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By Frederick N. Rhines

Pure copper that has been allowed to oxidize at an elevated temperature in the air is found to be covered with two distinguishable layers of oxide scale. The outer of these, which is very thin, is composed of cuprie oxide, while the inner layer, comprising the bulk of the scale, is made up chiefly of cuprous oxide (Fig, la). If a small quantity of an alloying element, such as silicon, is present in the copper, silica particles are found disseminated through the cuprous oxide, deposited most abundantly near the metal surface, and, in addition, silica particles occur to a limited depth within the copper itself (Fig. 1b). It is this inner layer, composetl of oxide particles precipitated in a matrix of metallic copper, that is known as the "subscale" or the zone of internal oxidation. Under a low oxygen pressure it is possible to produce the subscale without the formation of external layers of copper oxides, thus leaving the metal surface bright and apparently clean while oxidation has occurred, in fact, to a considerable depth within the metal (Fig. 2). Although little is yet known in a detailed way of the mechanism of internal oxidation, the general nature of the process is evident. By virtue of the considerable solubility of oxygen in copper,' it is possible to bring the alloying element in contact with oxygen within the metallic solid solution. If the oxide of the alloying element is more stable than cuprous oxide, the foreign oxide may form and, since most oxides are relatively insoluble in copper, it will not long remain in solution, but mill separate as a precipitate. As the metallic solute is exhausted in the zone of precipitation, oxygen that is constantly being supplied at the surface diffuses farther into the alloy and thus produces an ever-thickening shell of subscale. The distribution of the reacting elements in the subscale and adjoining zones must be somewhat as indicated in Fig. 3. The conditions requisite to internal oxidation to be anticipated are thus: (I) a solubility of oxygen in the alloy, (2) the ability of oxygen to diffuse at an appreciable rate into the alloy, (3) the possibility of the

Jan 1, 1940

By Frederick N. Rhines

Pure copper that has been allowed to oxidize at an elevated temperature in the air is found to be covered with two distinguishable layers of oxide scale. The outer of these, which is very thin, is composed of cuprie oxide, while the inner layer, comprising the bulk of the scale, is made up chiefly of cuprous oxide (Fig, la). If a small quantity of an alloying element, such as silicon, is present in the copper, silica particles are found disseminated through the cuprous oxide, deposited most abundantly near the metal surface, and, in addition, silica particles occur to a limited depth within the copper itself (Fig. 1b). It is this inner layer, composetl of oxide particles precipitated in a matrix of metallic copper, that is known as the "subscale" or the zone of internal oxidation. Under a low oxygen pressure it is possible to produce the subscale without the formation of external layers of copper oxides, thus leaving the metal surface bright and apparently clean while oxidation has occurred, in fact, to a considerable depth within the metal (Fig. 2). Although little is yet known in a detailed way of the mechanism of internal oxidation, the general nature of the process is evident. By virtue of the considerable solubility of oxygen in copper,' it is possible to bring the alloying element in contact with oxygen within the metallic solid solution. If the oxide of the alloying element is more stable than cuprous oxide, the foreign oxide may form and, since most oxides are relatively insoluble in copper, it will not long remain in solution, but mill separate as a precipitate. As the metallic solute is exhausted in the zone of precipitation, oxygen that is constantly being supplied at the surface diffuses farther into the alloy and thus produces an ever-thickening shell of subscale. The distribution of the reacting elements in the subscale and adjoining zones must be somewhat as indicated in Fig. 3. The conditions requisite to internal oxidation to be anticipated are thus: (I) a solubility of oxygen in the alloy, (2) the ability of oxygen to diffuse at an appreciable rate into the alloy, (3) the possibility of the

Jan 1, 1940

By H. F. Gossenberger, J. J. Tietjen, J. J. Gannon, C. J. Nuese

External quantum efficiency measurements at 300" and 77°K are presented for vapor-grown GaAs and GaAs1-xPx electroluminescent diodes as a function of junction depth and doping. In GaAs, external efficiencies are found to decrease exponentially with increasing junction depth, defining an average absorption coefficient of 900 cm-1 at 300°K and 350 cm-1 at 77°Kfor epitaxial layers of p-type GaAs. It is shown that photon absorption losses dominate at room temperature and, in fact, account for most of the external efficiency degradation between 77° and 300°K. Healever, the internal ('junction) quantum efficiency is also found to decrease by a factor of 3.5 between 77" ALTHOUGH rapid progress has been made in recent years with GaAs, Gap, and their alloys for use in electroluminescent diodes, there are still important unknown factors related to the performance of these de- and 300°K. The dependence of GaAs efficiencies on donor and acceptor concentrations is presented, illustrating best efficiencies at donor concentrations of 1.5 to 2x 1018 cm-3 . External efficiencies are found to be independent of acceptor concentrations less than 3 x 1019 cm-3 but to degrade at higher doping. The fabrication of GaAsi-xPx electroluminescent diodes is briefly discussed. External efficiencies here for planar uncoated diodes are about 0.035 pct at 300°K and 0.4 pct at 77°for x = 0.42. A brightness of about 8500 ft-Lamberts is attained at 77°K and of 315 ft-Lamberts at 300° K. for curvent densities of 10 amp per sq cm. vices. For example, although the external efficiency is known to decrease by factors of typically 10 to 30 between 77°K and room temperature, the exact causes of this are still uncertain. Experimental results of ill' and carr2 with zinc-diffused electroluminescent diodes suggest that this external degradation is almost entirely due to increased absorption losses at room temperature, with a relatively temperature-independent internal efficiency; recent calculations by Gonda et al.3 corroborate this hypothesis. In contrast, Pilkuhn and Rupprecht4 find the internal efficiency of solution-grown GaAs laser diodes to degrade from 100 to 66 to 40 pct as the temperature is increased from

Jan 1, 1969

By D. I. Bardos, F. X. Spiegel, R. K. Malik, Paul A. Beck

Study of the occurrence of elongated ß-Mn phase fields and of their direction of extension in fifteen ternary systems indicates that the ß-,mn phases formed by manganese with other transition elements and with either silicon, germanium, or tin may be considered as electron phases. In these phases the alloying behavior of silicon on the one hand and of germanium and tin on the other shows a significant difference . Formally all observations can be satisfactorily described by attributing to germanium and tin an apparent electron concentration of nine electrons per atom. This behavior may be interpreted by assuming that germanium and tin exclude itinerant electvons because of a strong repulsive potential arising fromthe requirement that their wave junctions be orthogonal to those of- the closed d shells of these atoms. The absence of a d shell in silicon allows this atom to admit itinerant d electrons. The following new ternary phases of unknown structure were identified by means of their X-vay difjraction patterns: (Mn,Co,Si)I , (Mn,Co ,Si)Y, (Mn.Co,Si)Q , (Mn ,Ni ,Si)W , and (Mn, Ti ,Si)A. The X-ray data suggest that these phases have large unit cells and that to some extent they may he related structurally to the 0 phase. The a phase and certain other phases formed by transition elements are characterized by their preferred occurrence at a constant electron concentration. AS a result, these "electron phases" have relation to electron concentration. The tendency of the B phase to form elongated phase fields in ternary systems along the directions of constant electron concentration has been previously demonstrated. The occurrence of an elongated 0-Mn phase field in the ternary system Mn-Co-Si was schematically indicated by Cherkashin et al.l0 The present study includes fifteen ternary systems, each containing in addition to manganese a second transition element from the group Ti, V, Cr, Fe, Co, Ni and one of the nontransition elements silicon, germanium, or tin. In each system the boundaries of the B-Mn phase were determined in the 900°, 950°, or 1000°C isothermal section, the temperature being dictated on the one hand by the requirement of sufficient rates of diffusion to approach equilibrium conditions in reasonably short annealing periods and on the other hand by the need to avoid as much as possible the partial melting of alloys during annealing.

Jan 1, 1967

By C. E. Ells, A. Sawatzky

The effect of neutron irradiation on tensile properties of the Zr-2.5 wt pet Nb-0.5 wt pet Cu alloy has been evaluated for integrated neutron fluxes up to 3 x 1020 n per sq cm (E > 1 Mev). Specimen temperature during irradiation was normally 300°C. The material was studied both in annealed and in quenched and aged conditions. When the alloy (fab-ricatedfrom sponge zirconium) is quenched from a temperature =40°C below the a + ß/ß transformation and aged 6 hr at 535oC, neutron irradiation up to the maximum studied has little effect 071 reduction in area, although there is a drop in uniform elongation and the yield strength is increased by = 25 pct. Conversely, irradiation of the alloy in an annealed condition can result in much greater changes in properties, with yield-strength increases of up to 200 pet. The dose dependence of irradiation hardening obeys the saturation equntion proposed by Makin and Minter to explain hardening in copper and nickel: Act = C[1 - exp(-Døt)/1/2 A rnodel is proposed to explain the effect of niobium content and metallurgical condition on irradiatiotz behavior. THE Zr-Nb alloys form a class of material susceptible to marked strengthening by quench and age heat treatment. With niobium concentrations as low as 2.5 wt pet, strengths can be developed which are double those of annealed zircaloy-2.1 Since the neutron-capture cross section of the Zr-2.5 wt pet Nb alloy is nearly identical to that of Zircaloy-2, significant gains in power-reactor neutron economy could be obtained by replacing stressed in-reactor components of Zircaloy-2 with the heat-treated Zr-Nb alloy. When the solution heat-treatment temperature is in the high (a + ß) phase, then the tensile properties of the quenched (and aged at 500°C) material have been shown to be relatively insensitive to neutron irradiation.1-3 Addition of small quantities of copper to the binary Zr-2.5 wt pet Nb alloy gives a useful reduction to the corrosion rate in air and carbon di- oxide,&apos; and a ternary alloy of composition Zr-2.5 wt pet Nb-0.5 wt pet Cu was chosen for one component in the Douglas Point Reactor. This application utilizes both the corrosion resistance to a moist air-carbon dioxide environment and the strength developed by a quench and age heat treatment. By suitable choice of solution heat treatment and aging temperatures, tensile properties of the ternary alloy can be made nearly identical to those considered as optimum for the binary alloy. One effect of the copper addition, however, is to give marked changes in the aging kinetics of the alloy.&apos; For this reason, it appeared that neutron irradiation might promote overaging in the ternary alloy, particularly at the elevated service temperature (=300°C). This paper describes the effect of neutron irradiation on the tensile behavior of the Zr-2.5 wt pet Nb-0.5 wt pet Cu alloy in several metallurgical conditions pertinent to its use as a reactor material. The metallurgical conditions included those for which aging occurs in the unirradiated material, and fully annealed conditions for which a higher degree of thermal stability could be expected. 1) EXPERIMENTAL Two batches of alloy were used, both made from sponge zirconium. The fabricator&apos;s analysis of principle constituents showed no significant difference between the two batches, Table I. The rod material was rolled to 1.5 in. diam, and then swaged to final sizes of 0.5 to 0.375 in. diam at nominal temperatures of 785" and 625°C for the AM and AS batches, respectively. Subsequent hydrogen analyses at CRNL confirmed that the hydrogen concentration of the as-received rod was indeed <20 ppm. However, it was found that the (a + ß)/ß transus for the AM material was approximately 25°C lower than that of the AS material, indicating rather more difference in oxygen concentration than given in Table I. Except for a small difference in yield-point behavior, the tensile prop-

Jan 1, 1965

By S. K. Tarby, A. E. Rathke

A series of 0.21 pci carbon steel melts was processed under conditions which sinzulated industrial vacuum degassing practices. The results indicated that the efliciency of carbon deoxidation was not significantly increased by vacuunz degassing at chamber pressures below 100 torr. The two common phenomena of vacuu?rz carbon deoxidation, i.e.,an unaccountable carbon loss and nonequilibrium deoxidation, were observed in this study. Oxygen from adsorbed and chenzically combined water of certain refractory structures was probably responsible for the unaccourttable carbon drop. The nonequzlibrium deoxida-tion phenomenon was adequalely correlated by a bubble nucleation )mechanism. Although the major limiting factor in oxygen removal from these melts contained in alumina crucibles could not be eslablished with certainty, there was some evidence that melt-refractory interactions were not the most imp-portant limiting factor. CONSIDERABLE attention has been given to the use of carbon in conjunction with vacuum degassing* as a deoxidation technique. An advantage of utilizing the reaction: for deoxidation purposes is that the reaction product is gaseous and hence can be effectively removed from the melt. The pressure dependency of Eq. [I] is illustrated by the expression for the thermodynamic equilibrium constant, K: where pco is the partial pressure of carbon monoxide, and hc and ho are, respectively, the Henrian activities of carbon and oxygen in molten steel. The thermodynamic aspects of the C-0 reaction in molten Fe-C-0 alloys have been investigated extensively. Theoretical predictions based on Eq. [2] indicate that, at the chamber pressures reached in most vacuum degassing units, carbon is the most effective deoxidizer that can be obtained. ~ornak&apos; has compared industrial values of carbon and oxygen contents with values calculated from theory, and has shown that on a commercial basis vacuum carbon deoxidation has not achieved the degree of success that is predicted from theoretical considerations of the C-0 reaction. The use of industrial units to determine the reason for this deviation is limited by economics and the difficulty in controlling critical process variables. Therefore laboratory-sized experiments in this area should yield valuable information. Investigations on vacuum carbon deoxidation have been made in experiments conducted under vacuum induction melting conditions where pressures in the low micron range, long treatment times, exposure to highly dynamic vacuum conditions, and relatively quiescent bath conditions have been maintained. Inve~ti~ators~~~ utilizing vacuum induction melting for the production of high-purity iron by carbon deoxidation have concluded that, under high vacuum conditions, melt-refractory interactions constantly supply oxygen to the melt. Thus, it has been suggested that refractory dissociation rather than the C-0 reaction establishes the lowest possible oxygen content of a melt. Thomas and Moreau4 and Bennett, Protheroe, and ward5 have studied carbon deoxidation of Fe-C alloys melted in magnesia crucibles under reduced pressures. The results of both studies differed considerably from those predicted by theory, and the limiting factor for lower oxygen contents was attributed to melt-refractory interactions. Because the refractory material used in both investigations was magnesia, no quantitative measure of crucible reaction could be made and the amount of carbon consumed during treatment was utilized as an indirect indication of the extent of crucible reaction. Studies concerned with the determination of the minimum oxygen content attainable in pure iron and Fe-C alloy material vacuum-induction-melted in various crucible materials have also been conducted."&apos; The suitability of a crucible refractory for use under vacuum conditions appears to depend upon the major refractory constituent, the amount and type of impurity oxides, and the composition of the melt. Meadowcroft and Elliott9 have presented a theoretical review of the type and extent of various refractory reactions which should be considered in vacuum refining. ~eadowcroft&apos;~ considered the vacuum degassing process to be dependent upon the "carbon boil" and has proposed that a part of the difference between the experimental and theoretical results for vacuum carbon deoxidation may be explained by the fact that the pco term in Eq. [2] is not the chamber pressure. Instead, the pressure necessary for carbon monoxide

Jan 1, 1970

By Peter Beardmore, Michael B. Bever

The effects of the temperature of deformation and the degvee of deformation on the annealing spectrum of a Au-Ag alloy have been determined by vesistance measurements. Specimens were deformed in torsion at 4°, 78K and room temperature up to strains nd/l of about 1.0 and were isochronally annealed. Discrete annealing stages similar to those found for pure metals were observed. Stage A occurred below room temperature; the decrease in reszstance associated with this stage increased as the temperature of deformation was lowered or the strain was increased. Stage B manifested itself as an increase in resistance; this is attributed to the restoration of short-range order promoted by vacancy or vacancy aggregate migration. At temperatures above 48S0K, recrystallization or Stage C occurred. Stages A, B, and C in the annealzng curves of this alloy may be considered to correspond to Stages II, Ill, and V, respectively, in the terminology used to describe the annealing spectrum of pure metals. ThE annealing behavior after deformation below room temperature has been thoroughly investigated on pure metals, in particular gold and copper. The occurrence of several discrete stages in the annealing spectrum of these metals has been established, but the interpretation of some of these stages in terms of specific mechanisms is still controversial.&apos; The annealing of alloys deformed below room temperature has been the subject of only a few investigations. In the investigation reported here, a Au-Ag alloy was annealed after deformation at and below room temperature. This continues a research program on the deformation and annealing behavior of Au-Ag alloys.2-8s EXPERIMENTAL PROCEDURE An alloy rod of composition 82.6 wt pct Au-17.4 pct Ag was reduced to wire, 0.0428 in. diam, by swaging and drawing. After a recrystallization treatment, the grain size was 0.031 mm, as obtained from the average linear intercept.7 The ends of wires about 6 in. long were flattened and sealed into short brass tubes with cold setting cement to form the grips of the torsion specimens. The equipment used for deformation has been described elsewhere.6 The specimens were deformed at room temperature, 78", and 4°K to various strains nd/l, where n is the number of turns, d the diameter of the specimen, and 1 its length between grips. The strain rate ?max was 0.1 min-&apos; at the sur- face of the specimen except where noted otherwise. The specimens were annealed isochronally for 30 min at intervals of approximately 30°K from the temperature of deformation to approximately 800°K, except that after deformation at 4°K the lowest annealing temperature was 78°K. A potentiometric method was used to measure the resistance: all measurements were made at 78°K with the exception of some measurements at 4°K mentioned below. Data obtained with a single specimen yielded a complete annealing curve: in several cases duplicate specimens were used to confirm the reproducibility of the curves. Since the surfaces of the specimens were rough after deformation, their diameters could not be measured accurately. The resistance increments after deformation and annealing are therefore reported as percentages of the resistance of the same specimen measured after completion of the annealing, that is, after full recrystallization. The corresponding resistivity values can be calculated by obtaining the effective diameter of a deformed specimen from the ratio of its resistance after recrystallization to the true resistivity, which was determined with a smooth specimen of known dimensions. This method of calculation was used to obtain data shown in several of the figures. RESULTS AND DISCUSSION The isochronal annealing curves after deformation to various strains at 4", 78K, and room temperature are shown in Figs. 1, 2, and 3, respectively. The resistance increment of the as-deformed specimens as a function of strain is shown in Fig. 4. For the specimens deformed at 4°K. values measured at 78°K are plotted with the exception of those for the as-deformed

Jan 1, 1970

By R. M. N. Pelloux

This study of aluminum-copper alloys had two aims: 1) To determine the effect of the amount and distribution of a second phase, CuAl2, on the creep-rupture strength, ductility, and fracture characteristics of the alloys. The work of Gemmell and grant&apos; on single-phase aluminum-copper alloys provided a basis for the present study. 2) To attempt to provide a relation between the microstructure and strength of two-phase alloys deformed at comparatively high temperatures (greater than 0.45 T,). The creep behavior of the two-phase magnesium alloys Mg;Ce and Mg-A1, has been treated by Roberts. 9 In work reported by Sully and Hardy4 and by Underwood, Marsh, and Manning~ on A1-Cu two-phase alloys, and also in a portion of the work of Gemmell and grant,&apos; aging took place during the creep tests. &apos;In the present work, overaged aluminum-copper alloys were subjected to creep deformation at two temperatures, 500 and 700OF. The overaging treatments to produce the precipitate dispersions were performed prior to the test, at temperatures which were the same as the ultimate respective test temperatures. Hence, the present study is concerned with the creep behavior of stable (in contrast to "underaged") two-phase A1-Cu alloys, i.e., alloys in which no depletion of the solid-solution matrix occurred during: creep. MATERIALS AND PROCEDURE A 2 and a 3 pct Cu alloy, supplied by Alcoa, were studied; Table I shows the compositions. The grain size of the specimens, 0.9 to 1.0 mm, was achieved by annealing the machined test bars for 2 hr at 1000°F, followed by furnace-cooling to 900°F, and homogenizing for 4 hr. Both compositions are in the single-phase condition at 900°F. Two types of overaged dispersions, termed "over-aged I" and "overaged 11" were prepared after the grain size and the homogenization anneals. The overaged I alloys were prepared by quenching to room temperature after homogenization, aging at either 500&apos; or 700°F for 72 hr, and air-cooling to room temperature. The overaged I1 alloys were prepared by furnace-cooling after homogenization, to either 500&apos; or 700°F, and holding at the necessary temperature for 72 hr. The times for furnace-cooling from 900°F to 700° and 500°F were, respectively, about 2 and 3.5 hr. The structures of the A1-2 pct Cu alloys are shown in Fig. 1 (overaged I) and in Fig. 2 (overaged 11). A comparison of Figs. 1 and 2 shows that in the overaged I alloys the precipitate particles along the grain boundaries are much more closely spaced and the grain boundaries are straighter than they are in the overaged I1 alloys. Further, the particle size and spacing in the grains are smaller than in the overaged I1 alloys. Microstructures of the A1-3 pct Cu alloys have not been shown; the structures of these alloys differed from those of the A1-2 pct Cu alloys only in that the distribution density of the particles was greater. The creep specimens had a gage section 1 in. long with a diameter of 0.155 to 0.195 in. Before testing, specimens were electropolished in a solution of 100 cc glacial acetic acid, and 30 cc of 60 pct perchloric acid, at 40&apos; to 50°F, at 24 v. The specimens were kept refrigerated prior to testing to avoid precipitation at room temperature. Constant stress creep tests were conducted; the load was applied 75 min after heating of the specimens to test temperature had begun. EXPERIMENTAL RESULTS Creep-Rupture—Fig. 3 shows the log stress-log rupture life plotfor the overaged alloys studied, and also for the underaged A1-2 pct Cu alloy.&apos; At 700°F, the stress-rupture life relationship is nearly independent of both the amount of precipitate (i.e., composition) and of the type of overaging treatment (i.e., precipitate dispersion). At 500°F it is apparent that the increase in rupture life that was ex-

Jan 1, 1960

By O. R. Wagner, R. O. Leach

Immiscible displacement tests were performed in a consolidated sandstone core over the interfacial tension range from less thdn 0.01 to 5 dynes/cm to better define how interfacial tension (IFTJ reduction can lead to increased oil recovery. Data obtained were displacement efficiency at breakthbrough vs IFT for both drainage and imbibition conditions. These tests simulate water flooding under oil-wet and water-wet conditions, respectively. Results of the study have shown that displacement efficiency under both oil-wet and water-wet conditions can be markedly improved by a sufficient reduction in IFT. In the particular porous media used and for the low pressure gradients employed, the IFT must be reduced to a value less than about 0.07 dynes/cm to achieve increased recovery at the time of breakthrough of the injected phase. Below 0.07 dynes /cm, further small reductions in IFT result in large increases in displacement efficiency. Observed increases in recovery were obtained at pressure gradients which are well below those which can exist in the interwell area of a reservoir under water flood. The effect of pressure gradient on recovery is discussed. INTRODUCTION A residual oil saturation remains in rock which has been water flooded because, under usual reservoir conditions, the driving force which can be generated is inadequate to expel oil trapped by capillary forces. Since these capillary forces can be reduced by reducing the IFT a frequently studied method of increasing oil recovery has been the use of surfactants to reduce the water-oil interfacial tension. Mungan l observed improved recovery in both water-wet and oil-wet systems at 1.1 dyne /cm IFT, finding that the amount of improvement was greater in oil-wet systems. Moore and Blum,2 working with visual flow cell micro-models, con- cluded that recovery cannot be improved in water-wet systems by injecting surfactant solutions. They calculated that, for a pressure gadient of 1 psi/ft in their model, the IFT must be reduced to 0.03 dynes/cm to release oil trapped under water-wet conditions. Berkeley et al.3 indicated that, at representative field flooding rates, the IFT must be reduced to 0.001 dyne/cm to improve recovery, Thus, there is a wide variation of opinion about the IFT levels needed to improve recovery under field conditions. These previous investigators all have used as their experimental method the addition of surfactants to the injected water. The use of surfactant solutions to reduce IFT creates two experimental problems: (1) the loss of surfactant through adsorption on reservoir rock can obscure the true IFT value which exists at the displacement front, and (2) at very low values of IFT emulsifica-tion of oil and water commonly occurs. It is difficult, therefore, to determine whether the increased recovery is caused by IFT reduction as such, or is instead caused by emulsification. Also the properties of the available surfactants limit the IFT range which can be studied. In the present study the purpose is to better define how interfacial tension reduction can lead to increased oil recovery. A matter of great interest is the amount of recovery improvement potentially achievable in this way. The study was made using very low pressure gradients which was well within the range achievable by water flooding in the interwell region of petroleum reservoirs. A unique experimental approach was chosen to avoid adsorption and emulsification problems, and to allow convenient control of IFT. The fluid phases used were the equilibrium vapor and liquid phases of the methane-n-pentane system. The interfacial tension level was varied by changing the equilibrium pressure of the methane-pentane system over the range from 1,200 psia to near the critical pressure (2,420 psia). All tests were performed at a controlled temperature of 100F. The IFT-vs-pressure relationship for the methane-pentane system was based on the data of Stegemeier and Hough,6 and on new data obtained in this study. With this experimental approach it has been possible to study displacement at lower values of IFT than have been previously investigated.

Jan 1, 1967

By F. Weinberg

Measurements have been made of solute segregation during dendrilic growth by using radioactive solute elements and ,measuring the activity of den(12-ites cut from decanted specimens. This has been done for both lead awl tin based binary alloys contaitzing the following solute additions: Ag, T1204, was dependet on ko, the equilibrium distribution coefficient in the following way Fay k &apos;c 0.1, C/C 0.6; for k0 >0.1. 0.6 <c,/c,< I. Qualitative obse?-vations were madc of dendritic segregation, by using autoradiographic techniques, for the Sn + Ag110 and Sn + Tlo4 systems. The observation were found to he in general agreement with the measurements ofCA/Co. Autoradiographic were also obtained of scctiolccl delzr11-iie stalks. These indicated that the stalks had a substructure, dclileated by solute corzetlt?atio?zs nlolg the substructure walls. A new dendrite growth direction <JI2> is reported for tila. SOLUTE segregation in dilute binary alloys has been investigated by Pfann,&apos; Smith, Tiller, and Rut-ter,&apos; and others. They considered the case of a slowly advancing plane solid interface, and derived expressions for the distribution of solute in both solid and liquid during solidification. To determine these expressions, they assumed no diffusion in the solid and either complete mixing in the liquid:&apos; or diffusion controlled solute movements in the liquid without any convective mixing.&apos; The present investigation considers solute segregation during dendritic growth, in which case the solid-liquid interface is not plane, and the growth rates are rapid. Segregation under these growth conditions has not been treated mathematically, because of the relative complexity of the system. It has been suggested by Chalmer, on the basis of preliminary results, that an alternative to the diffusion and heat flow controlled conditions during growth is &apos;diffusionless" dendritic growth in which solid is formed with the same composition as the liquid. He suggests this type of growth may depend upon a solvent-solute relationship that permits some solid solubility without excessive increase in internal energy, as is the case for solutions of tin in lead. On the other hand, Montariol,4 and others, have shown experimentally that some segregation does occur during dendritic growth in metals using etching and radioactive tracer techniques to indicate the concentrations of the solute. The present investigation was undertaken to determine, both qualitatively and quantitatively, the extent of solute segregation associated with dendritic growth in a series of binary alloys, as a function of solute concentration. PROCEDURE The solvent materials used were Vulcan Electrolytic tin (99.997 pct purity) and Tadanac lead (99.998 pct purity). The solute materials were Zn, Sn, and Sb (better than 99.998 pct purity), Ag and Co (99.5 pct purity), and T1 (Fisher "purified" metal sticks). Activation of the solute metals was carried out in the reactor at Chalk River, Canada. Master alloys were prepared by induction heating from the radioactive solute metal and the pure solvent, under argon, in graphite crucibles. Pieces of these alloys were then added to the solvent to give the required solute concentration. Dendrites were grown in essentially the same manner as that described by Weinberg and Chalmer, , in which controlled orientation single crystals were grown dendritically in horizontal graphite boats, and the liquid decanted. The crystals were grown and decanted in an atmosphere of tank argon. Before decanting, a sample of the liquid was drawn up in a glass tube and allowed to solidify rapidly. The orientations of the single crystals were such that <loo> was parallel to the growth direction, and (100) in the horizontal plane for lead, and [1101 and (110) respectively for tin. With these orientations long dendrite stalks formed along the bottom of the boat in the dendrite direction (<100> for lead and [I101 for tin) from which secondary branches grew. Only these secondary branches, which grew freely in the liquid from the dendrite stalk to the liquid surface, were used in the measurements. Accordingly, effects due to substrates and oxides on the surface of the liquid need not be considered. In order to measure the solute concentration C, of the dendrites, individual dendrite stalks were cut from the decanted specimens, remelted, and formed

Jan 1, 1962

By W. O. Philbrook, R. S. Kaplan

Rates of oxidation were studied for levitation-melted samples of Fe-C, Fe-Si, Fe-C-Si, Fe-C-P, Fe-C-Mn, and Fe-C-S alloys oxidized by mixtures of either 5 or 10 pct O2, in helium at several temperatures in the range 1850o to 2050°C. The concentrations of the oxidized elements decreased linearly with time. Mass transport in the gas phase was found to be the rate-controlling step. Ilowever, a mulliple -film model was necessary to account for the flux of iron and manganese vapor counter to the oxygen flow. THE advent of the basic oxygen and spray-refining processes of steelmaking has generated considerable interest in the kinetics of reactions between oxygen-bearing gases and liquid iron alloys. The object of this research was the determination of the role of mass transport in the gas and metal phases and of surface chemical reactions in the overall oxidation process. Of the reactions for elimination of elements dissolved in liquid iron, the oxidation of carbon has been investigated most extensively. Studies by Fuji and Ura,1 Fuji,&apos; and Gunji et a1.,3 done with pilot-scale basic oxygen furnaces, indicated that mass transport of gaseous oxygen was rate controlling when the metal carbon content was greater than 0.15 to 0.30 pct. When the carbon content was less than this critical amount, diffusion of carbon dissolved in the iron was thought to be rate limiting. L. A. Baker et a1.4,5 levitated samples of iron-carbon alloys and oxidized them in CO-CO2, CO-C02-He, and O2-He atmospheres at 1660°C. These investigators found that the metal carbon concentration decreased linearly with time and their samples exploded when the carbon content fell below about 0.8 pct. They concluded that the rate-limiting step was the transfer of oxidant to the gas-metal interface. A model based on this rate-limiting step predicted decarburization rates within a factor of two of those experimentally observed. The explosion of the samples was attributed to a shift in rate-controlling step from gas-phase mass transport to transport of carbon dissolved in the metal. L. A. Baker and R. G. ward6 and R. Baker7 used freely falling droplets to investigate oxidation kinetics. In both papers, the authors speculated that flame fronts may have been partially responsible for the lack of better agreement between experiment and theory. Swisher and Turkdogan8 oxidized liquid iron having an initial carbon content of 0.97 pct with CO-CO2 and CO-C02-Ar mixtures at 1580°C. They concluded that a surface reaction was the rate controlling step. Iron-silicon alloys have been oxidized by R. Baker7 and Filipov and Martynov.9 R. Baker 7 also studied iron-carbon-silicon alloys falling as liquid droplets through oxygen. He found that the rate of both carbon and silicon oxidation varied inversely with the drop radius. When the initial silicon concentration was greater than 6 pct, the samples cooled during their fall. Manganese oxidation has been studied by R. Baker,7 and by Filipov and Martynov.9 ward10 investigated the loss of manganese from liquid iron under vacuum. He found that mass transport of manganese vapor was rate limiting in argon atmospheres of 0.02 torr to 700 torr pressure. Iron-sulfur alloys were desulfurized with H2-He and H2-Ar mixtures by Peters et al.11 A model based on the transport of H2S from the gas-metal interface into the bulk gas gave fair agreement between the predictions of the model and the experimental results. EXPERIMENTAL TECHNIQUE Essentially, the technique consisted of using helium-oxygen gas mixtures to oxidize levitated samples of liquid binary and ternary iron-base alloys. The fused silica reaction tube is shown in Fig. 1. The coil design is similar to that of L. A. Baker et al.4&apos;5 A Tef-lon-sheathed, ferritic stainless steel lifter (B) and an alumina pedestal (C) were used to support the sample in the coil prior to levitation and for the recovery of the sample. Samples were inserted into

Jan 1, 1970

By Ronald K. Linde

Metastable Ag-Cu solid solutions at two compositions beyond the maximum limits of solubility obtainable by quenching from the solid state were obtained by rapid quenching from the liquid state. The process of transformation of the metastable solid solutions into the equilibrium phases was studied by means of X-ray diffraction intensity measurements and electrical-resistance measurements; metallographic examination was also performed. Results are compared with those for an alloy quenched from the solid state at a composition which exists as a solid solution at elevated temperatures. Activation energies for the trans-formation were computed to be 33,600 * 2500 and 33,100 * 2000 cal per g mole for the 60.1 and 75.0 at. pct Ag;Cu compositions, respectively THE kinetics of precipitation in supersaturated solid solutions obtained by quenching from high temperature has been thoroughly studied in many alloys, and detailed investigations of the early stages of nucleation and subsequent growth of the equilibrium phases have been carried out. All of these studies have been made on alloys quenched from the solid state, however, and it is the purpose of this paper to present some of the results on the kinetics of transformation of metastable solid solutions in Ag-Cu binary alloys whose compositions lie outside of the solid-state limits of solubility. Limits of solubility in the solid state can be increased by rapid quenching from the liquid state. This was first demonstrated by Falkenhagen and Hofmann, who obtained appreciable increases in solubility limits of the elements of the first transition series in aluminum by rapid cooling of liquid alloys through contact with a copper mold maintained at liquid nitrogen temperature.&apos; The same basic idea of cooling a liquid alloy by conduction onto a substrate rather than by convection of a gas or liquid (conventional quenching) has been recently revived and extended to very high rates of cooling by Duwez and his collaborators. The new technique was first applied to Ag-Cu alloys because the existence of a eutectic in this system is not predicted by the Hume-Rothery rules of alloy phase formation. Rapid quenching from the liquid state resulted in metastable solid solutions at all concentrations. The kinetics of decomposition of these metastable solid solutions containing 60.1 at. pct Ag;Cu (eutectic composition) and 75.0 at. pct Ag;Cu is the subject of the present paper. EXPERIMENTAL TECHNIQUES Alloys were made in 10- to 20-g heats using silver of purity 99.99 pet and copper of purity >99.999 pct. Components were weighed accurately to 0.1 mg and melted by induction heating in an alumina crucible under an atmosphere of hydrogen. Weight losses amounted to less than 0.02 ~ct in all cases. Rapid cooling from the liquid state was achieved in an apparatus of the type described by Pietrokowsky. 3 In this technique a freely falling drop of molten alloy is caught between a stationary anvil and a fast moving piston, both anvil and piston being lined with copper. The resulting foils were approximately circular (about 2 cm in diam) and from about 50 to 150 u in thickness, depending on the pressure driving the piston. Metallographic samples were prepared for polishing by edge-mounting foils in Quickmount. The mostef-fective etching procedure was found to be: 10 parts NH4OH (concentrated), 1 part H2O2 (30 pct), 5 parts H2O, swab for 5 to 10 sec. The transformation of the metastable alloys to equilibrium was followed by X-ray diffraction and electrical-resistivity measurements. The peak intensity and the integrated intensity of suitable Bragg reflections of the metastable and stable solid solutions were studied with a Norelco dif-fractometer, using nickel-filtered copper KO radiation. The peaks were step-scanned at intervals of 0.05 deg. Using either a Kelvin bridge or a null circuit with a Leeds and Northrup K-2 potentiometer, the changes in electrical resistance due to phase transformation were measured for specimens cut into strips about 20 mm long and 4 mm wide. All resistivity measurements were carried out at liquid-nitrogen temperature. The isothermal heat treatment was accomplished by sealing the samples in argon-filled aluminum containers with stainless-steel O-rings. Containers were then suspended in wax baths with temperatures in the

Jan 1, 1967

By W. A. Jr. Slippy, E. P. Dahlberg, R. B. Reed-Hill

A large room-temperature mechanical-hysteresis effect under cyclic tensile loading was observed in zivconium specimens prestrained at 77°K so as to form large numbers of (1121) twins. The observed hysteresis loss was a maximum when the prestrain was just under 1 pct It also depended strongly on the maximum applied cyclic stress, but only moderately on loading rate and temperature (-72°to 100°C). The phenotnena have also been studied in terms of the elastic aftereffect where the data has been found to cotlforln closely to the functional relationship between strain and time, c = -RT/a In tank ft. t to)/Zr, for strains cts large as about 10-4 This eyication can be derived directly from the strain-rate equation There may be important commercial implications to the present discovery since it appears that within rather wide limits it may be possible to obtain any desired magnitude of damping capacity in zirconium melal. The damping propevties may also be given directional characteristics. It is shown that the observed anelaslic phenomena can he explained on the assumiplion that they are the resuilt of stress-induced twin-boundary movements in which the average twin increases its thickness by only a few percent. In polycrystalline zirconium, a grain is least favorably oriented for slip when its basal plane, containing the (1130) slip directions, lies nearly perpendicular to the principle normal stress. Mechanical twinning is favored by this orientation and under simple tensile deformation at room temperature the primary twinning mode is {1012).&apos; The (1012) twinning shear is small (0.17) so that, during deformation, twin growth does not greatly enhance ductility. At 77°K, on the other hand, the predominant twinning mode shifts to {1121), and many thin (1121) twins can form at small strains.&apos; Twins thus nucleated can grow readily during subsequent room-temperature deformation and permit easy deformation in unfavorably oriented grains. In addition, the (1131) twinning shear is large: 0.63. These facts have lead to a process&apos; for greatly improving the room-temperature ductility of zirconium when it contains a sizable fraction of grains with basal planes nearly normal to the stress axis. Optimum results are obtained by slightly less than 1 pct prestrain. The effect is large so that a 50 pct elongation increase is readily attained. A large room-temperature mechanical-hysteresis effect has also been observed in zirconium specimens prestrained at 77°K. The present paper is concerned with some aspects of this effect which the experimental observations strongly indicate is primarily the result of strain-induced {1121) twin-boundary movements. This clearly suggests that mechanical twins formed by plastic deformation can cause anelastic effects similar to those previously observed2 for annealing twins and twins associated with phase transformations. EXPERIMENTAL PROCEDURES All specimens were prepared from arc-melted sponge zirconium plate stock as previously described,3 which has a preferred orientation with basal planes aligned parallel to and uniformly distributed around the rolling direction. Both lonti-tudinal and transverse tensile specimens, with axes parallel and transverse, respectively, to the plate rolling direction, were cut from this plate. In a longitudinal specimen most grains are favorably oriented for slip, while in a transverse specimen a large fraction are unfavorably oriented. Prestraining at 77°K was performed in two ways. In one, annealed zirconium plate stock was cooled in liquid nitrogen and then rolled in the transverse plate direction to strains varying from 0.5 to 12 pct. Cylindrical 1/8-in.-diameter by 1-1/4-in.-gage-length tensile specimens were machined from this material. In the other, previously machined tensile specimens were prestrained in tension at 77°K between 0.2 and 3.8 pct. Type FA 25-12 SR4 strain gages were cemented to all specimen gage sections. All tests were performed on an Instron testing machine of 10,000-lb capacity. EXPERIMENTAL RESULTS Fig. 1 shows a typical two-cycle room-temperature stress-strain diagram for a specimen prestrained 0.65 pct by rolling at 77°K. The maximum stress in both cycles was 14,500 psi. Note that in the first cycle the loading and unloading curves are unsymmetrical so that a residual strain, er, remains after unloading. In the second cycle the stress-strain curves form a nearly symmetrical hystere-

Jan 1, 1965

By J. H. Waxweiler, L. C. Ikenberry, R. J. Bendure

Carbon which is present as insoluble carbides in austenitic stainless steels can be measured quantitatively by dissolving the steel in iodine-methanol and analyzing the residue for carbon. Severe sen-sitization was observed in Type 302 due to precipitation of only 0.003 pet carbon. Both cold work and the presence of delta ferrite caused a marked acceleration in rate of carbide precipitation. Carbide precipitation rates in 17-7 PH were stzulied for the austenite conditioning and also the aging heat treatment. CARBON and its compounds exercise a major influence on the properties of stainless steels and their response to thermal treatment. Sensitization in 18-8 type stainless steels has been the subject of numerous investigations throughout the years. Bain, Aborn, and utherford," and Binder, Brown, Frankss all studied the effects of heating austenitic stainless steels in the temperature range of 1000° to 1500°F. The primary purpose of most of these studies was the investigation of susceptibility to in-tergranular attack in acids due to these sensitizing heat treatments. Intergranular precipitation of carbides was always associated with intergranular attack but it was recognized2 that severe attack could occur with but minute quantities of precipitated carbide. Mahla and ielsen utilized the electron microscope to make a significant contribution in illustrating the appearance and method of growth of chromium carbides during sensitizing heat treatments. However, as they stated, their studies of residues could not be used to obtain a quantitative measurement of the amount of carbon which was actually precipitated. The aim of the present investigation was to devise a relatively fast, simple method for the quantitative measurement of carbides in stainless steel. EXPERIMENTAL WORK The initial investigations were made to determine the best means of separating carbides from the matrix. A number of dissolving media were tried using both chemical and electrolytic attack. Qualitative examination of the extracted residues by X-ray diffraction indicated that solution in iodine-methanol would furnish a good means of separation. Consequently, further work was pursued along this line. The method is quite simple. The sample in the form of millings or nibblings is dissolved in iodine-methanol solution at room temperature (6-g iodine, 25-ml methanol per g of sample). The insoluble residue containing the carbides is separated by suction filtration through an ultra-fine glass filter disc. This is a very fine filter medium that will retain particles as small as 0.1 to 0.2 p in diameter. After washing with methanol and drying, the filter disc and residue are placed in a conventional combustion carbon-tube furnace and the carbon determined gravimetrically. Using this technique it was found that reproducible insoluble carbon values were obtained. However, since such small amounts of insoluble carbon were obtained on Type 302 after sensitizatipn at 1250°F and 1500°F, the values were confirmed by a second method. In the second method the sample was dissolved with copper potassium chloride and filtered through a millipore paper. This treatment dissolves the matrix but leaves undissolved practically all of the carbon irrespective of how it is present in the steel. The amount of insoluble carbon present as chromium carbide is determined by calculation from the analysis of the residue for chromium and iron. The derivation of the formula used for this calculation is discussed later. The values obtained by the indirect copper-potassium-chloride method were in agreement with those obtained by the iodine-methano1 method. See Table I. It should be pointed out that the sensitivity of the direct combustion method is not too high when the amount of carbide present is small. This is due primarily to inherent blanks and to analytical errors such as weighing. For this reason it cannot be stated with any degree of certainty that there is a significant difference between values of 0.002 and 0.005 pct. Having confirmed that the iodine-methanol extraction gave a quantitative measurement of the precipitated carbides in Type 302, exploratory tests were conducted on Armco 17-7 PH stainless steel. Samples from commercial Heat 54807 were solution annealed at 2000°F, water quenched and heated at 1250" and 1500°F, and water quenched. The analysis of Heat 54808 is as follows:

Jan 1, 1962

By R. W. Armstrong, P. C. Jindal

The hardness dependence on grain size for polycrys-talline cartridge brass and a leaded brass has been measured by Brine11 and Rockwell B testing. In each case, the hardness, H, depends on the average grain diameter, 1, according to: H =Ho + kHl-1/2 where Ho and kH are experimental constants. Diamond pyramid hardness values have also been measured as a function of the indentation size and grain size to give additional information on the nature of the hardness test and the dependence of hardness on micro-structure. The hardness of polycrystalline brass depends on its grain size. Bassett and Davis&apos; demonstrated this as early as 1919 by making Brinell hardness measurements on cartridge brass. Since then, the hardness of this type of material has been measured as a function of grain size by making Rockwell,2&apos;3 Vickers,4 and Brinell5 tests. he hardness dependence on grain size has also been measured for other materials. Angus and summers6 investigated the grain size dependence of the Brinell hardness of polycrystalline copper and a Cu-4.5 pct Sn bronze. In other studies, nickel,? Armco iron,Big an Fe-0.07 pct C alloy,I0 and an 0.39 pct C-12.45 pct Cr stainless steel" have been investigated. In some of the preceding cases, the hardness results have been analyzed to show that the hardness varies with the average grain diameter, 1, according to an l-l\4, l-1/4 or I-2 dependence,11-13 The studies of the influence of grain size on hardness have not been based on any theoretical model. This may be because the hardness of a material is itself a complicated property. However, attempts have been made to correlate, experimentally and theoretically, the hardness of a material with its unidirectional stress-strain behavior.14-l6 On this basis, Hall" proposed that the polycrystal hardness dependence on grain size might follow directly from the Hall-Petch18,19 relation for the grain size dependence of the yield stress. Thus, the hardness-grain size relation was given as: H = Ho + kHl-1/2 [1] where Ho and kH were taken as experimental constants. The relation was applied to the measurements on brass,&apos; copper,6 bronze,= and Armco iron.&apos; More recently, this relation was shown by Armstrong and jindal20 to adequately describe the measurements on cartridge brass made by Bassett and Davis&apos; and Babyak and Rhines.5 In this case, the relationship was taken a step further by independently relating the values of Ho and kH to the values of oyand ky, previously reported by Armstrong, Codd, Douthwaite, and petch21 from measurements of the yield stress dependence on grain size for this type of material. In the present investigation, new Brinell and Rockwell B hardness measurements have been made as a function of grain size for a cartridge brass and a leaded brass. In addition, diamond pyramid hardness values were measured as a function of the indentation size. All these results are applied to a further analysis of the hardness dependence on grain size. MATERIALS AND EXPERIMENTAL METHODS Cartridge brass and a leaded brass were selected for this investigation for two main reasons: it was anticipated 1) that these materials could be cold-worked and recrystallized to a wide range in grain size and 2) that the results to be obtained on these typical industrial materials could be usefully compared with previous investigations. The chemical analyses of the actual materials which were employed are given in Table I. The as-received 1/2- and 3/4-in.-thick plates were given various reductions in thickness by cold rolling. The rolled material was heat-treated at various temperatures between 330" and 850°C for differing time periods from 5 min to 9 hr to achieve a variation in the average grain diameter between 0.0339 and 0.000543 cm.22 During heat treatment, the brass was protected from zinc loss by packing it in chips or foils of the same composition material. Reasonably equi-axed grain structures were obtained in each case. The metallurgical grain sizes of the specimens were determined from measurements of the average linear intercept on a random line. Annealing twin interfaces were not counted along with grain boundaries. The

Jan 1, 1970

By S. K. Basu, H. H. Kellogg

THE physical-chemical behavior of the system Pb-S-0 is of prime importance to the understanding of lead smelting processes, yet little accurate information is available on either equilibrium or kinetic behavior in this system. This paper is the first report of a program designed to fill gaps in our knowledge of this system. In the total ternary Pb-S-0, the region of greatest metallurgical interest is that bounded by the compositions Pb-PbS-PbS0,-PbO-Pb. Systems richer in sulfur, or richer in oxygen,* than those essentially pure SO2. This conclusion follows from the fact that all systems are in a highly reduced state, since either PbS or Pb is a constituent of all the equilibria. The content of 02, SO3, S2, S6, S8, and so forth, can be shown to be negligible compared to SO, in all such systems.* corresponding to this region can only be obtained at gas pressures exceeding 1 atm, a condition seldom met in lead smelting practice. Not only is the present study limited to condensed phases within this portion of the total system, but it is limited to temperatures at which all phases are pure solids, except for lead, which is liquid. In this limited system the following seven condensed phases are known to exist: Pb(l), PbS(c), PbO(c), PbSO,(c), PbSO,•PbO(c), PbSO4 • 2PbO(c), and PbSO, -4PbO(c). PbO exists in two crystal modifications,&apos; but only the high-temperature yellow form is considered here. Schenck and co-workers2-4 reported the compound PbSO4 3Pb0 to be stable at high temperature, but the more recent work of Lander,5 and the present work, prove that the tetra-basic sulfate, rather than the tri-basic sulfate is stable. Fig. 1 shows the composition diagram for the binary PbO-PbSO2, based primarily on the work of Lander. In this study the univariant boundaries and invariant points existing among these seven condensed phases and the gas phase have been determined. In a ternary system, the phase rule indicates that an invariant point involves the simultaneous equilibrium of five phases—four condensed phases and the gas phase. A univariant relation involves four phases—three condensed phases and the gas phase. The gas phase in the systems studied is The following stable univariant equilibria between SOz and the condensed phases were identified: (a) PbS + 7PbS04 = 4(PbSO, - PbO) + 4SO2 (b) PbS + l0(PbS04 • PbO) = 7(PbSO4- 2PbO) + 4SO2 (c) PbS + 8(PbSO4 • 2PbO) = 5(PbSO4 . 4PbO) + 4SO2 (d) Pb + PbSO, • 4PbO = 6PbO + SO2 (e) 3PbS + PbSO4 . 4PbO = 8Pb + 4SO2 (f) 3PbS + 16(PbS04 PbO) = 7(PbSO4 . 4PbO)+ 12SO2 (g) 2PbS + PbSO,2PbO = 5Pb + 3SO2 (h) Pb + 3(PbSO4 . 2PbO) = 2(PbSO,. 4PbO) + SO, Of these eight univariant equilibria, five were measured in this work (a, b, c, d, and g) and the behavior of the other three (e, f, and h) was calculated by thermodynamic analysis of the measured data. Two invariant points were found corresponding to simultaneous equilibria as follows: Point 1: PbS, PbSO4PbO, PbSO4.2PbO, PbSO, - 4PbO, and SO2 Point 2: Pb, PbS, PbSO, . 2PbO, PbSO, - 4PbO, and SO2, From the measurements it was also possible to calculate the thermodynamic properties of the three basic sulfates of lead at 298.16°K. EXPERIMENTAL Apparatus—The experimental method consisted of the measurement of the gas pressure exerted by a given reaction mixture at a given temperature. An iridium crucible was used to contain the reaction mixture. There was no evidence of attack of the iridium,* but after use at high temperature for a week

Jan 1, 1961

By H. Pew, J. H. Field

To alleviate pollution more restrictive legislation is being enacted, either limiting emission of pollutants or the type of fuel that can be utilized. The nature and magnitude of air pollution problems affecting the mining, preparation, coking and combustion of coal are described. Methods for combatting particulate emissions by use of mechanical separators and electrostatic pre-cipitors are discussed. Proposed methods to meet the problem of gaseous emissions currently receiving considerable attention are described, with special emphasis on methods to decrease pollution by sulfur oxides. Concern about air pollution goes back several centuries, but until very recently most effort has been aimed at coal smoke and other visible pollutants. The classic example of a &apos;successful&apos; campaign for smoke abatement and control is the fruitful combined effort of the city of Pittsburgh and its surrounding Allegheny County, which eventually led to the reconstruction of downtown Pittsburgh at an estimated cost of one billion dollars. Historically, the city&apos;s downtown Golden Triangle district had been afflicted by pollutants evolving from steel mills, from a variety of other industries, and from railroad locomotives. Efforts to alleviate the situation prior to 1943 were virtually ineffective. In 1945, however, a comprehensive redevelopment plan was prepared and backed by state authority. Within a few years a clean, modern metropolis has evolved where once stood America&apos;s famous &apos;smoky city.&apos; But the victory in Pittsburgh, as in various other American cities, has not solved the national problem. Current estimates indicate that 133 million tons annually of air pollutants from all sources still are emitted annually into the atmosphere above the United States. About 10% of this annual effluent is particulate matter so that most of the remaining pollution problems will be solved only when other effluents are reduced. Essentially, these are sulfur oxides, nitro- gen oxides, hydrocarbons, and carbon monoxide. Over the years, both states and local communities have tended to increase the restrictions on smoke and fly ash — problems mostly of concern in the combustion of coal. Prior to the middle 1950&apos;s, ordinances sometimes permitted emissions of smoke equivalent to as much as No. 3 on the Ringlemann scale. Since 1956, no ordinance has been passed which allows smoke of greater than No. 2. Under today&apos;s conditions of improved fuels, equipment and practice, a few communities have passed laws prohibiting emission of smoke of any density darker than Ringlemann No. 1. The majority of existing laws on fly ash emission in the U.S. limit emissions equivalent to 0.85 lb of fly ash per 1000 Ib of flue gas. In recent years, however, regulations which have been adopted give cognizance to the higher level of performance now obtainable with improved equipment. A comparison of the restrictions of five codes adopted since 1960 is given in Table I. The most stringent of these is the one for New York City which provides for a maximum emission of 0.6 lb fly ash per million Btu heat release (equivalent to roughly 0.51 lb/1000 lb of flue gas). The first comprehensive effort to restrict the emission of SO2 resulted from the passage of a 1937 law in St. Louis. This regulation stipulated that coal containing in excess of 23% volatile matter and 2% sulfur must be washed, thereby presumably producing some effective reduction in the input sulfur content. This was followed in 1949 by a Los Angeles County law which prohibited the emission of SO2 in concentrations greater than 0.2%. Most SO2-restrictive legislation passed since that date has been based on this limiting 0.2% SO2 by volume, although modifications are occasionally permitted under selected conditions, sometimes based on the fact that certain limiting ground concentrations are not exceeded — such as in the rules adopted by the San Francisco Bay area. To date, no legislation has been passed in the U.S. to limit the generation of nitrogen oxides from the combustion of fossil fuels. However, such oxides are considered to be of potential importance in air pollution control because of their possible detrimental effects on health and their reported role in the formation of photochemical smog. Interest in reducing oxides of nitrogen from powerplant and auto exhausts is increasing and regulations limiting their quantity can be expected in the future.

Jan 1, 1968

By W. B. Morrison

The principal factors influencing the total percent elongation of a lead-tin eutectic and several low-alloy steels which exhibit superplasticity were investigated. These factors are: a) Strain-rate sensitivity of the stress (m). b) Specimen geometry; in particular, diameter-to-length ratio (d0/l0), and surface irregularity (e.g. notches). A feature of the tensile deformation of a superplastic alloy is the early appearance of a neck which continues to extend throughout the test. As a result the total elongation is directly related to the diameter-to-gage-length ratio. The strain-rate sensitivity of the stress varies during extension, mainly because of microstruc-tural changes. A satisfactory correlation exists between the minimum strain-rate sensitivity and total elongation, as indicated in the equation shown below. Notches cause a considerable reduction in total elongation and their effect is greatest at high values of strain-rate sensitivity. An initial notch depth exists below which there is no appreciable effect on elongation. An equation relating elongation to strain-rate sensitivity and specimen geometry is proposed, THE total percent elongation of a tensile specimen is usually regarded as a measure of superplasticity. However, little attention has been given to the fact that total elongation is also a function of specimen diameter and gage length, even though the importance of geometry has long been recognized in the tensile testing of materials in which elongations are relatively small.* In the present study, the effect on superplas- tic extension of the ratio of specimen diameter to length was investigated and an analysis was made of strain distribution along the gage length. Superplastic alloys are characterized by having a flow stress sensitive to strain rate but relatively insensitive to strain.2"&apos; In an earlier study,5 it was found that the strain-rate sensitivity of several low-alloy steels changed during the test and that the minimum value correlated best with total elongation. In the present study, the variation of strain-rate sensitivity during the straining of a lead-tin alloy was investigated. EXPERIMENTAL PROCEDURE Lead-tin eutectic alloy (32 pct Pb 68 pct Sn), made from high-purity lead and tin, was cast in the form of 1-in. diam rod. The rod was cold-rolled in stages to 0.25 in. diam and then swaged to 0.125 in. diam. Samples were cut from the rod at various stages of the mechanical working process. Tensile test specimens were then made by attaching threaded steel ends to the rods by an epoxy-base thermosetting adhesive which required a setting treatment of 2 days at room temperature. The rods were seated in the steel ends in holes approximately 0.01 in. oversize. The test pieces thus made were of various diameters and gage lengths. These were stored at a temperature of about -70°C (-94°F) until required for testing. The distribution of strain along the gage length of a specimen was determined at various stages of the tensile test. The lead-tin alloy was superplastic at room temperature and direct observations during testing were simple. The gage length was divided by reference marks into five initially equal units. These reference marks were made with ink and were reinforced during the test when the initial marks became faint. Photographs were taken, at intervals, of the deforming specimen and measurements of the elongation in each of the gage units were made on these photographs. Tests were also done on several superplastic low-alloy steels whose properties were described earlier.5 The chemical compositions of these steels are given in Table I. A diagram of the notched tensile specimen used in the steel tests is shown in Fig. 1. The specimens were tested at 900°C (1650°F) in a furnace through which a mixture of He + 2 pct H was continuously circulated.5 RESULTS Strain Distribution. Approximately 20 tests on lead-tin alloy specimens were conducted to determine the strain distribution during the test. An example is shown in Fig. 2 of the strain distribution in the gage

Jan 1, 1969

By O. D. Sherby, J. E. Dorn

For elevated temperature-constant load creep tests of a solid solution alloys, the creep strain is a function of a temperature-compensated time parameter 0 = je H/RT dt. The activation energy H is equal to o constant of about 36,000 cal per mol. The substructures resulting from a given creep stress condition are functions of the creep strain independent of temperature. Each new creep stress gives a new unique set of grain substructures; this is one of the factors responsible for the failure of the mechanical equation of state for creep. IN this report an attempt is made to correlate the creep properties of dilute a: solid solutions in aluminum with the subgrain structures that are developed during creep. The possibilities of such correlations have already been suggested by Wood et al. and others1-" who demonstrated that the subgrain structures are functions of the creep stress, creep strain, rate of creep, and temperature. Investigations by Sherby and Dorn&apos; have shown that the creep strain, E, at constant load for dilute a solid solutions of aluminum is given by the functional relationship: e = f(8,u,) [1] where: 0 equals te-AH/RT = temperature-compensated time; t, time; AH, activation energy, - 35,800 cal per mol; R, gas constant; T, absolute temperature, above 400°K; and u,, initial creep stress. Consequently, it was anticipated that the subgrain structure that develops during a constant load creep test should also correlate with any two of the three significant variables C, 8, and Another possible correlation between the subgrain structure and the creep variables is obtained by differentiating Eq. 1 with respect to time, whence the creep rate, 2, becomes: = (2L) (2) =f (, u,) e-AHRT [2] or: e = F (c e H/RT, 0) [3] For the minimum creep rate, ;,, 8 is solely a function of U, as revealed by Eq. 1. Consequently, at the minimum creep rate Eq. 3 reduces to: = F (eAH/RT) [41 Correlations between U, and i, eAH/RT were found valid for solid solution alloys of aluminum where AH was a constant of about 35,800 cal per mol. The parameter ;, eH/RT is identical to the Zener-Hollo-mon parameter8," used by them in evaluating the tensile properties of copper and other metals. Eq. 4 suggests that the subgrain structure developed during secondary creep might be correlatable with either of the two variables 2, e H/RT or u,. Some of the solid solution aluminum alloys which were discussed in an earlier report&apos; were also used in the present investigation. Sheets of these alloys were homogenized, cold rolled from 0.100 to 0.070 in. in thickness and then recrystallized to about the same grain size. Their chemical composition and grain size are recorded in Table I. Creep specimens were selected with their tensile axes in the rolling direction. The details for creep testing have been described10 and will not be repeated here. All creep tests were performed under constant load conditions. Experimental Results and Discussion Metallographic Structure of Creep Specimens: In order to obtain a preliminary concept of creep on the metallographic structure of high purity aluminum, the various ruptured specimens previously used to obtain the creep data for pure aluminum were polished and etched electrolytically in a dilute solution of fluoroboric acid. Oblique illumination was used to reveal the substructures which, for convenience, are shown in correlation with the vs. ;, eH/RT curve in Fig. 1. It is necessary to emphasize that the data for the curve refer to the various secondary stages of creep whereas the micrographs refer to the fractured creep specimens. Nevertheless a regular and systematic correlation is observed between E, eAH/RT (or the creep stress) and the micro-structure at fracture. For In (e, eAH/RT) = 42.3, which refers to creep at a high creep rate and a low creep temperature, the fractured aluminum specimen, as shown by the micrograph in the upper right-hand corner of Fig. 1, exhibited extensive deforma-

Jan 1, 1954

By R. F. Sheldon

The discovery of the Carlin deposit was the result of discriminating geologic research and prospecting devoted to the objective of finding a gold deposit that could be mined by open pit methods. By the late 1950s, Newmont Mining Corp. was becoming increasingly concerned about the trend of rapidly rising underground mining costs unless bulk mining methods could be applied. The desirability of finding an open-pittable gold deposit was apparent. The attention of Newmont geologists was directed to Nevada by the publication of two papers: "Paleozoic rocks in North-central Nevada" (1958) and "Alinements of Mining Districts in North-central Nevada" (1960), both authored or co-authored by Ralph J. Roberts of the United States Geological Survey. John Livermore, geologist of Newmont Exploration Ltd., attended a talk given by Roberts in Ely, Nevada in the summer of 1961. These papers and the address by Roberts gave details concerning the Roberts Mountain overthrust, a 483 km (300-mile) long, shallowdipping fault which pushed clastic and volcanic rocks of early and middle Paleozoic age eastward over younger marine formations. Subsequent uplift and doming with consequent erosion had locally removed the upper plate strata exposing windows of lower plate carbonate rocks. Roberts noted that the principal mineral deposits of the region, including gold, were associated with these windows which exhibited a preferred alinement. In the summer and fall of 1961 Newmont&apos;s exploration geologists John Livermore and J. Alan Coope began a systematic examination of gold occurrences associated with these windows, aided by further discussion with geologists of the US Geological Survey. Attention was directed to the Lynn and Carlin windows, particularly to those formations lying immediately above and below the Roberts Mountain fault. It was appreciated at the time that many of the gold occurrences in the region were unusual in that no colours were obtained even when panning high grade samples. A large number of rock samples were collected and analysed using fire assaying procedures, and background values for gold were established. This systematic rock sampling resulted in the identification of a distinct area of anomalous gold values, and a block of claims was staked in late October, 1961. These claims, plus an adjoining optioned 32.4 ha (80 acres) of ground, cover the main area of the present Carlin gold mine. Prior to snowfall that winter, one of the bulldozed assessment pits required to establish a claim&apos;s discovery exposed 24 m (80 ft) of mineralization assaying 0.007 kg/t (0.22 oz per st) gold. In the spring of 1962 a program of trenching, sampling, and geological mapping followed by rotary drilling was underway. Other properties in the area were acquired. The generally undistinguished nature of the dolomitic siltstones and silty dolomitic limestones hosting the micron-sized gold particles, coupled with the lack of visually associated guide minerals, made identification of the gold bearing areas very difficult. The entire drill column had to be assayed to ensure that values were not overlooked, as very often sections that might be assumed to be waste turned out to be high grade. On September 10, 1962 a high grade intersection of 24 m (80 ft) assaying over 0.03 kg/t (1 oz per st) gold was encountered in the third hole drilled. An expanded program of both rotary and diamond drilling led to the further delineation of the ore body. By December 1963, the exploration program had established an initial reserve of 10 Mt (11 million st) grading 0.01 kg/t (0.32 oz per st) gold. A 1.8 kt/d (2,000 stpd) processing plant was constructed and the first gold bullion was poured in May, 1965, just two years and eight months after the discovery hole was drilled. REFERENCES Roberts, R.J., Holz, P.E., Gilluly, J., and Ferguson, H.G., 1958, "Paleozoic Rocks in North-central Nevada," Bulletin American Association of Petroleum Geologists, Vol. 42, No. 12. Roberts, R.J., 1960, "Alinements of Mining Districts in North-central Nevada," Professional Paper 400-B, US Geological Survey, Article 9.

Jan 1, 1985