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By R. E. Miner, J. K. Jackson, T. L. Wilson

THE nature of the decomposition reactions producing hardening in aluminum-rich A1-Ag alloys is now fairly well understood. The silver is not uniformly dispersed even at temperatures above the solvus line: rather, it is clustered into zones and associated with dislocations.' During quenching, nearly all of the silver segregates into zones' and some is attracted to dislocations, producing stacking faults. Growth of these faults produces the semicoherent y precipitate.1 During aging, the larger zones and the y precipitates grow at the expense of the smaller zones. The large zones persist up to about 350°C; where they redissolve in favor of the y' and y precipitates.' The equilibrium hcp y precipitate occurs both by a cellular reaction at the grain boundaries1 and by growth of the Y' plates to a critical size where incoherency results. Damask and Nowick 4 observed an internal friction peak in an A1-6 at. pct Ag alloy at about 140°C (0.25 cps). The peak was found to exhibit a systematic instability. After aging at successively higher temperatures between 155' and 23Z°C, the peak first migrated to higher temperatures while increasing in height, then returned to lower temperatures and decreased in height. After aging at temperatures above about 200°C, the peak position remained constant while the height decreased very slowly. In quenched specimens, elastic after-effect measurements inhcated a rapid initial transient in peak position from low temperatures up to 155°C. The authors concluded that a stress induced growth and resolution of the clusters and the 7' was the most reasonable mechanism to account for the behavior. It would seem, however, very unlikely that both the clusters and the y' precipitate would provide damping contributions whose relaxation time and activation energies were identical, which is required for them to produce the same internal friction peak. The present investigation was motivated by this apparent anomaly and the development of a very low thermal inertia torsion pendulum5 capable of monitoring transient behavior. Low frequency internal friction measurements were made on four binary A1-Ag alloys nominally containing 5, 10: 15, and 20 at. pct Ag. The results of measurements made on a 10 at. pct Ag alloy in the quenched condition are shown in Fig. 1. There are two peaks apparent in the spectrum, one centered at about 160°C, the second at about 210°C. The two peak spectrum was observed in each alloy, but it was best resolved in the 10 pct Ag specimens. Because of the instability in the internal friction, 4 it seemed possible that the second peak was not a peak at all, but simply a manifestation of a single, sharply transient, peak. This effect has been observed in Au-Ni alloys.6 The existence of the higher tempera-

Jan 1, 1970

By Henry Fay

LAWRENCE ADDICKS, New York, N. Y., (communication to the Secretary *).-There are two points regarding gun erosion on which I want to say a few words: The first is about the analogy to hardening of wire by drawing and the second the possible role played by thermal conductivity of the metal. The ductile metals do not necessarily become brittle when cold-worked as it is possible to draw copper from 3. in. in diameter soft rod down to the finest hair wire without annealing. This results, as stated in the paper, informing a hardened core with a very hard skin. The electrical conductivity is depressed some 3 per cent. and the tensile strength nearly tripled. A soft copper wire 0.08 in. in diameter and 6 in. long may be twisted 150 or more turns before the wire will snap under torsion. A hard-drawn wire will break after perhaps a dozen twists, the skin breaking down at one spot. Just wiping the wire with a cloth clamp with dilute nitric acid has a remarkable effect in increasing the number of twists without appreciably lowering the tensile strength, showing the skin to be very thin. On the other hand, pickling the rod, from which the wire is to be drawn, in dilute nitric acid also greatly increases the number of twists which can be applied to the resulting wire. This indicates that the copper oxide scale produced when the wire bar is rolled hot is more or less rolled into the rod and may have much to do with the skin effect. We also know that if the conditions of drawing are not correct, the heat of deformation in the die may produce quite an annealing effect. The application of this analogy to what occurs in a gun to produce the effects noted offers some difficulty. The second point is that as the temperature of the surface of the gun bore has undoubtedly a great deal to do with the amount of erosion, one natural remedy would be to conduct the heat away fast enough to keep this temperature within desired limits. This brings up the question of the thermal conductivity of the metal of which the gun is made. We know that the conductivity of pure metals is greatly altered by alloying and that the alloy is usually, though not always, lower in conductivity than the metal before alloying. This is interesting when it is considered that the high-nickel and manganese-steel alloys show greater erosion as stated. Would it not be instructive to study the question from the point of view of heat conducted away from the eroded surface?

Jan 3, 1917

By Herbert Hoover, Harlod Washburn

This paper is in the nature of a rough preliminary report on the progress that has been made in the application of the mass spectrometer to various problems arising in the petroleum industry. A few years ago the authors considered a number of the problems that were arising in the qualitative and quantitative measurement of small amounts of hydrocarbons. The methods available of making analyses by chemical techniques appeared to leave much room for improvement. Without going into the reasons at this point, attention was turned to the possibility of employing physical instead of chemical methods of accomplishing the desired results. A preliminary investigation disclosed that the mass spectrometer presented a possibility of solving many problems which could not easily be accomplished by other methods. Work was begun in developing the necessary apparatus and technique. A great deal of encouragement and many valuable suggestions were received from Dr. Robert A. Millikan, Dr. W. R. Smythe, and Dr. W. N. Lacey, of the California Institute of Technology, and from Dr. E. 0. Lawrence, who recently received the Nobel Prize, of the University of California. The authors particularly wish to acknowledge the very great willingness of these outstanding scientists to be helpful in solving many of the problems that were involved. So far as the authors are aware, this was the first application of the mass spectrometer to commercial work. The results were considerably better than had at first been anticipated. Briefly, it is possible to run a qualitative and quantitative analysis of an unknown mixture of hydrocarbon gases, with an accuracy of better than plus or minus 5 per cent of each of the various constituents. An exceedingly high degree of sensitivity has been obtained, and a relatively short time is required to complete an analysis. Furthermore, it is unnecessary to separate a mixture of gases into its various components in order to complete the analysis. The Mass Spectrometer The mass spectrometer should not be confused in any way with the optical 01 grating type of spectrograph now in general use. The operation of the mass spectrometer is entirely different in principle and bears practically no resemblance to the optical or grating instruments. The original conception and development of the mass spectrometer dates from and is generally credited to Aston, of Cambridge, England. An early accomplishment of his research, about 20 years ago, was the discovery that the inert gas neon was actually a mixture of two kinds of atoms, one of the atomic weight 20 and the other of atomic weight 22. These two components occurred mixed in such proportion as to yield the usual atomic weight of 20.2. The study was continued and most of the elements were shown to be mixtures of components whose atomic weights can, to in

Jan 1, 1941

By L. B. Ticknor, M. B. Bever

An isothermal calorimeter suitable for measurements of heats of solution in liquid tin as solvent is described. Measurements of the heats of solution of gold, silver, copper, and a gold-silver alloy are reported. The heat of formation of this gold-silver alloy is also reported. HEATS of solution in liquids can be determined directly, but few such data have been published for metals as solvents. Knowledge of heats of solution is desirable because it contributes to the general understanding of energy relations in metallic solutions. Thermochemical measurements of this type also furnish answers to specific problems: For example, from the heats of solution of an alloy and of a mixture of its constituent elements in a given solvent, the heat of formation of the alloy may be found. Similarly, differences in the energy content of samples of the same metal in two different states, such as the annealed and cold worked states, may be determined. In the work reported here, gold, silver, and an alloy of gold and silver were dissolved in liquid tin at 240°C and gold, silver, and copper were dissolved in tin at 300 °C. The experiments yielded the heats of solution of these metals in tin. The heat of formation of the gold-silver alloy was also determined. The same calorimetric method is being used to measure the energy stored in metals during cold working and preliminary results have been published.' Equipment and Experimental Procedure The isothermal calorimeter used in this work, Fig. 1, consisted of a Dewar flask completely immersed in a constant-temperature salt bath. A long neck provided space for thermocouple leads and a stirrer shaft and permitted the injection of solute samples. The metal bath in the calorimeter flask was stirred at about 100 rpm by a small glass impeller driven by a constant-speed motor. The shaft of the stirrer passed through a Wilson vacuum seal.2 All measurements were made under vacuum in order to eliminate temperature disturbances resulting from gas convection and to prevent the oxidation of tin. The calorimeter flask was joined by an all-glass connecting line to a gas-control system which made possible the use of a protective atmosphere of deoxidized and dried hydrogen. At the operating temperature of the calorimeter tin oxide was not reduced by hydrogen, presumably because the reaction rate was too slow. Part of the closed system was a removable side tube through which the solute sample could be introduced and in which it was held at a temperature of 0°C prior to injection into the metal bath. The salt bath containing a mixture of sodium, lithium, and potassium nitrates was similar to that described by Beattie3 and was equipped with a stir-

Jan 1, 1953

By Harlod Washburn, Herbert Hoover

This paper is in the nature of a rough preliminary report on the progress that has been made in the application of the mass spectrometer to various problems arising in the petroleum industry. A few years ago the authors considered a number of the problems that were arising in the qualitative and quantitative measurement of small amounts of hydrocarbons. The methods available of making analyses by chemical techniques appeared to leave much room for improvement. Without going into the reasons at this point, attention was turned to the possibility of employing physical instead of chemical methods of accomplishing the desired results. A preliminary investigation disclosed that the mass spectrometer presented a possibility of solving many problems which could not easily be accomplished by other methods. Work was begun in developing the necessary apparatus and technique. A great deal of encouragement and many valuable suggestions were received from Dr. Robert A. Millikan, Dr. W. R. Smythe, and Dr. W. N. Lacey, of the California Institute of Technology, and from Dr. E. 0. Lawrence, who recently received the Nobel Prize, of the University of California. The authors particularly wish to acknowledge the very great willingness of these outstanding scientists to be helpful in solving many of the problems that were involved. So far as the authors are aware, this was the first application of the mass spectrometer to commercial work. The results were considerably better than had at first been anticipated. Briefly, it is possible to run a qualitative and quantitative analysis of an unknown mixture of hydrocarbon gases, with an accuracy of better than plus or minus 5 per cent of each of the various constituents. An exceedingly high degree of sensitivity has been obtained, and a relatively short time is required to complete an analysis. Furthermore, it is unnecessary to separate a mixture of gases into its various components in order to complete the analysis. The Mass Spectrometer The mass spectrometer should not be confused in any way with the optical 01 grating type of spectrograph now in general use. The operation of the mass spectrometer is entirely different in principle and bears practically no resemblance to the optical or grating instruments. The original conception and development of the mass spectrometer dates from and is generally credited to Aston, of Cambridge, England. An early accomplishment of his research, about 20 years ago, was the discovery that the inert gas neon was actually a mixture of two kinds of atoms, one of the atomic weight 20 and the other of atomic weight 22. These two components occurred mixed in such proportion as to yield the usual atomic weight of 20.2. The study was continued and most of the elements were shown to be mixtures of components whose atomic weights can, to in

Jan 1, 1941

By D. Turnbull

RECENTLY it has been shown that aggregates of small liquid droplets of tin,' mercury' or gallium' kept from intercommunicating by suitable films do not solidify at an appreciable rate unless the supercooling is very much greater than that usually necessary to cause a large continuous mass of the metal to solidify. For example oxide-coated tin droplets1 (1 to 10 micron diam) must be supercooled 100" to 110°C before their rate of solidification becomes rapid, although large continuous masses of liquid tin usually begin to solidify when supercooled 30" or less." These experiments have been interpreted' on the hypothesis that nucleation of crystals in large continuous metal samples is almost always catalyzed by accidental inclusions. Therefore, if the metal is dispersed into a number of isolated droplets large in comparison with the number of inclusions, most of the droplets should not crystallize until a temperature sufficiently below the thermodynamic melt- ing point, T0, has been reached to permit an ap-preciable rate of homogeneous (noncatalyzed) nu-cleation. In general this temperature is very much less than the temperature at which the rate of heterogeneous (catalyzed) nucleation is appreciable. If this interpretation is correct then investigation of the kinetics of crystallization of small droplet aggregates should be one of the most fruitful methods of obtaining information about the homogeneous formation of crystal nuclei in liquids. In this paper the results obtained on gallium and mercury are reported more fully. In addition, results on the supercooling of aggregates of liquid bismuth and lead droplets are included. Experimental Procedure Some care must be exercised in the choice of a barrier to prevent the liquid droplets from coalescing lest the barrier itself catalyze the formation of crystal nuclei. From this standpoint, the most desirable barrier is vacuum or inert gas, but, because of the difficulty of experimental arrangement, solid compounds and adsorbed films have been selected. There are two guiding principles in the selection of compounds as barriers in addition to the requirement that they prevent coalescence of liquid droplets. First, the compound should be almost insoluble in the liquid metal and second, its lattice structure should be quite unlike that of the forming metal crystal. Even so, there is no a priori assurance that the solid compound film will not catalyze to some extent the formation of metal crystal nuclei. An adsorbed protective monolayer is less likely to be catalytic than a crystal compound film, but it is not often possible to find a monolayer that is stable under the experimental conditions. Also, it is desirable, though not generally essential, that the aggregate of droplets be prepared by breaking up the massive metal rather than from a powdered compound of the metal.

Jan 1, 1951

By R. I. Jaffee, H. R. Ogden, D. J. Maykuth

Phase diagrams for the Ti-W and Ti-Ta systems were determined. The Ti-W system is characterized by a wide, two-phase region of ß plus tungsten which is derived from a peritectic reaction between the liquid and tungsten solid solutions. The ß field terminates in a eutectoid reaction between a titanium and tungsten terminal solid solution. Tantalum and ß titanium form a complete series of solid solutions. Other features of this system are the extensive a-ß field at low temperatures and an appreciable solubility of tantalum in a titanium. BOTH tungsten and tantalum were first thought to form ß-isomorphous systems with titanium as a result of early work' using powder-metallurgical techniques. Later work2 on arc-melted Ti-Ta alloys, made using a commercial titanium base, showed that, in the range of 0 to 10 pct, tantalum was soluble in ß titanium and that the a solubility extended to between 2 and 5 pct Ta at 790 °C. The present investigation covered the entire alloy range in both systems and was chiefly concerned with high-purity alloys at the titanium-rich end. The constitution of titanium-rich alloys made with a commercial titanium base was reported by Holla-day, Kura, and Jackson.3, 4 As will be shown in detail later, the early prediction of a isomorphism was true for the case of the Ti-Ta system, but not for the Ti-W system. The results of this investigation will be presented first. The experimental methods used are described in the Appendix. Ti-W System The entire Ti-W phase diagram is shown in Fig. 1. Details of the titanium-rich side are shown in Fig. 2. The chief features of the system are a ß eutectoid and a high-temperature peritectic between liquid and tungsten solid solution. Melting Range: Examination of cast structures of low and medium-tungsten-content ingots showed cored ß phase as the primary constituent. Fig. 3a illustrates a typical cast structure for alloys in the range of 20 to 30 pct W. From 30 to 72 pct W, coring was very severe. Alloys containing 72 through 88 pct W, however, showed definite evidence of a peritectic reaction between the liquid and a terminal solid solution of titanium in tungsten. Fig. 3b shows the cast structure for an 80 pct W alloy. A 95 pct W alloy, shown in Fig. 4, consisted primarily of primary tungsten solid solution plus a small quantity of ß probably rejected during cooling. Incipient-melting experiments located the peritectic temperature between 1850" and 1900°C and indicated that the reacting phases are liquid containing about 25 pct W and tungsten terminal solid solution containing about 8 pct Ti. Figs. 5 and 6

Jan 1, 1954

By E. Miller, J. M. Eldridge, K. L. Komarek

Aclivilies of magnesium in liquid Alg-Si alloys have been delermined between 5 and 60 at. pcl Si, close to the melling point of Mg2Si, by an improved isopieslic melhod. Silicon specinrens, held in alumina crucibles and graplrile conlainevs of special design, were healed in a letrlpevalure gvadient and equilibrated with mag-nesilcrrl rapor in a closed lilanium system. The ther-madynamic Junctions were calculated and compared with the thermodyuamic properties of the other three mg- Gvoup IVB systems. Lattice paramelers of three Mg2X compounds were measured. The bonding in the Mg2X compounds is largely covalent with small and uarying amounts of metallic and ionic conlvibutions. The Mg-Si phase diagram1 has one congruent melting compound, Mg2Si, of essentially stoichiometric composition, two eutectics, and very limited terminal solid solubilities. Little information is available on the thermodynamic properties of this system. The free energy of formation of Mg2Si has been determined by the Knudsen cell technique2 in the range 572" to 680oC, by the transportation method3 between 858" and 950oC, and by the electromotive-force method4 in the range 400o to 600°C. Kubaschewski and villa5 and caulfield6 have measured the heat of formation of Mg2Si. An electromotive-force study of magnesium-rich liquid alloys was recently published by Sryvalin el al.7 The present investigation was undertaken to complete a general survey of the thermodynamic properties of the homologous series of Mg-Group IVB systems, i.e., Mg-Pb,a9,Mg-Sn,10,11 mg-Ge,12and Mg-Si. An isopiestic technique, previously developed for similar measurements on liquid Mg-sn11 and Mg-Ge alloys,12 was modified for the Mg-Si system. Specimens of the nonvolatile component, silicon, were contained in dense alumina crucibles placed inside covered graphite crucibles which were heated in a temperature gradient in an evacuated and sealed titanium reaction tube and equilibrated with magnesium vapor of known vapor pressure. The alumina crucibles prevented contact between the highly corrosive liquid Mg-Si alloys and graphite. The graphite cruci- bles effectively preserved the high-temperature equilibrium composition of the liquid alloys containing highly volatile magnesium on termination of the experiments during the quench to room temperature. EXPERIMENTAL PROCEDURE Silicon of semiconductor-grade purity (E. I. du Pont de Nemours and Co., Brevard, N.C.) and 99.99+ pct Mg (Dominion Magnesium Ltd., Toronto, Canada) were used. Graphite crucibles with press-fitted lids were machined from high-density (1.92 g per cu cm) rods (Basic Carbon Corp., Sanborn, N.Y.) which had a maximum ash content of less than 0.04 pct. The alumina crucibles had a purity of 99.7+ pct (Triangle RR grade, Morganite, Inc., Long Island City, N.Y.). In preliminary runs the liquid alloys were contained in graphite crucibles following the exact procedure developed for the Mg-Ge system.'2 These runs failed due to appreciable reaction between the molten Mg-Si alloys and graphite, and the results have been discarded. The procedure was then modified and the Mg-Si alloys were subsequently held in alumina crucibles. For most of the runs alumina crucibles of known weight and approximately 6.3 mm ID, 12.5 mm height, 1.0 mm wall thickness were loaded with weighed amounts of silicon and encapsuled in tightly covered weighed graphite crucibles 5/16 in. ID, 2 in. helght, 3/32 in. wall thickness). The graphite crucibles were machined from rods which were 85 pct of the theoretical density. These crucibles were therefore sufficiently porous so as to permit magnesium vapor to effuse through the silicon under the experimental conditions of approximately 970O to 1220°C and 1 day equilibration time. However, negligible magnesium was lost from the crucible during the quench due to the slow effusion rate through the pores of the graphite. The inner alumina crucible prevented the liquid alloys from contacting the graphite, and the very tightly fitting graphite crucible lids served to retain any magnesium vaporizing from the alloys inside the crucibles during the quenching step.12 The loaded silicon-alumina-graphite cells were positioned, one above another, on a 16-in.-long titanium thermocouple well and tied securely to the titanium tube with thin molybdenum wires held in grooves around the circumference of the graphite crucibles. A thin (0.005-in.) molybdenum strip prevented contact between the graphite crucibles and the titanium. This assembly was lowered into a titanium reaction tube (la in. ID, 16 in. long, $ in. wall thickness) closed on one end which contained a 11/2-in.-long cylinder of magnesium at the bottom. The inner titanium thermocouple well was positioned eccentrically in the large tube because of the eccentric mounting of the cells on the well. Appropriate modifications of the titanium cap"'12 were made to join the inner and outer titanium

Jan 1, 1968

By J. M. Oblak, W. A. Owczarski

A cellular appearing recrystallization product formed by annealing a cold-worked nickel-base super-alloy at 1800°F has been studied by electron nzicroscopy. Prior to deformation, an equilibrium micro-structure of fcc matrix y and cuboidal ,,', Ni (Al, Ti), precipitates of CuzAu structure had been established by an age at 1825°F. The strain-free recrystallization cells consist of very large rodular y' particles in a y matrix. They precipitate is oriented and coherent both before and after recrystallization. The results showed that y' coarsening accompanies recrystallization at 1800°F. However, it does so as a secondary effect and does not necessarily take place at lower temperatures. The structural similarity of this reaction to cellular precipitation in other systems indicates that lattice strain may also play a significant role during some cellular precipitation reactions. THERE have been numerous microstructural investigations of recrystallization in single-phase materials but two-phase systems have received much less attention. The second phase can either remain inert or be altered along with the matrix during recrystallization. If the second phase is an oxidelm3 or a relatively inert pre~ipitate,~, recrystallization is retarded when the interparticle spacing is less than 1 p. Prior to the onset of recrystallization, these materials show a well-polygonized substructure with the subgrain size limited by the interparticle spacing. Since recrystallization by the motion of preexisting grain boundaries6 is not observed, retardation has been related to particle pinning of the subboundaries. This pinning prevents coalescence' or growth8 of subgrains to a critical size (formation of a high-angle boundary) necessary to initiate recrystallization. In a material such as a nickel-base superalloy both y matrix and y' precipitate are altered by the recrystallization reaction. Haessner et al.' studied the recrystallization of a cold-rolled Ni-Cr-A1 alloy by electron microscopy. The material was initially cold-rolled in the supersaturated condition. upon annealing at 750°C, immediate precipitation of 7'occurred. Presence of this 7' greatly retarded the onset of recrystallization which eventually took place by the development of randomly oriented, strain-free grains. The original •/ was dissolved at the recrystallization interface and reprecipitated as oriented, coherent par-tiles in the new grain. Recrystallization caused a refinement of .)' particle size. Recently ~hillips'' investigated recrystallization of Ni-12.7 at. pct Al. Reduction by cold rolling presumably elongated the p' precipitate into lamellae that remained coherent with the matrix. After recrystallization at 600" to 750°C, there was no unusual change in y' particle size al- though there was a tendency toward clustering along the prior rolling direction at 750°C. Above 750°C, the recrystallized grains were generally free of precipitate. Studies in the somewhat analogous Cu-3.23 wt pct CO" and Cu-2 wt pct'2 systems demonstrated that the coherent cobalt-rich fcc precipitate in these alloys obstructed softening, initiation, and completion of recrystallization. The precipitates were deformed into lam~llae during rolling and those of diameter less than 250A remained coherent. Recrystallization took place by the growth of new grains into the recovered or poly-gonized material. In the first study," both matrix and precipitate reoriented in the same manner upon passage of the recrystallization interface. There was no change in particle size or morphology. Tanner and ~ervi,~ on the other hand, observed that motion of the recrystallization fronts was strongly hindered by the pinning action of coherent precipitates in the deformed material. Particles in contact with a pinned boundary coarsened and coalesced leaving a denuded zone in the unrecrystallized region. When the number of pinning points was sufficiently reduced by coalescence, the boundary swept past these particles and through the denuded zone. The authors1' considered this as a variation of discontinuous precipitation with both chemical driving force and deformation strain energy contributing to recrystallization. Preliminary observations by the present authors had revealed that recrystallization in Udimet 700, a nickel-base superalloy, occurred in an entirely different manner. Optical metallography showed that the recrystallized product formed as cellular colonies containing coarse y' particles elongated in the direction of cell growth. In this investigation the structural features of this reaction were investigated by transmission electron microscopy. EXPERIMENTAL PROCEDURE As-received I$-in. rounds of Udimet 700* were (wtpct) 18.4 15.2 4.95 4.42 3.43 0.06 0.031 0.14 Bal. solution-annealed for 4 hr at 2150" and then fast air-cooled. An initial y-~' structure was established by a 4-hr age at 1825°F followed by a fast air,cool. Essentially the equilibrium volume fraction of ?' at 1825°F is precipitated within 4 hr. Microstructural examination showed no measurable increase in the amount of precipitate after longer aging times. Deformation consisted of swaging to 52 pct RA with 6 pct reduction per pass at room temperature. To reduce the precipitation potential to a negligible amount, recrystallization anneals were conducted at 1800"~ (982"~). Microstructures were investigated by optical and transmission electron microscopy. To prepare foils for electron microscopy, the material was first sliced into 30-mil slabs parallel to the swaging direction. Discs were dimpled and electrolytically cut from

Jan 1, 1969

By M. Murakami, Y. Murakami, O. Kawano

The formation and growth of Guinier-Preston zones in Al-Zn alloys containing 4.4, 6.8, 9.7, and 12.4 at. pct zn have been studied by the X-ray small-angle scattering method. Particular attention was paid to the effects of small amounts of third elements silver, silicon, and magnesium on the formation and growth of G.P. zones. It was noticed that an appreciable number of G.P. zones were formed during the course of rapid cooling and that the size, volume fraction, and number of these G.P. zones were influenced by the existence of the third elements. During subsequent aging it was also found that the addition of both silver and silicon lowered the temperature for the growth of G.P. zones, whereas the addition of magnesium raised it. These results were explained in terms of the mutual interactions among zinc atoms, vacancies, and the third elements. A number of studies on the formation and growth of Guinier-Preston zones in Al-Zn alloys have been reported.1-4 Panseri and Federighii have found that the initial stages of zone growth take place at temperatures as low as around -100°C. For investigation of the mechanism of the initial stages of zone growth, growth studies must be carried out at low temperatures. In order to investigate the possibility of the formation of G.P. zones by the nucleation mechanism or the spinodal decomposition during quenching which was reported by Rundman and Hilliard,5 the examination of the as-quenched structure must be performed. In this paper the investigation of the early stages of the formation and growth were determined by means of the X-ray small-angle scattering method. With this technique, change of X-ray scattering intensities was measured while quenched specimens were heated slowly from liquid-nitrogen temperature to room temperature. At as-quenched state and after heated to room temperature, investigation of zone size, volume fraction, and zone number per unit volume was carried out. Measurements on these specimens yielded information on the early stages of zone formation and growth. Measurements were made also on specimens quenched to and aged at room temperature. From these measurements the previously reported model6 for the later stages of growth is confirmed; namely, the larger zones grow at the expense of smaller ones. Three elements, silver, silicon, and magnesium, were chosen as the third elements for the following reasons: Silver. In the binary A1-Ag alloy the spherical disordered 77' zones were observed immediately after quenching.7 Therefore, in the Al-Zn-Ag alloys, it is suggested that silver atoms might induce cluster formation during quenching. Also, since the migration energy of the zinc atoms was found to be raised by the addition of silver atoms,' silver atoms may have a great effect of the zinc diffusion, especially during low-temperature agings. Silicon. The effects of the addition of silicon atoms were found to be marked, especially at low-tempera-ture aging. In the binary Zn-Si system, no mutual solid solubilities between silicon and zinc9 and no in-termetallic compounds10 are reported to exist. Shashkov and Buynov11 investigated the behavior of silicon atoms in Al-Zn alloys and showed that silicon was not in the G.P. zones. The interaction between silicon atoms and vacancies is strong enough to increase the quenched-in vacancy concentration.* Magnesium. Magnesium atoms are reported to trap quenched-in vacancies and after much longer aging times these trapped vacancies will become free and act as diffusion carriers.13 Therefore at intermediate aging times, the diffusion of zinc atoms in Al-Zn-Mg alloys will be slower than in the binary Al-Zn alloys, whereas at longer times zinc diffusion will become faster. EXPERIMENTAL PROCEDURE The alloys used in this investigation had compositions of 4.4, 6.8, 9.7, and 12.4 at. pct Zn with or without 0.1 and 0.5 at. pct Ag, Si, or Mg. The alloys were prepared from high-purity aluminum, zinc, silver, silicon, and magnesium, with each metal having a purity better than 99.99 pct. The analyzed composition of the specimens is given in Table I. The measurements of the X-ray small-angle scattering were carried out with foils of 0.20 mm thick. The change of the scattering intensity was always measured at the fixed scattering angle of 20 = 2/3 deg. This angle exists nearly on the position of the intensity maximum. The value of the interparticle interference function14 which has large effect in this range of angles may not change abruptly in the case of the spherical shape of small zones. Therefore, from the above considerations, it is concluded that an increase of the intensity measured at this constant angle corresponds to an increase of the average radius and volume fraction of G.P. zones. The specimens were homogenized at 500°, 450°, and 300°C for 1 hr in an air furnace. For the study of the formation and growth at low temperatures, the foil

Jan 1, 1970

By Willard L. Hunter

Four solvent extraction systems were studied to determine their efficiency jor extraction and separation of tantalum and columbium. Aqueous feed solutions of varying HF-HCl concentrations and metal content were contacted with equal volumes of cyclohexanone, 3-methyl-2-butanone, and 2-pentanone and solutions of varying HF-H2S04 concentrations were contacted with equal volumes of 2-pentanone. One multistage continuous test was made in a polyethylene pulse column using cy clohexanone as the organic phase. In each system studied, columbium and tantalum purities in excess of 95 pct with respect to each other were obtained in single-stage tests at low acidities in the feed solution. Separation factors ranging from 1700 to 2400 were obtained when rising HF-HCl mixtures in the aqueous phase. Best results were obtained when a solution of HF-H2S04 was used as the aqueous phase and 2-pentanone as the organic phase. A separation factor in excess of 6000 was obtained in one stage with aqueous solution concentrations of 2 _N HF and 2N H2S0,. When acid concentrations were increaszd to 52 HF and 10 _N H2S0,, 99.9 pct of the tantalum and 98.2 pct of the columbium initially present in the feed solution were transferred to the organic phase. The separation of columnbium and tantalum obtainable by means of the solvent extraction systems presented in this paper was found to corn -pare favorably with other systems, including the HF-H2SO4-methyl isobutyl ketone system currently used by most producers for the extraction and separation of these metals. TANTALUM and columbium are always found together in minerals of commercial significance, although the proportion of the two metals in ores varies within broad limits. Columbium is estimated to be 13 times more abundant than tantalum. Five methods generally employed for the separat:ion of these metals are: 1) fractional crystallization (the Marignac process),2 2) solvent separation, 3) fractional distillation of their chlorides, 4) ion exchange, and 5) selective reduction. Of these methods, the one currently used by industry to the greatest extent is that of solvent separation. One of the early technical developments in solvent separation of tantalum from columbium was reported by the Bureau of Mines: the HF-HC1-methyl isobutyl ketone system; data were presented for both laboratory and pilot-plant experimentation.3 Of twenty-eight organic solvents tested for their ability to extract tantalum from an HF-HC1 solution of columbium and tantalum, 3-pentanone (diethyl ke-tone), cyclohexanone, 2-pentanone, and 3-methyl-2-butanone were chosen for further study. Data on the HF-HC1-diethyl ketone system has been published4 and data describing the use of cy clohexanone, 2-pentanone, and 3-methyl-2-butanone as the organic phase are included in this report. RAW MATERIAL The source of tantalum and columbium oxides for this study was ('Geomines" tin slag from the Manono Smelter, Cie Geomines, Gelges, S.A., Congo. In order to extract the valuable Ta-Cb content, the slags were carbided, chlorinated, and the sublimate from chlo-rination was hydrolized and washed free of chloride with water. The washed material was air-dried and stored in a stoppered container. Throughout the paper, "feed material" refers to this mixture of hydrated oxides which was employed because of its high solubility in aqueous solutions. Typical analysis of the hydrated oxides is shown in Table I. I) HF-HC1-CYCLOHEXANONE SYSTEM Batch Separation. Effect of Acid Concentration. To determine the effect of varying the acid concentration upon the transfer of tantalum and columbium, a series of tests was made in which approximately 2.5 g of feed material was added to 25 ml solutions of 2, 4, 6, 8, and 10 N HF and 0 through 5 N HC1. Tantalum pentoxide concentration of the solu%ons was approximately 21 g per liter and columbium pentoxide was 14 g per liter. These starting solutions were shaken with equal volumes of cyclohexanone in 100 ml polyethylene bottles for 30 min. The phases were carefully separated in 125 ml glass separatory funnels. The time of contact of the solutions with the separatory funnels was kept at a minimum to reduce silica contamination. The measured phases were separated into 400 ml polyethylene beakers and the metal contents of each were precipitated by addition of an excess of ammonium hydroxide. Precipitate from each phase was filtered on ashless filter paper, ignited at 800" to 1000°C for 45 min, weighed, and analyzed by X-ray fluorescence.5 Data tabulated in Table I1 and illustrated in Fig. 1, show that maximum separation of tantalum from columbium for each HF concentration was obtained with no HCl present. The purest tantalum product was obtained with some HCl present. The highest separation factor was obtained at 2 N HF and

Jan 1, 1970

By V. Pasupathi, R. E. Hummel, J. W. Koger

Specimens of P1 brass were plastically deformed at room temperature to various degrees of deformation and subsequently cooled in order to transform them to low-temperature martensite. Deformation shifts Ms. A, , and the temperature of minimum resistivity to lower temperatures, and also decreases the temperature coefficient of electrical resistivity. These properties change rapidly up to about 15 pct reduction but vary very little with higher deformation. The possible relationships between martensite formed by deformation and the M, temperature of low-temperature martensite are discussed. Evidence is given that deformation martensite delays the formation of low-temperature martensite. BETA' brass undergoes at least two different types of martensitic transformations. One of these transformations (B1- B2) was first observed by Kaminski and ~urdjumov' and occurs when 81 brass with a zinc content between 38 and 42 wt pct (quenched from the single-phase region) is cooled below room temperature. Jollev and Hull' determined the structure of 0" from X-ray and electron-diffraction data as ortho-rhombic. Kunze came to the conclusion that the super-lattice cell of 0" is one-sided face-centered triclinic (pseudomonoclinic). The second martensitic transformation (B1-A1) occurs when the specimens are deformed at or somewhat above room temperature. This type of martensite will be called deformation martensite. Horn-bogen, Segmuller, and Wassermann4 determined the structure of deformation martensite to be bct. (An intermediate phase, az, occurs before the final phase appears.) At deformations higher than 70 pct, a, transforms into a.4 A critical temperature Md exists above which no transformation occurs during deformation and is estimated to be around 400°C in P1 brass.5 This martensite has elastic properties.6 When the sample is stressed, martensitic plates appear; when the stress is released, the plates disappear. The present paper studies the effect of deformation martensite on the formation of low-temperature martensite. The experiments involved samples of 8, brass which were plastically deformed by various amounts and were subsequently cooled below the transformation temperature. EXPERIMENTAL PROCEDURE The 13 brass investigated was made from 99.999 pct pure copper and 99.9999 pct pure zinc and contained 38.8 wt pct Zn. The specimens, consisting of foils 0.1 mm in thickness, were heat-treated at 8'70°C for 15 min in an argon atmosphere and then quenched into ice water. They were then deformed by cold rolling and subsequently cooled at a rate of 1°C per min. The martensitic transformation that occurred during cooling was followed by electrical resistivity measurements. The resistance measurement technique and its accuracy have been described in a previous paper. Because the transformation 81 —-8" occurs below room temperature, the samples were placed in a cryo-stat which contained isopentane as a cooling medium. The isopentane was cooled by liquid nitrogen pumped under pressure through a 15-ft coil of copper tubing which was immersed in the isopentane. The nitrogen flow was regulated by a temperature controller using two thermistors in the cooling medium. The cryogenic liquid could be heated with an immersion heater. The useful temperature range with this device was from +25° to approximately -155~C. EXPERIMENTAL RESULTS Resistivity Measurements. The following abbreviations are used in this paper to label the characteristic temperatures during the martensitic transformation. M, is the starting point of the martensitic transformation and is defined as that temperature where the resistivity vs temperature curve on cooling first deviates from a straight line. Mf is the temperature at which the martensitic transformation is completed. On reheating, the transformation from martensite to the parent phase starts at a temperature A, and ceases at a temperature Af. Fig. 1 presents five different resistivity vs temperature curves corresponding to the transformation of brass from Dl to 8" after different degrees of reduction in thickness. The following observations can be made from these curves. 1) With increasing degree of deformation the Ms temperature is shifted to lower temperatures. This shift ranges up to 35°C compared to the undeformed state. This is also indicated in Fig. 2, where AM, (the shift of Ms, compared to the undeformed state) is plotted vs the degree of deformation. AM, increases rapidly until a reduction of about 15 pct is reached. With higher deformations, no additional increase in AM, was found. 2) With increasing degree of deformation the temperature of minimum resistivity (M) is also shifted to lower temperatures. The shift, attains a maximum of about 61°C compared to the undeformed state. In Fig. 3, AM is plotted as a function of deformation. It can be seen that, as in 1 above, AM increases rapidly and no further shift of M occurs for deformations greater than 15 pct. 3) The temperature coefficient of resistivity, is given by the slopes (dp/dT) of the linear portions of

Jan 1, 1969

By W. P. Sykes

IN CONNECTION with a study of tungsten steels, Honda and Murakami1 reported an investigation of the system iron-tungsten. This report included a tentative equilibrium diagram, photomicrographs of various alloys in the series, and qualitative measurements of hardness and magnetic properties. The present investigation originally had as its object the study of the hardness and tensile properties of a series of carbon-free iron-tungsten alloys. But, as the work progressed it became evident that the system possessed other features of interest, so the scope of the investigation was enlarged. MATERIALS The iron powder used in preparing the alloys was obtained as follows: Iron oxalate was precipitated from a ferrous-sulfate solution by the addition of a solution of oxalic acid. This oxalate, after thorough washing, was ignited to iron oxide, which after reduction in hydrogen at about 1000° C. yielded iron powder containing but about 0.2 per cent. iron oxide and about 0.005 percent. carbon. Tungsten metal in the form of powder, such as is used in the manufacture of filaments for incandescent lamps, was the other constituent. This material analyzed 99.8 per cent. tungsten and contained no carbon, The metal powders, in the desired proportions, were mixed by tumbling and formed, under pressure of 20 tons per sq. in., into rods 3/8 by 3/8 by 10 in. To form the alloys without contamination, sections of the pressed rods were placed on alundum slabs and heated in an alundum tube wound with a tungsten resistor and packed in heat-insulating material. While the resistor was heated, a stream of hydrogen was continually passed through both the tube and the case containing it. The tungsten winding on the tube, as well as the material heated within the tube, was thus protected from oxidation. Such a furnace will operate constantly

Jan 2, 1926

By W. D. Robertson, H. Conrad

Incremental loading creep tests were conducted on magnesium single crystals in tension and direct shear at 78" to 364°K. The creep curves were transient in character and exhibited waves or periodic behavior, especially at small strain rates. A sigmoidal curve was frequently observed following the first occurrence of creep. Repeating of segments of a master curve was observed at all temperatures indicating that identical conditions for flow existed after various stress and strain histories. A logarithmic time law with a independent of temperature whs observed at 78°and 203°K, while a parabolic (power) time law was approximated at 298" and 364°K. The departure from logarithmic creep was attributed. to recovery, which was observed at 298" and 364°K. The temperature independence of a represents a serious objection to the theory of low-temperature creep based on the intersection of dislocations. IN a previous paper1 it was found that the initial creep rate of magnesium single crystals, y, following the addition of a stress increment in the range of 78° to 364°K, was given by the expression ? = C exp - {?H/kT} exp {B(T- h ?)} [1] where B and C are constants, AH is an activation energy of 10,300 cal per mole, T is the applied stress, ? is the total strain at the time of the stress increment, and h is the strain-hardening coefficient. The present paper is concerned with certain other features of creep behavior observed during this investigation; namely, the form of the creep curves, time laws for creep, recovery, and microscopic and X-ray observations of the structural manifestations of the creep flow. To the authors' knowledge the temperature range of the present investigation (0.08 Tm to 0.40 Tm) has not been covered previ-

Jan 1, 1959

By C. P. Proctor, J. T. Crawford

TROUGH washers were among the earliest methods used for concentrating ores; they are referred to by Agricola about the middle of the sixteenth century as already being used while the hand- operated jigging sieve had only recently come into use. For cleaning coal the trough washer apparently was first used in France and Belgium .about 1841. The early trough washers were intermittent and the refuse at least was shoveled out by hand. The invention of a continuous jig washer, by a Frenchman, Berard, in 1848, acted as a stimulus to coal washings in jigs and retarded progress in trough washing' in the nineteenth century. Chapman and Mott describe a number of trough washers developed in England and on the Continent from 1850 to 1900, such as the Bell and Ramsay, Ramsay, Bell and Green, Wunderlich, Scaife, McLellan; Lodge, Elliott, Blackett, and Murton. , The later of these removed the refuse mechanically, either intermittently or continuously, but in ways that interfered with stratification. THE RHEOLAVEUR A Belgian engineer, Antoine France, is responsible for the development of means to remove refuse materials continuously from a trough washer while preserving stratification and preventing the loss of coal with the refuse. The methods and equipment devised, which have become known throughout the world as Rheolaveur, were initiated at the St. Nicholas mine near Liége, Belgium, about 1912. This installation consisted of two units to wash 20 to 8-mm. (13/15 to 5/16 in.) and 8-mm. to 0 (5/16-in. to 0), each having only two superimposed inclined troughs. The first few "Rheo" boxes on the top trough removed refuse directly and the remaining Rheo boxes discharged impure refuse to the lower trough for rewashing. On the lower trough the first few boxes removed refuse and the following boxes removed a middling product

Jan 1, 1943

By H. B. Smith, B. Egererg

In a previous paper1 the authors dealt with the physical properties of cold-rolled and heat-treated Britannia metal of the approximate composition Sn, 91 per cent., Sb, 7 per cent. and Cu, 2 per cent. It was found that cold rolling to more than 50 per cent. reduction produced a continuous softening of the metal when measured by the Brinell machine, whereas the Shore instrument indicated increased hardness; that the strength of the material followed the Brinell hardness and that the metal therefore became weaker the more it was cold-rolled; and further, it was found that hardness and strength could be largely restored to the cold-rolled metal by "baking" for about one hour at any temperature between 200" and 450" F., the melting point. The higher the baking temperature, the more effective was the heat treatment as far as increased hardness was concerned. It seemed to be of little importance whether the metal was soaked or not at the baking temperature for a great length of time and the rate of cooling seemed to be immaterial. The present paper deals with the same alloy and more particularly with the resistance towards various forms of stress — tensile, bend and deep drawing. The metallography of Britannia metal has in part also been covered and an explanation attempted for the abnormal behavior of this alloy. Tensile and Bend Tests Two ingots 73/4 in. wide, 11 in. long and ¾ in. thick were cast from the same pot. One ingot was cold-rolled in one direction to a strip 0.241 in. thick, which furnished the tensile test specimens; the other ingot was rolled in the same way to 0.253 in. and furnished the specimens for the bend tests. The ingots were cast as described in the previous paper and cold-rolled in six passes.

Jan 1, 1930

By P. H. Dudley

The piping and segregation of ingots of steel is a comprehensive subject, and must be studied in reference to the different grades of soft, medium, and hard steel, rather than to discuss it in a general manner, as though applicable to all grades. Rail steel, however, will receive the most consideration in this paper, for the wheel-loads of the motive power and rolling stock have doubled from 1890 to 1910. Steel rails and tires which were efficient under the light loads, became less serviceable under the double wheel-loads, quadrupled tonnage, and higher speeds. Bessemer Steel. Bessemer steel of from 0.10 to 0.15 per cent. of carbon, for splice-bars, spikes, and tie-plates, rises in setting, and is cast in bottle-mouthed molds, which must be capped to prevent an overflow from the top. This grade of steel rises in the molds and makes a longer ingot than the volume of molten steel when first teemed. The ingots which are allowed to cool and then cut open, show, particularly in the upper part, large occluded blow-holes, and when they are not oxidized or do not contain foreign matter, weld more or less completely when the steel is rolled or forged above 1,100° C., and it is in this way that the blow-holes are closed in the low-carbon steels. Boiler-Plate and Fire-Box Steel. These grades often contain more or less minute laminations, which are the remains of small blow-holes forming after the setting metal has reached a pasty condition. The blow-holes in the low-carbon steels have not been prevented by usiug deox-idizers, though the ingots are slightly improved so far as the soundness of the steel is concerned. This grade of steel also rises in the molds in setting.

Jan 1, 1914

By T. E. Kihlgren

SYSTEMATIC data are presented on the relation of composition of nickel silvers to color, tarnish resistance, hardness and liquidus temperatures, for alloys containing up to 30 per cent nickel and 50 per cent zinc, further modified at certain nickel and zinc contents by 0 to 8 per cent of tin and 0 to 10 per cent of lead. Attention has also been directed, using a still more limited range of alloys, toward a study of tensile properties and such casting properties and characteristics as fluidity, shrinkage and pressure tightness. In some of these, rather broad ranges of composition are dealt with; in others, it has been expedient to focus attention on the Federal Specification 20 per cent nickel silver casting alloy, WWP-541. INTRODUCTION The demand for an alloy essentially white in color, which could be cast and worked by simple methods and which possessed strength and corrosion-resisting properties superior to the usual brasses, led to the discovery and early use of cupronickel alloys containing zinc, and some-times tin, lead and other metals. This type of alloy was generally known as German silver until the war, when the term "Nickel Silver" became generally accepted. The element principally responsible for the white color of the alloy and for its strength and corrosion resistance is nickel, which may constitute from 8 to 30 per cent of the alloy. The functions of the other elements will be described later. The manifold uses of nickel silver are largely due to its color, corrosion resistance, ease of casting, fabrication, joining and rather moderate cost. In many instances the alloy is finished by grinding and polishing while in others it may be finished with a silver or nickel plus chromium plate. Electroplates

Jan 1, 1935

By Juhani Pulkkinen, Pekka Lappalainen

Preplaced cable bolts - fully grouted old hoisting cables or stress relieved steel strands - have been used succesfully to pre- reinforce ore contact zones and pillars in sublevel stoping at Outo- kumpu Oy mines for ten years. The purpose is to make open stoping methods possible even in "poor'' conditions and to decrease waste rock dilution. Since 1971 more than 120 km cable bolting has been done, and plans for this year in five mines amount to 33 km. In order to understand the function of cable bolt, pull-out tests have been done both in the laboratory and in situ. Bond strength between cable and cement is highly dependent on cable structure and cable surface dirtiness. Steel cables with steel core and rough surface structure have highest bond strength ( 6 MP~). A cable bolt is a friction bolt. After losing its peak bond strength - after starting to move - a cable bolt still has a high loading capacity due to the friction caused by the uneven surface of the cable. Cable bolting is done before actual stoping from existing drifts, sublevel drifts, e.g. or from special bolting drifts. In general stress relieved steel strands are used; 2 x 15.2 mm dia per hole. FEM or BEM calculation is utilized in cable bolting design. Bolts 2 are in fan shape, 10 m ... 50 m long and are spaced 1/20 m ... 1/50 m2 at stope walls. Pretensioning of cable is not needed, when bolting is done before rock deformations. Bolting costs vary between 0.3 USD ... 1.0 USD/ore ton. In the beginning only manual cable installing technique bras used. Now bolting can be done as fully mechanized with the developed cable bolting machine; i.e. drilling of the hole, installing and cutting of cables and grouting of hole.

Jan 1, 1983

By Holbrook G. Botset

Experiments performed in this laboratory on the flow of gas-liquid mixtures through unconsolidated sands have been described and discussed in an earlier paper.4 In these earlier experiments a definite relationship was found between the liquid saturation of a sand and its permeability to the liquid or gas phase. Furthermore, the nature of the sand, the permeabilities of the sands over a range between 17 and 260 darcies, appeared to have a negligible effect upon the saturation-permeability relation. Likewise experiments indicated that the viscosity of the liquid, or the substitution of an immiscible liquid for the gas phase, had only a very slight effect on the permeability-saturation relation. This conclusion has since been definitely confirmed by the experiments of M. C. Leverett3 on the flow of oil and water through unconsolidated sands. The sands used by Leverett were of very low permeability (between 6.8 and 1.04 darcies), while the oil-water viscosity ratio varied between 90 and 0.057. Since the sands that constitute petroleum reservoirs are largely consolidated, although of widely varying degrees of consolidation, it was desirable to extend the experiments on gas-liquid mixtures to consolidated sand. In the study of consolidated sands additional variables are involved, but for the initial experiments the only new variable to be introduced was the cementing material. Experimental Procedure A comparatively limited assortment of sandstones was available for the selection of the experimental material. Of these, the Nichols buff sandstone appeared to be most suitable. It gives no visual evidence of any bedding planes, it has a firm structure, permitting easy handling, and its permeability is about 0.5 darcy. Its only disadvantage is the fact that it contains an appreciable amount of ferric oxide which, for experiments involving water, will hydrate and reduce the permeability. This

Jan 1, 1940