounds or the more expensive secondary, tertiary and quaternary amines. Perhaps the fact that the long-chain amines are good collectors for the common gangue minerals has led investigators to omit them from consideration as collectors for the selective flotation of metallic sulphides. The work reported in this paper was designed to investigate the use of a typical long-chain amine salt, laurylamine hydro-chloride, as a collector for the flotation of galena-sphalerite ores. The results show that laurylamine hydrochloride (LAmHCl), when used in small amounts, is a good collector for the selective flotation of sphalerite and galena from the common gangue minerals. The differential flotation of sphalerite from galena was not accomplished but the amine flotation of sphalerite after the standard xanthate flotation of galena is possible. The experimental work reported herein is not complete enough to be able to say whether amine flotation of lead-zinc ores would prove superior to xanthate flotation, or whether the method is even applicable to a more complex ore than the one used for this work. However, the apparent reagent costs for the flotation operations described in this paper seem to be less than for xanthate flotation. This fact alone should be sufficient to encourage the millman to investigate the use of these amine reagents, especially as these reagents are available on a commercial scale at a reasonable price. This paper has as its secondary purposes to illustrate how contact-angle measurements have aided in this investigation, and to bring forward some evidence concerning the mechanism of the collecting action of primary amines. Contact-angle Tests The contact-angle measurements were made by the method described by del Giudice6 and used in recent work by Taggart and his collaborators.7-9 The mineral specimens for the contact-angle tests were carefully chosen, to avoid cracks and inclusions of other minerals. All specimens were mounted in "transoptic" plastic mounts and the surfaces were cleaned by polishing with levigated alumina on a cloth-coverkd glass polishing wheel. Distilled water was used on the lap during the polishing and at all subsequent steps in the contact-angle tests. The mounted mineral specimens were handled with glass forceps and special care was exercised to prevent exposure of the clean surface to air or any other source of contamination.

Jan 1, 1947

By Herbert H. Kellogg, Hugo Vasquez- Rosas

Recently the long-chain primary amines have been used extensively for the flotation of silicate minerals. The use of amines to float sulphide minerals has been investigated by several authorsl-5-l8 but most of this work has been done with the short-chain (less than six carbon atoms) primary amine compounds or the more expensive secondary, tertiary and quaternary amines. Perhaps the fact that the long-chain amines are good collectors for the common gangue minerals has led investigators to omit them from consideration as collectors for the selective flotation of metallic sulphides. The work reported in this paper was designed to investigate the use of a typical long-chain amine salt, laurylamine hydro-chloride, as a collector for the flotation of galena-sphalerite ores. The results show that laurylamine hydrochloride (LAmHCl), when used in small amounts, is a good collector for the selective flotation of sphalerite and galena from the common gangue minerals. The differential flotation of sphalerite from galena was not accomplished but the amine flotation of sphalerite after the standard xanthate flotation of galena is possible. The experimental work reported herein is not complete enough to be able to say whether amine flotation of lead-zinc ores would prove superior to xanthate flotation, or whether the method is even applicable to a more complex ore than the one used for this work. However, the apparent reagent costs for the flotation operations described in this paper seem to be less than for xanthate flotation. This fact alone should be sufficient to encourage the millman to investigate the use of these amine reagents, especially as these reagents are available on a commercial scale at a reasonable price. This paper has as its secondary purposes to illustrate how contact-angle measurements have aided in this investigation, and to bring forward some evidence concerning the mechanism of the collecting action of primary amines. Contact-angle Tests The contact-angle measurements were made by the method described by del Giudice6 and used in recent work by Taggart and his collaborators.7-9 The mineral specimens for the contact-angle tests were carefully chosen, to avoid cracks and inclusions of other minerals. All specimens were mounted in "transoptic" plastic mounts and the surfaces were cleaned by polishing with levigated alumina on a cloth-coverkd glass polishing wheel. Distilled water was used on the lap during the polishing and at all subsequent steps in the contact-angle tests. The mounted mineral specimens were handled with glass forceps and special care was exercised to prevent exposure of the clean surface to air or any other source of contamination.

Jan 1, 1947

By Gerhard Derge

Metallurgists have used borax as a fluxing agent traditionally, but until recently elemental boron has played an insignificant role as an alloying element. Neither the metal nor its compounds have been regarded as important metallurgical materials and there is a surprising lack of knowledge concerning their metallurgical behavior. The new applications to steel-making of both boron and borates, which arose in part from wartime incentives and restrictions, have been seriously handicapped by this lack of data. For example, rasorite, a naturally occurring sodium borate, has been shown to be an effective substitute for aluminum as a ladle deoxi-dizer in rimming steels.' Likewise, the effectiveness of boron as an alloying agent has been demonstrated,2,3 giving deep hardening when used in restricted amounts. The exploitation of both of these uses has been retarded by the difficulty of attaining suitable metallurgical control. Recognizing that the most important information required was a knowledge of the equilibrium between boron and oxygen dissolved in liquid iron. Gurry4 calculated this relation from the best thermal data available. However, estimates of the entropy of melting of boron, the activity coefficient of boron in liquid iron and the activity coefficient of B2O3 in slag were involved, and experimental work on this problem was obviously desirable. The experiments to be described were planned to establish the boron-oxygen relations in liquid iron and to demonstrate at the same time the ferroborate slag compositions in equilibrium with various amounts of oxygen in liquid iron. Accordingly, slags containing varying proportions of iron and boron oxides were held in contact with molten iron, and samples of both slag and metal were analyzed. The limitations upon the accuracy of the data will be considered, but in a practical sense the oxygen levels that can be attained in iron by iron borate slags, and the amounts of boron in iron at these oxygen levels were established. Experimental Procedure No entirely suitable refractory was found for the mixtures of iron oxide and boron oxide used as slags. Crucibles of silica, magnesia, Ramix, beryllia, and zirconia were all tried unsuccessfully. The must satisfactory method discovered for handling them was the rotating-crucible technique, which creates a parabolic crucible of liquid iron.5,6 Even this was not entirely successful, for at steelmaking temperatures (1600°C.) the slags had such a low surface tension that they crept up to the refractory and slowly dissolved it. These difficulties made it impossible to maintain a constant slag composition for an unlimited period Of time. However, by using the rotating technique, short runs could be made in

Jan 1, 1947

By Gerhard Derge

Metallurgists have used borax as a fluxing agent traditionally, but until recently elemental boron has played an insignificant role as an alloying element. Neither the metal nor its compounds have been regarded as important metallurgical materials and there is a surprising lack of knowledge concerning their metallurgical behavior. The new applications to steel-making of both boron and borates, which arose in part from wartime incentives and restrictions, have been seriously handicapped by this lack of data. For example, rasorite, a naturally occurring sodium borate, has been shown to be an effective substitute for aluminum as a ladle deoxi-dizer in rimming steels.' Likewise, the effectiveness of boron as an alloying agent has been demonstrated,2,3 giving deep hardening when used in restricted amounts. The exploitation of both of these uses has been retarded by the difficulty of attaining suitable metallurgical control. Recognizing that the most important information required was a knowledge of the equilibrium between boron and oxygen dissolved in liquid iron. Gurry4 calculated this relation from the best thermal data available. However, estimates of the entropy of melting of boron, the activity coefficient of boron in liquid iron and the activity coefficient of B2O3 in slag were involved, and experimental work on this problem was obviously desirable. The experiments to be described were planned to establish the boron-oxygen relations in liquid iron and to demonstrate at the same time the ferroborate slag compositions in equilibrium with various amounts of oxygen in liquid iron. Accordingly, slags containing varying proportions of iron and boron oxides were held in contact with molten iron, and samples of both slag and metal were analyzed. The limitations upon the accuracy of the data will be considered, but in a practical sense the oxygen levels that can be attained in iron by iron borate slags, and the amounts of boron in iron at these oxygen levels were established. Experimental Procedure No entirely suitable refractory was found for the mixtures of iron oxide and boron oxide used as slags. Crucibles of silica, magnesia, Ramix, beryllia, and zirconia were all tried unsuccessfully. The must satisfactory method discovered for handling them was the rotating-crucible technique, which creates a parabolic crucible of liquid iron.5,6 Even this was not entirely successful, for at steelmaking temperatures (1600°C.) the slags had such a low surface tension that they crept up to the refractory and slowly dissolved it. These difficulties made it impossible to maintain a constant slag composition for an unlimited period Of time. However, by using the rotating technique, short runs could be made in

Jan 1, 1947

By J. Stuart Warner

The reaction COSO4(c)?CoO(c) + So3(g)was investigated from 950° to 1170OK by two different methods. The sulfate was decomposed in a previously evacuated space and Pso3 calculated from the measured total pressure on the assumption that Pso2 = 2P02. The sulfate was also decomposed under conditions of controlled oxygen pressure. The difference in the results obtained by these experimental techniques is attributed to the effects of thermal diffusion. The standard free energy change for the reaction is given by ?F° = 66,292 + 17.273T log T — 102.57 T (±300 cal/mole). It was found by DTA and X-ray diffraction studies that CoS04 undergoes a transformation at 617°± 4°C. THE metal sulfates may decompose directly to the oxide or pass through one or more intermediate basic sulfates. Provided the oxidation state of the cation does not change in the course of the reaction, the decompositions may be described in general as follows: One of the major objectives of this work was to determine the validity of Eq. [3] as much of the existing sulfate data has been calculated from decomposition pressures by Eq. [5]. The type of apparatus generally used for these measurements consists of a reaction vessel at high temperature which communicates with a manometer at room temperature. A temperature gradient is thus imposed on the gas phase causing thermal diffusion which brings about a partial separation of the different gaseous species present in an initially uniform mixture. The basic theory and experimental facts associated with this phenomenon are summarized elsewhere1 and it will suffice to state here that the heavier gaseous species diffuses down the temperature gradient. Since thermal diffusion destroys the homogeneity of the gas phase, it is not necessarily true that Pso2 = 2Po2 in any particular volume element of the gas phase even though there are twice as many molecules of SO, as of 0, in the gas phase considered as a whole. Under these conditions, the decomposing sulfate gives off SO, which dissociates to SO, and 0, and all three species are distributed throughout the system by thermal diffusion. However, the sulfate will continue to dissociate until the equilibrium value of PSo3 is established on the hot zone. Thermal diffusion may distribute SO2 and O2 throughout the gas phase in any way so long as Eq. [2b] is satisfied in the hot zone; i.e. Pso2(Po2)1/2=K3pso3. When a steady state is reached, we can characterize Pso2 in that

Jan 1, 1962

By George D. Dub

INTRODUCTION OWENS LAKE is at present a source of important nonmetallic minerals, sodium carbonate (soda ash, Na2CO3); sodium sesquicarbonate (trona, Na2CO3.NaHCO3.2H20) and borax, (Na2B407.10H2O). Owens Lake is a closed basin in the southern part of Inyo County, California, at the southern end of Owens Valley, east of the Sierra Nevada Mountains and west of the Coso and Inyo Mountains. Broadly considered, it is in the Great Basin area, but at no time was it a part of Lake Lahontan. CLOSED BASINS Closed basins are phenomena of arid or semiarid regions where outflow is considerably less than inflow and where accordingly soluble salts concentrate in residual liquid. When inflowing waters originate in areas where the rocks are predominantly marine sediments, the residual basin liquid is primarily a chloride brine; if the rocks are largely igneous, the residual brine tends to be alkaline containing carbonates, and sometimes borates as well. Since normally, both types of rocks occur in regions contiguous to closed basins, residual liquids do not often fit into the two broad divisions mentioned. No two residual brines are exactly alike, just as no two ore deposits are exactly alike. Even out of the same closed basin, it is possible to get widely different analyses of liquids since underground and surface flows, as well as local evaporation rates and other conditions might have a marked influence on residual-liquid compositions. At Searles Lake, The American Potash and Chemical Corporation is building a plant to process a lower-level brine which is considerably higher in sodium carbonate and borax, and lower in potassium chloride, than that company has processed for many years. F. W. Clarke1 has classified waters of closed basins as follows: I Chloride type; largely sodium chloride (NaCI) and of oceanic type, such as Great Salt Lake. Related is the Dead Sea, a bittern residue of magnesium, potassium and sodium chlorides. 2. Sulphate type; largely sodium sulphate (Na2S04) with considerable sodium chloride such as Sevier Lake, Utah; Laramie Lakes, Wyoming; Dale Lake, California. 3. Carbonate type; high in carbonates and fairly high in sulphates, such as Moses Lake, Eastern Washington; and the Nebraska Potash Lakes. 4. Carbonate-chloride type; lower in carbonates than type 3 and about equally rich in sulphates, such as Pyramid Lake, Nevada. 5. Sulphate-Carbonate type; quite high in sulphates and carbonates, such as Pelican Lake, Oregon. 6. Triple type; considerable quantities of carbonates, sulphates and chlorides

Jan 1, 1947

By R. C. Ku, R. G. Davies

The stress-strain behavior of Fe-C and Fe-Ni solid-solution alloys has been investigated at 25°C. It is found that the rate of solid-solution strengthening is dependent upon the strain at which the yield stress is measured, the macroyield stress being much more concentration-dependent than the microyield stress. In fact the addition of nickel does not lead to any increase in the microyield stress of iron. The primary effect of increasing the carbon or nickel content is to increase the slope of the stress-strain curve in the microyield region; this effect has been correlated, by means of transmission electron microscopy, with a decreased ability of the dislocations to cross-slip. It is concluded that the Mott-Nabarro theory is a good description of true solid-solution hardening in these and other iron-base alloys. A.LL theories of the solid-solution strengthening1-4 indicate that the flow stress of an alloy increases both with solute concentration and "misfit" between the solvent and solute atoms. The functional relationship between strength, solute concentration, C, and misfit depends upon the particular theory. Mott and Nabarro1,2 and Schoeck and Seeger3 both predict a linear increase in strength with concentration, while Fleischer4 indicates that the strength should be proportional to C1/2; there are in the literature experimental observations to support both these compositional dependencies.1'8 The experimental evidence used to support the theories is the change in macroscopic yield stress (strain, e, = 10-3) with composition. However, recent investigations have revealed that solid-solution strengthening in a Cu-Al single crystals7 and in Fe-V polycrystal-line" alloys depends upon the strain at which the flow stress is measured; a flow stress in the microplastic range (e = 10-6 to 10-5) is much less concentration-dependent than the macroyield stress. Since the theories of solid-solution strengthening are concerned in particular with the stress to move a dislocation in a dislocation-free matrix, they should only be compared with microyield-stress data; it will be shown that in a material deforming homogeneously the microyield stress (e = 10-6) is approximately the stress to move through the matrix those dislocations which have been nucleated by stress concentrations such as particles or grain boundary ledges.9-11 In contrast, the macro-yield stress is more complex in that it is affected by several phenomena: dislocation multiplication, dislocation interactions, and the ease of propagating slip across grain boundaries. For example, it is experimentally observed that when long-range order12'13 or solute effects10 restrict cross alip the grain boundary

Jan 1, 1967

By F. L. Ruhlman, Max C. Eastman

The termination of the recent war marked a major changc in the oil-field operations at. Elk Hills. Production was greatly curtailed, various experimental production projects were started, and a long-range exploratory program was inaugurated. Production was reduced from the wartime peak of 65,000 bbl per day to the current rate of about 8ooo bbl per day in order to maintain an available source of crude that can be drawn upon during a national emergency. The existing production rate is deemed essential to carry on the experimental production projects. These projects are being conducted to determine the best methods and means of maintaining the Reserve, shut in, but in a state of readiness to produce the maximum quantity of oil in the most expeditious manner. Projects now being investigated include: (I) protection of surface equipmerit; (2) repair of wells that might damage the reservoir; (3) gas injection; (4) water eneroachment, (5) gravity drainage. An exploratory program is being carried on to determine the amount of recoverable oil in the unexplored portions of the Reserve. The Shallow-zone exploration is practically completed, but owing to the complexity of the Stevens structure and the magnitude of the oil discoveries in the Stevens, exploration will probably continue in that zone for another two years. Introduction Summary of Development History of Elk Hills Although a detailed history of Elk Hills oil field is presented in various publications,1,2 a summary of its unusual development and production history will be given in order that the present problems may be more readily understood. The first development that resulted in commercial production was in the central part of the Reserve. The first well, Hay No. I, in sec 36-R,* was completed in January I9I9, and was soon followed by 37 Others in the same general area. It is commonly referred to as the Hay-Carman area and was shut in in stages from 1925 to 1934 as a result of litigation regarding the title to the land. Not being highly producti,, only about 6½ million barrels of oil with a large volume of gas was produced from the area prior to the shutdown. Shortly after the start of the development of the Hay-Carman area, drilling was started 6 miles east in sec 36-S' Tupman NO. I came in for 5000 bbl per day early in I92o, It was followed by more than 200 others in the next few years, and the field became one of major importance. Produc-

Jan 1, 1949

By C. S. Smith, E. W. Palmer

IN 1934, when Gregg and Daniloffl wrote their excellent monograph on the alloys of iron and copper, the most recent literature on the constitution of the alloys indicated a narrow single-liquid area for 20" above the liquidus with a closed liquid mis-cibility gap above this. Since that time, however, a number of investigators have confirmed the much earlier studies of Mushet2 and Stead3 who, among others in the nineteenth century, had described the true state of affairs. Liquid copper and iron are completely miscible in the absence of carbon, but small amounts of carbon cause liquid segregation. In 1934, one of the writers' mentioned evidence for the absence of liquid separation in carbon-free alloys at temperatures up to 1700°C. Two years later, Mad-docks and Claussen5 unequivocally established the absence of liquid segregation and published a revised diagram, reproduced in fig. 1. They also studied the limits of the two-liquid area in ternary alloys of iron, copper, and carbon as a function of carbon and iron content. In the same year Simpson and Bannister" and Schumacher and Souden7 described in some detail the properties of alloys containing 50 to 75 pct Cu. More recently Hodges et al.16 have developed the copper-rich alloys for use as high-strength conductors. In 1937, Iwase, Okamoto, and Ameniya8 published data on the miscibility gap in ternary alloys of iron, copper, and carbon that supported the conclusions of Maddocks and Claussen, and definitely located the two-liquid area at temperatures of 1450" and 1540°C. They also reported that additions of 1 pct Al, Ni, Pb, Sn, or Zn caused no segregation in 50 pct Cu alloys at 1540°C. The use of copper in amounts approximating 1 pct has found industrial employment to an increasing degree in both wrought and cast steels, for such steels are capable of being precipitation-hardened following normalizing, and have high yield strengths. This is summarized by Gregg and Daniloff,1 Sallitt,9 and Lorig and Adams,10 while Alexander" gives additional information on the heat treatment of copper-steel castings. Lippert12 has described Digby's two-phase steels containing copper and chromium. The work described in the present paper was done in the years 1932 to 1934, at which time much of the information was new. The excellent work subsequently done in other laboratories but more promptly published makes the present paper in part only a confirmation of what is now well known. There has not, however, been published any unified study of

Jan 1, 1951

By G. Sachs, E. J. Ripling, S. I. Liu, J. J. Lynch

INTRODUCTION IT is a generally recognized fact that by repeated straining the fracture stress of any metal is reduced to a fraction of its value for static loading. The value of this fatigue strength depends upon numerous factors, such as the states of strain and stress, the limits of straining, and the number of repeated loadings or cycles.1.2,3 The large volume of previous investigations on fatigue is concerned entirely with large numbers of cycles, say exceeding 10,000 and up to 500,000,000. However, the changes in fracture stress and fracture strain occurring after a small number of repeated loadings have attracted little attention. Apparently the only investigations of this type are those byLudwik4,5 who subjected steel, copper, and aluminum wire to repeated torsion. In each test the torque was varied between identical values in the two directions of twisting. Depending upon the magnitude of the moment, fracturing occurred after a number of cycles, up to 10,000. The results of Ludwik's tests will be discussed later. Such torsion does not readily yield actual stress and strain values. Therefore a preliminary study was made of the effects of repeated direct stresses, i.e., tension and compression stresses. Because such tests are considerably more tedious than torsion tests, only high stresses were used in the preliminary work, yielding definite changes in metal properties after a few cycles. It was found in these tests that strains could be controlled more readily than stresses in the investigated range of high stresses. This paper, consequently, deals with the effects of strains of equal magnitude but different signs. The metal was first prestrained in static tension by a certain amount then subjected to compression to yield the same amount of strain after unloading. This loading cycle was repeated up to a maximum of seven times. After various cycles, the stress-strain curves in tension were determined, up to fracturing. As material for these tests, the aluminum alloy 24ST was selected because it exhibits a comparatively small amount of necking in the tension test. This alloy permitted, therefore, rather accurate control at the high strains necessary to produce fatigue failures at less than seven cycles. The results of this investigation appear sufficiently interesting to extend the method of attack in various directions. It is intended to study (I) the effects of cycles up to a few thousands and (2) the effects of strains of different magnitude in tension and compression, respectively. The latter variable also includes as a special case the effects of compressive strains.

Jan 1, 1948

By G. W. Cullen

Niobium-tin has been prepared on insulating suhstrates hby simultaneous hydrogen reduction of gaseous niobium and tin halides. Stoichiometric material is greater than 98.8pct theoretical density, appears to he single-phase, and has a total impirity level less than 0.3 at. pct. Transition temperatures and lattice constants may he related to composition. Typical current densities in various fields and orientations are given. IT is known that Nb3Sn carries large current densities in high fields, 1 and exhibits an unusually high transition temperature2 and critical field.3 For these reasons high-field solenoids have been constructed of this material.4 Because of the emphasis on solenoid fabrication, much of the materials research has been directed toward development of wire geometries wherein the brittle Nb3Sn is supported by a more malleable metal or alloy. There are, however, basic studies and applications that can be carried out only on Nb3Sn supported by an insulator. Insulating substrates are desirable for a number of reasons: the substrate does not interact with applied or induced currents and fields; diffusion of metallic species into the de- posit is avoided, both during the preparation and during subsequent heat treatment; irradiated samples are not more active than the deposit itself. Unsupported Nb3Sn geometries may also be prepared by preferential chemical dissolution of the insulating substrate. This report describes the preparation and properties of Nb3Sn deposits on ceramic substrates. Experiments currently utilizing material prepared in the manner described in this report include the following: dependence of current-carrying properties on field strength and orientation 5,6 radiation damage,7,8 tunneling,9 thermal conductivity (substrate removed),1° microwave surface impedance," tube magnetization,6,12 resistivity as a function of temperature,13 and current density and transition temperature as a function of annealing.14 Possible practical applications include magnetic shielding, superconductor generators, and frictionless bearings. PREPARATION Methods for the deposition of elemental niobium and tin by hydrogen reduction of the gaseous metal halides have been known for some time,15,18 but only recently a procedure was developed in this laboratory17 for the codeposition of these two metals on a hotwire as the intermetallic compound, Nb3Sn. This method of simultaneous hydrogen reduction of the gaseous niobium and tin chlorides is used for the preparation of Nb3Sn On ceramic substrates. The procedure differs from that employed on a hot wire in that insulating substrates cannot conveniently be heated to temperatures greater than their surround-

Jan 1, 1964

By William J. Craig, Harold L. Walker

INDUSTRY has for many years recognized the dependence of certain mechanical and physical properties, as well as workability, upon grain size variations in brass. Although the dependence of properties upon grain size has been recognized there are not many instances where a planned program of testing has been conducted and where the only intentional variable has been grain size. In particular the literature is limited with respect to the effect of grain- size on the endurance limit, though there are many industrial applications where the brasses are subjected to cycles of repetitive stresses. LITERATURE A number of the physical and mechanical properties of a given brass sheet, in the annealed condition, will depend upon: (I) The ready-to-finish grain size before final rolling, (2) the percentage deformation by cold working, and (3) the time and temperature of annealing, The first and second variables affect the recrystallized grain size, and the third variable affects the coalesced grain size. Gibbs1 has shown the effect of two different ready-to-finish grain sizes upon the tensile strength and hardness of deep drawing brass strip after a definite amount of cold rolling. The smaller the ready-to-finish grain size, the higher the tensile strength and hardness, but with lowered ductility, Gibbs also demonstrated, for a given time and temperature of anneal, that the tensile strength, hardness, and elastic limit are higher for the smaller ready-to-finish grain size, but the elongation is lowered, Townsend and Greenall2 have reported data which show that cold working increases the tensile strength, hardness, and load carrying ability of deep drawing brass sheet under reversed stress. Greenall and Gohn3 have reported data which show that the smaller grain sizes have higher tensile strength and hardness properties, and the data also show that increased cold working increases the tensile strength and hardness properties of deep drawing brass sheet. Kommers4 has reported data for tests of brass of known ready-to-finish grain size, a specific amount of cold reduction, and annealed at different temperatures above and below the recrystallization temperature. Kommers' results indicate that annealing below the recrystallization temperature does not change the tensile strength and hardness properties, but the endurance limit may be increased from 22,000 to 28,000 psi. The increased endurance limit is explained as resulting from the reduction of internal stresses by a stress-relief anneal. Burghoff5 and associates have reported data on creep tests, over

Jan 1, 1948

By R. S. Wagner, C. E. Miller, H. Brown

A dc field was applied to liquid BI-Sx or Au-Ge alloys of eutectic composition. The liquid alloys were kept at a temperature slightly above the eutectic. The concentration changes due to electrodijfusion are large enough to cause nuclcation and growth of the primary phases at the respective electrodes. Nearly complete separation of Bi-Sn eutectic was obtained as well as substantial separation of Au-Ge eutectic. The effect of an electric field on the solute distrihn-tion was itluestignted itt tlirectiortally solidified rods of a dilute Bi-Sn (0.5 al. pc,t Bi) alloy. Field-freezing was carried out in small-diameter cupillay tubes to avoid cotuectice mixing -of the liquid. The relative sollcte corzcentratioi, Cs/Co , was rneusred by n radioac1il.e tracer netlod. Cs/Co can be made both largev than unity or srialler than the equilibiuwz distvibrrlion c.oejyicienl, k, , oiler a substattiul portion of the soliclifi&apos;erl rocls. A direct current, passed through a liquid-metal solution, can cause substantial concentration changes by electrodiffusion. The magnitude of the change depends on the difference in ionic mobilities of the atomic species in solution. Electrodiffusion has been studied in many binary and ternary liquid alloys.&apos;y2 It was found that the rate of material transport decreases with time for a constant applied field, as a concentration gradient is established in the solution. A steady-state concentration profile is achieved when electro-diffusion is compensated by chemical diffusion. This may seem to limit the use of electrodif fusion for metallurgical application. However, a way of utilizing the effect of electrodiffusion is to combine it with crystallization or controlled freezing. rakin was first to propose this as a new method of separating metal alloys of eutectic composition at temperatures slightly above the eutectic temperature. It was possible by this method to separate Bi-Sn and Bi-Cd eutectics into their component phases. Angus et al discussed the possibility that the effective distribution coefficient, keff, could be varied by proper application of an electric field during solidification. The combination of electrodiffusion and solidification, called field-freezing, was discussed in detail by Pfann and aner. It was shown that field-freezing can be used as a crystal-growth process, an efficient method for eutectic separation, and a new means of changing the effective distribution coefficient. k,ff, beyond the usual range of ko < k,ff < 1. The liquid layer adjacent to the solid-liquid interface can be either increased or depleted in solute due to

Jan 1, 1967

By George Krauss, Seth R. Thomas

One complete cycle, allstenite to martensite to aus-tenite, of Martensitic transformation was induced in a commercial 18 Cr-8 Ni stainless steel. Transmission electron microscopy showed that the reverse transfarmation, martensite to austenite, perpetuated the dense defect substructure of the martensite produced by the direct transformation, austenite to &apos;martensite, and reproduced the retained austenite matrix orientation. A general precipitation of lathlike M,,C, particles was noted to be present in, and is suggested as cause for, regions of martensite that Izad formed after a complete cycle of transformation. The habit plane of the precipitate particles was found to be within 5 a plane previously established as the habit of nitride precipitates of similar morphology in bcc iron. The direct transformation of austenite (y) to martensite (a) in metastable 300 series stainless steels has received considerable attention in the past,&apos;-8 and the martensite product given special emphasis in recent years,9"*u but little information has been published about the reverse martensitic transformation during which bcc a martensite is converted to fcc y austenite."-" The reversal mechanism and the resulting crystallographic relationship between parent and product austenite are of fundamental concern. The reversal product, fully austenitic, and hereafter referred to as reversed austenite, exhibits a defect structure far different from its virgin counterpart. Some studies have been reported in which the structure of reversed austenite in iron nickel alloys is compared to annealed austenite with respect to austenite strengtheningM and Stabilization.&apos; The martensite in these Fe-Ni alloys, however, shows a basic difference from that produced in stainless steels. Structurally, the Fe-Ni martensite is profusely twinned," while the (low-carbon) Fe-Cr-Ni martensite contains a high density of tangled dislocations and is apparently twin-free.I0 reediis" has recently shown in an Fe-16 Cr-12 Ni stainless alloy that this typical martensitic defect structure and the reverse transformation directly influence the structure of the reversal product. He found that much of the reversed austenite had returned to the orientation of the virgin austenite and that fine twins were formed in the austenite after the reverse transformation. This investigation was undertaken in order to describe as completely as possible the structural changes produced by a cycle of transformation in a typical 18-8 stainless steel. EXPERIMENTAL PROCEDURE The 301 stainless steel under investigation (17.44 Cr, 7.75 Ni, 0.80 Mn, 0.60 Si, 0.40 Mo, 0.40 Cu, 0.08 C, 0.03 N, bal Fe)was received as 0.060-in.-thick

Jan 1, 1968

By M. Cohen, W. J. Harris

The recent application of lineal analysislt2 to the austenite-martensite reaction has made possible a quantitative study of the kinetics of this transformation during rapid cooling. Martensite range curves can thus be constructed to portray the onset of the reaction at Ma and its subsequent progress as a function of temperature down to and below the ambient. It now seems in order to investigate other aspects of the martensite transformation, using this quantitative method of approach. One of the least understood characteristics of the austenite-martensite reaction is that of stabilization which has been defined by Troiano and Greninger3 as &apos;la lowering of Ma, resulting from aging, without change in chemical composition of the parent solid solution." In other words, if the hardening quench is arrested at a predetermined subcritical temperature (TA) for a sufficient period of time, more austenite may be retained at a given lower Or reference temperature (Tr) than if the steel had been cooled directly and rapidly to Tr in the first place. For the purposes of the work at hand, the extent of stabilization produced by the isothermal treatment at Th is measured explicitly in terms of the excess austenite (6) that exists in the steel at T,, over and above the amount that is normally present after direct quenching to T,. T, is conveniently taken to be room temperature, but this choice is not essential and is sometimes undesirable. The holding temperature (TA) may be above or below M,, and still cause stabilization depending upon the themistry of the austenite. stabilization has been found to occur in the presence of bainite4 and of martensite6,6,7,8 as well as in the absence of either,g The phe-nomenon of stabilization is not concerned with (and may even be obscured by) ferrite formation or any other type of phase change occurring at T~ that alters the chemistry of the remaining austenite. Such a structural change would obviously influence the martensite transformation during subscquent cooling. Stabilization, however, is more subtle; it appears to manifest itself without detectable variation of the austenite composition, whether in the presence or absence of transformation products. There are relatively few direct references to stabilization in the literature. The stabilizing effect of room temperature aging and tempering on the subzero transformation of retained austenite has been clearly shown in plain carbon,6,8 low alloy6s7.8 and high alloy tool steels.10&apos;5 ssa- with the as-hardened steel, the degree of stabilization increases with tempering time and temperature through

Jan 1, 1949

By C. R. McEwen

The displacement equations of Buckley and Lever-ett&apos; have been successfully applied to the prediction of oil recovery in frontal drives for a number of years. Commonly, the capillary pressure term is omitted from Leverett&apos;s fractional flow formula. The resulting satura-tion-vs-distance curves become multi-valued, however. Buckley and Leverett, recognizing that the neglect of capillarity was most likely the cause, proposed that this part of the solution he ignored. An ingenious method of propagating a discontinuity in place of the multi-valued portlon of the curve was devised by Cardwell using "non-capillary displacement theory". However, it would seem that a completc description of the displacement pracess would require the inclusion of capillary forces. Three publications on displacement theory have appeared in which capillary pressure was included. Ter-williger. et al&apos;, calculated saturation profiles which matched those which they observed when gas displaced water vertically downward. Based on their study, Jones-Parra and Calhoun5 roposed a method of computing saturation distributions sufficiently removed in time from the initial conditions so that all saturations in the flood front region were assumed to move with the same velocity. This latter assumption corresponds to the tangent construction on the flowing fraction-vs-satura-tion curve proposed by Welge." A numerical solution to the problem of water displacing oil from a water-wet porous medium was recently presented by Blair, ef at&apos;. The initial conditions included a uniform saturation slightly above interstitial water saturation. that is, the permeability to water ahead of the front was not zero. This appeared to result in a region of slowly rising water saturation ahead of the front, at least for the particular set of relative permeability and capillary pressure data used to illustrate the computation. The authors also postulated an "end-effect" at the outflow face of the system, whereby no water could pass out of the system until the water saturation had built up to a high value. The saturation profiles computed under these assumptions show water accumulating at the downstream end of the system while the flood front proper is still traveling toward the outlet. The purpose of this paper is to present the results of a numerical solution to the one-dimensional water-flooding equation in which no outlet end-effect is considered and where there is no flow of water ahead of the flood front. It should be noted that the contemporary paper of Fayers and Sheldon8 deals with the problem under discussion. For a thorough treatment including both capillarity and gravity the reader is referred to their paper.

By Norman Brown, J. V. Rinnovatore

Substructures in explosively deformed and annealed ß brass have been examined by electron microscopy. In the explosively deformed condition, the structure contains a large density of straight screw type dislocations. Subsequent annealing up to 300oC produces low angle boundaries, which are characterized by superlattice dislocations, and expanded and contracted nodes. Evidence is given where two a(111) superlattice dislocations combine to form two a(001) superlattice dislocations. It is also shown that annealing at 400°C the networks disappear and that quenching from 400" C produces square and circular prismatic dislocation loops that lie on (100) and (111) planes, respectively. THE purpose of this work was to determine the effects of explosive deformation and subsequent annealing in a superlattice using electron microscopy. One of the first observations of explosively deformed structures was made by Hornbogen1 on a iron. Hornbogen found that screw dislocations were most prominent in the explosively deformed structure. He explained this result by suggesting that the edge components of dislocation loops move with the velocity of the shock front leaving a trail of extended screw components. Kressel and Brown2 observed explosively deformed Fe3A1, which is basically a body-centered type of superlattice in terms of dislocation geometry, and found that, as in the case of iron, screw dislocations were most prominent. It was also observed2 that, in cold-rolled and explosively deformed nickel, screw dislocations did not predominate, but rather a uniform network of dislocations was present in which the orientation of the dislocations was random. (Cell structures also have been observed by Nolder and Thomas3 for copper and by Johari and Thomas* for nickel). Kressel and Brown2 discussed the difference between dislocation morphology for bee and fee metals in terms of dislocation mobilities. They suggested that edge dislocations have a greater mobility than screw dislocations in bee metals but not in fee metals. Thus, the idea offered originally by Hornbogen1 is not valid since it should apply equally to fee and bee systems but does not. The results of recent work by Mikkola and cohens on explosively deformed Cu2Au are consistent with other observations for fee metals. They found that dislocations were randomly arranged but there was no significant cell formation. At high shock pressures, deformation twins are produced in fee metals.&apos; High pressures in bee metal should induce the bee — fee transformation while the metal is under pressure. EXPERIMENTAL PROCEDURE The Cu-Zn alloy used in this work contained 51.4 wt pct Cu. Specimens of 0.5 in. diam and 0.012 in.

Jan 1, 1968

By Robert A. Colten, Frederick C. Hull, Robert F. Mehl

It is known that pearlite forms from austenite by a process of nucleation and growth, and that the rate of formation of pearlite may be described by a rate of nucleation and a rate of growth.l,2 The manner in which these two quantities operate to produce the observed isothermal reaction curve has been analyzed in a paper published in I939.3 Two types of process were described: (I) that in which nucleation occurs at the grain boundaries of the parent phase, with the nodules growing toward the centers of the grains, initially as hemispheres and then after impingement as roughly radial-columnar structures; and (2) that in which nucleation occurs generally, with the nodules growing to full spheres until impingement with other growing nodules restricts growth. Both cases are met in the formation of pearlite from austenite (Fig. I);2,4 the former, occurring near the knee of the S-curve, has been named "grain-boundary transformation," and the latter, occurring at temperatures near Ael, has been named "group-nodule transformation." In developing our knowledge of the factors that determine the rate of formation of pearlite from austenite, it is important1,2 to obtain data on the rate of nucleation and the rate of growth of pearlite. Such data, when obtained near the knee of the S-curve, will furnish information of use in understanding the factors that affect hardenabil-ity; when obtained at higher temperatures, such data will be useful in understanding the behavior of steels that during heat-treatment react to pearlite.2 It is the purpose of this paper to present data on the rate of nucleation and the rate of growth of pearlite in dependence upon composition, grain size, temperature, and the degree of homogeneity of the parent austenite. The studies are restricted chiefly to plain carbon commercial steels." Previous Data on Rate of nucleation and rate of Growth Data on the rate of nucleation and the rate of growth of pearlite have been published by Scheil and Lange-Weise,5 by Mirkin and Blanter,6,7 by Meh1,l and by Dorn, De Garmo and Flanigan.2, It is difficult to interpret the data, for in most cases too little information is given on austenitizing temperatures and times, the state of homogeneity of the austenite (presence or absence of carbide, etc.), austenite grain size, and mode of formation of pearlite at the temperatures given. Except for the approximations of Mehl and the work of Dorn, austenite grain size was disregarded, though it is well known

Jan 1, 1942

By Robert A. Colten, Frederick C. Hull, Robert F. Mehl

It is known that pearlite forms from austenite by a process of nucleation and growth, and that the rate of formation of pearlite may be described by a rate of nucleation and a rate of growth.l,2 The manner in which these two quantities operate to produce the observed isothermal reaction curve has been analyzed in a paper published in I939.3 Two types of process were described: (I) that in which nucleation occurs at the grain boundaries of the parent phase, with the nodules growing toward the centers of the grains, initially as hemispheres and then after impingement as roughly radial-columnar structures; and (2) that in which nucleation occurs generally, with the nodules growing to full spheres until impingement with other growing nodules restricts growth. Both cases are met in the formation of pearlite from austenite (Fig. I);2,4 the former, occurring near the knee of the S-curve, has been named "grain-boundary transformation," and the latter, occurring at temperatures near Ael, has been named "group-nodule transformation." In developing our knowledge of the factors that determine the rate of formation of pearlite from austenite, it is important1,2 to obtain data on the rate of nucleation and the rate of growth of pearlite. Such data, when obtained near the knee of the S-curve, will furnish information of use in understanding the factors that affect hardenabil-ity; when obtained at higher temperatures, such data will be useful in understanding the behavior of steels that during heat-treatment react to pearlite.2 It is the purpose of this paper to present data on the rate of nucleation and the rate of growth of pearlite in dependence upon composition, grain size, temperature, and the degree of homogeneity of the parent austenite. The studies are restricted chiefly to plain carbon commercial steels." Previous Data on Rate of nucleation and rate of Growth Data on the rate of nucleation and the rate of growth of pearlite have been published by Scheil and Lange-Weise,5 by Mirkin and Blanter,6,7 by Meh1,l and by Dorn, De Garmo and Flanigan.2, It is difficult to interpret the data, for in most cases too little information is given on austenitizing temperatures and times, the state of homogeneity of the austenite (presence or absence of carbide, etc.), austenite grain size, and mode of formation of pearlite at the temperatures given. Except for the approximations of Mehl and the work of Dorn, austenite grain size was disregarded, though it is well known

Jan 1, 1942