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By Carl J. McHargue

Rods of 99.99 + pct Al which had initial orientatzons of <001>, <118>, <115>, <111>, and random were swaged at room temperature. Changes in orientation as a function of deformation were studied on axis distribution charts. The <001> orientation appeared to be relatively stable due to the inhomogeneity of the deformation process. near the <100> zone were quickly reoriented towards <001>. Orientations on the <110> zone between <118> and <115> appeared to be stable to reductions of about 50 pct, then were reoriented toward <001>. At very high reductzotzs. movement away from the <111> orientation was observed. the requirement that a circular cross section be maintained. In addition to these mechanical factors, there are grain-boundary effects in poly crystalline materials which are not yet understood. Hartmann and Macherauch conclude, for example, that multiple slip occurs for all orientations in fine-grained aluminum and copper and that the choice of operative slip systems has no simple relationship to orientation.? Many investigators have attempted to avoid problems of interpretation caused by an initial texture by treating the starting material to obtain as ran- IT has been generally accepted that the deformation texture obtained at high reductions, e.g. 90 pct, will not be noticeably affected by a prior texture; whereas, that obtained at reductions of 40 to 50 pct may be significantly influenced by the specimen history.&apos; Some recent studies, however, have been interpreted as showing that an initial texture strongly influenced the deformation textures in rods at reductions greater than 90 pct. Freda and Cullity suggested that the <001> texture in a heavily cold-worked copper rod was due to a <001> texture in the original casting. McHargue, Jetter? and Ogle concluded that the <001> component in an aluminum rod extruded at liquid nitrogen temperature was remanent from a <001> texture in the cast extrusion billet.3 Most of the published work on the effect of initial orientation on deformation textures has been for cold-rolled or compressed single crystals,4-6 The primary interest in these studies was to examine various orientations with regard to their stability under flow? thus determining the possibility of such orientations being stable end orientations. There appears to be no published studies on the effect of initial orientation on fiber textures in polycrystalline specimens. A recent study, however, is concerned with the reorientation of individual grains in polycrystalline specimens pulled in tension.? Although the reorientation of single crystals loaded in simple tension is well known, the movements in the forming of wires and rods would be expected to be different due to the circular array of radial-compressive stresses exerted by the die walls or the rolls, and to

Jan 1, 1962

By W. C. Winegard, E. L. Holmes

The effects of the solute elements lead and bismuth on grain growth in zone -refined tin have been investigated. At low temperatures, viz. below 160°C. or at high concentrations, viz. greater than 0.03 at. pct, the temperature dependence of grain growth was found to be constant. A correlation was found to exist between the rates of grain growth in the presence of solute impurities and the factor [C Ir - 1]2 , where C is the solute concentration, r is the radius of solvent atom, and r&apos; is radius of solute atom. It is shown that the Liicke and Detert theory does not give a satisfactory explanation of the results obtained. INVESTIGATIONS of grain growth in zone-refined lead and tin and some effects of solute elements on grain growth in these metals have been reported by Bolling and winegardly2 and Holmes and winegard? The present investigation is an extension of the previous work, and was undertaken to provide additional results which might make it possible to discover the mechanism whereby the rate of grain growth is affected by the presence of foreign solute atoms. The experimental procedure was exactly the same as that described previously.3&apos;4 Figs. 1 and 2 show the results obtained with lead and bismuth additions over the same temperature range, viz. 167" to 220°C, as that used for the investigation of grain growth in zone-refined tin.3 Fig. 3 shows the results obtained for zone-refined tin and for this tin with lead solute additions over an extended temperature range. DISCUSSION OF RESULTS As mentioned previously,3 the character of grain growth in the particular zone-refined tin used in these experiments appears to change as the temperature of annealing falls below about 160°C. The grain growth became somewhat irregular and was characterized by a jaggedness of many of the grain boundaries. The reason for this change is not known, but may be due either to residual impurity effects or possibly an oxide precipitation. It was obvious that normal grain growth only occurred in the zone-refined tin through the high-temperature range 167" to 220°C, and so the effects of solute atoms on grai11 growth over the two temperature ranges will be discussed separately. a) Effect of Impurity on Grain Growth in the Temperature :Range Above 167°C. It is apparent from Figs. 1 and 2 that, for low concentrations of solute, the rates of grain growth tend towards a common value as the melting temperature of tin is approached. As the concentration of lead is increased, the rate of grain growth close to the melting temperature is also reduced, and at high concentrations the temperature dependence of the rate of grain growth appears approximately constant. It should be noteil that the effect of bismuth is greater than that of the same concentration of lead, but both these solutes have a smaller effect on the rate of grain growth than silver, as seen from an earlier investigation of Holmes and Winegard. It should

Jan 1, 1962

By J. L. Lytton, T. E. Tietz

UNALLOYED arc-cast molybdenum sheet is typically supplied in the cold-rolled and stress-relieved condition, hereinafter denoted CRSR. Such processing eliminates the yield-point phe-

Jan 1, 1964

By Charles Wurms, Robert Steinitz

DURING an investigation to determine the compatibility of several metals with tungsten, the degree of reaction between tungsten and lead was determined. A literature survey showed considerable disagreement between the results of various earlier investigators. Information presented by M. Hansen1 states that, according to S. Inouye,2 tungsten has very poor resistance against attack by molten lead, even at the low temperature near the melting point of lead. A phase diagram in the same reference indicates a solubility of 30 wt pct W in molten lead at 1300°C. Contrary evidence was shown by Parkman and shepard3 in their investigation of materials for use in heat transfer systems containing liquid lead alloys; they performed experiments at 980°C for times up to 50 hr without noticing any appreciable attack on the tungsten. Tungsten sheet was immersed in molten lead contained in Vycor tubes evacuated to at least 10-4 mm Hg. R. Bernard4 and R. I. Jaffee5 also indicate that no reaction occurs between molten lead and tungsten. However, no experimental data were included in these reports. In order to settle the question of the solubility of tungsten in molten lead, tungsten powder with an average Fisher subsieve particle size of 6µ was pressed in a double-acting die at 6 tsi to small compacts. They were then sintered in an atmosphere of hydrogen for 2 hr at 1700°C, resulting in a sintered density of 64 pct of theoretical with final dimensions of 0.260 in. in height and 0.245 in. in diameter. For all tests, the tungsten pellets were immersed in molten lead. Table I is a summary of the experimental procedures showing atmospheres, temperatures, and times. The first experiments were performed at 650°C; at this temperature, the liquid lead should wet the porous tungsten better than at its melting point, and penetrate into the pores. The lead was heated in a graphite crucible with a graphite cover. No protective atmosphere was used, as it was expected that the formation of CO would be sufficient to prevent oxidation. This, however, proved to be wrong, and all tungsten samples showed a slight oxide film after treatment. The tungsten samples were immersed in the molten lead for times of 5 min, 10 min, 1/2 hr, 1 hr, and 2 hr. After this time, the melt was poured into a form and the

Jan 1, 1962

By J. L. Brimhall

Slip-line formation during bending has been studied on neutron-irradiated molybdenum single crystals. For equivalent strains, the slip lines are coarse and distinct in the irradiated molybdenum and not resolvable in the unirradiated molybdenum. The slip lines have been directly correlated with dislocation channels present in the irradiated and deformed thin foils. The heterogeneous distribution of the dislocations during deformation in the irradiated material results from dislocation interaction with the dejects produced during irradiation. Impurities , in the form of&apos; carbides, affected the dislocation channeling Principally by acting as dislocation sources. ALTHOUGH the mechanical behavior of irradiated materials has been studied extensively, the precise mechanism of irradiation hardening has not been established. Some information on the microstructural species responsible for hardening of irradiated materials has been derived from direct and indirect observations. The direct observation of the structure of deformed irradiated metals, particularly by transmission electron microscopy, is a relatively new and unexplored area. Slip-line studies in fcc metals have been restricted primarily to copper.1-3 Very coarse slip lines, representing slip on many closely spaced planes, have been observed in deformed, irradiated copper. Coarse slip lines have also been observed in irradiated aluminum.4 Clear channels in irradiated copper caused by dislocation motion through the defect structure have been seen by transmission electron microscopy and correlated with slip lines.5-6 To date, little work has been reported on the irradiated bcc metals. Eyre described the slip lines around hardness indentations on irradiated iron and found them to be more distinct than lines in unirradiated material.&apos; Mastel et al.&apos; have observed channels in deformed irradiated molybdenum similar to those reported in copper. As part of a program concerned with the effect of neutron irradiation on metals, the slip-line

Jan 1, 1965

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 O. N. Carlson, K. E. Solie

The brittle-ductile transition temperatures of single and poly crystalline chromium metal were studied as a function of nitrogen concentration and chromium nitride distribution. It was observed that In recent years there has been an increasing interest in chromium-base alloys for high-temperature applications. The principal disadvantages, however, have been the difficulties of fabrication and the design problems associated with a material of such limited ductility. Various studies have been the effects noted in the poly crystalline material are essentially reversed in the single crystals. These observations are discussed in terms of existing theories for the brittleness of chromium. conducted recently directed toward a determination of the cause of this brittleness and to find ways for minimizing its effects. Allen et al.,&apos; Wain Abrahamson and rant,&apos; and weaver4 have carried out studies on the effects of interstitial impurities on the brittle-ductile transition of chromium metal of various degrees of purity. These investigations have shown that oxygen has little or no effect on the transition temperature of chromium in all conditions studied but that carbon increases the transition temperature under all conditions tested. Nitrogen was found to increase the transition temperature in the wrought condition and in the quenched or cast conditionS but reportedly has no effect in the furnace-cooled condition.

Jan 1, 1964

By J. B. Clark, A. J. McEvily, R. L. Snyder

The nonuniform distribution of precipitate particles has been recognized as a leading factor contributing to the relatively low fatigue resistance of aluminum alloys. The structure of many of these alloys is characterized by narrow precipitate-free zones adjacent to the grain boundaries. Alloys with such zones exhibit a tendency for brittle inter crystalline fracture. The interrelation between this type of structure and mechanical properties was investigated in an Al-10 wt pct Mg alloy. It was found that deformation during fatigue occurs preferentially along these zones and cracks initiate there. In Al-10wt pct Mg, the zones were found to be supersaturated even after extensive general precipitation and are due to the absence of proper precipitate nuclei in the region near the grain boundaries. Cold working the alloy prior to aging improves the mechanical properties by inducing precipitation within the zones and also by jogging of grain boundaries. The mode of fracture is changed from brittle inter crystalline to more ductile trans granular fracture. THE process of fatigue is highly structure sensitive, with the strength of the whole often dependent upon some localized discontinuity, either geometrical or metallurgical in nature. Much has been learned about the role of geometrical discontinuities, e.g., notches, in fatigue, but with the exception of the effects of inclusions or the shapes of carbides, relatively little is known about the specific effects of discontinuities in metallurgical structure such as nonuniform precipitation. In most age-hardening aluminum alloys, metallo-graphic studies have shown that the extent of precipitation adjacent to grain boundaries is much less than that which occurs in the interior of the grains. The width of these almost precipitate-free regions, which are sometimes called denuded zones, and the extent of solute depletion within them, are dependent upon the particular alloy and its aging treatment. It has been observed1 that these zones are relatively soft with the result that plastic deformation takes place preferentially within them. It has also been shown 2-4 that there exists a tendency for intercrys- talline cracking in fatigue when such zones are present. It is of interest to note that Broom et al.2,3 were able to reduce the incidence of this type of failure in an A1-4 wt pct Cu alloy by stretching the material 10 pct prior to aging. In the present study, the effects of precipitate-free regions on the fatigue properties of an A1-10 wt pct Mg alloy were studied in detail, and the effects of deformation prior to aging on the nature of the precipitation process as well as on fatigue properties were also investigated. MATERIAL AND PROCESSING An A1-10 wt pct Mg alloy was selected for this study, because it was known that well-defined precipitate-free regions along the grain boundaries are readily obtained in this alloy after aging at 200oC.5 The starting materials were 99.998 pct A1 and singly sublimed magnesium of about 99.9 pct purity. The aluminum was induction melted in a graphite crucible, and then the magnesium addition was immersed until dissolved. Chlorine gas was then bubbled through the molten alloy for 4 min to degas the melt, after which the melt was cast at a pouring temperature of 730" to 760°C into a cold, graphite-coated, tapered steel mold. Since A1-Mg alloys are difficult to homogenize,5 special care was taken to obtain a uniform composition. Two-in. cubes were cut from the ingot and heated at 446°C for 30 min. These cubes were then hot forged approximately 35 pct in each of the three cube directions and homogenized for 16 hr at 446°C. Sheet specimens were then obtained by pressing 40 pct and rolling 35 pct per pass with reheating between reduction steps to a final thickness of approximately 0.10 in. The sheet was then solution treated for 16 hr at 446°C and water quenched. The age hardening behavior of this material at 200°C was then determined, and the results are shown in Fig. 1. The age hardening of this alloy when subjected to cold work prior to aging is also shown in this figure. Preliminary work indicated that extensive deformation after quenching was required to affect drastically the precipitate-free regions in this alloy, and a rolling reduction of 50 pct was chosen. For purposes of comparison the following three conditions were studied: a) Solution treated, quenched, and aged 20 hr at 200°C

Jan 1, 1963

By C. G. Dunn, F. Lionetti

The energy associated with grain boundaries in polycrystalline aggregates is believed to play a major role in grain growth processes and, when growth ceases, to determine the final equilibrium grain boundary angles. Further, the energy of grain boundaries of recrystallization nuclei is a factor in nucleation processes. It is important to know, therefore, how the energy per unit area of a grain boundary, that is, the grain boundary surface tension y, depends on the difference in orientation of the two lattices of the grains producing the boundary. Although the problem is important, surprisingly little has been done toward a quantitative evaluation of the effect of orientation difference on grain boundary energies. C. S. Smith1 recently has discussed this problem and in addition to showing effects of orientation difference on equilibrium angles has shown a variety of interesting effects of surface tension on the appearance of microstructures. Fig 1 and the following relations expressed in Eq 1, which connect equilibrium grain boundary angles and surface tensions, illustrate equilibrium conditions which are believed to hold true in metals. ?l2 _ ?23 _ ?l3 [1] sin ?3 sin ?1 sin ?2 Clearly any two of these surface tensions can be expressed in terms of the third when the equilibrium angles ?1, ?2, and ?3 are known. Applied to the present problem for solid state equilibrium of three grains, the angles ?1,?2 and ?3 must be measured in a plane perpendicular to the line of junction of the three grains. Normally a direct determination of these angles from random microsections is impossible. Consequently Harker and Parker2 and Smith1 (except for some measurements on flat specimens) resorted to a statistical method to determine equilibrium grain boundary angles. Smith reported that grain boundaries meet the surface of a piece of metal nearly perpendicularly. He reported also, in connection with direct angle measurements on flat specimens with grains extending through the thickness, that angles varied appreciably from 120" and concluded that there was a measurable effect of orientation difference on surface tension. Another direct way of determining equilibrium angles and a method adaptable to studying particular configurations, recently suggested by Dunn,³ is to use a three-grain flat specimen with orientations of grains so chosen that the junction line of the three grains will be straight throughout the thickness and perpendicular to the surface of the specimen. Choice of orientations is possible when individual grains of each group can be grown to predetermined orientations through the reorienting and growth of " seed crystals " as described.³ Not only is it possible, for example, to have grains with the same crystallographic plane in the plane of the specimen, but a given orientation difference between two grains can be made a common factor to an unlimited number of three-grain groups while a series of orientation differences is investigated. Any effect of anisotropy of gas-solid surface tension due to grain orientation should be minimized by having all gains oriented the same with regard to crystallographic plane in the plane of the specimen. Another feature of the three-grain group is the notched grain boundaries as shown in Fig 2 for one specimen (S4). The notches serve to anchor the end positions of the grain boundaries (especially at high temperatures) while the central and junction point of the grains moves toward an equilibrium position. Final equilibrium should produce straight grain boundaries if the notches are very narrow and if changes in orientation* of the grain boundary do not alter the surface tension.† If one assumes the straight line condition and no change of surface tension with small changes in grain boundary orientation and finds the equilibrium configuration by a minimization of the grain boundary energy, one obtains the relations given in Eq 1. The approach to straight line boundaries or to minimum energy configurations in specimens containing large grains, such as those used in the present investigation, may be very slow compared with the approach to equilibrium conditions for the grain boundary angles. It may be desirable, as proved to be the case in the present investiga-

Jan 1, 1950

By C. G. Dunn, F. Lionetti

W. G. BURGERS*—It seems almost certain that this investigation shows the way which finally, when more analogous data have been obtained, must lead to the understanding of many features of preferential growth-directions of crystals and of the occurrence of recrystallization textures. In this connection I should like to mention that Mr. Tiedema in my laboratory succeeded in developing an analogous method for preparing crystals in aluminum plates with a chosen crystal-lographic plane and direction parallel to the surface of the plate (to be published in Cryst. Ada). If such crystals were grown in high purity aluminum and test-pieces containing a few crystals such as the authors describe were prepared for this metal, it might be possible that due to the absence of growth obstructing particles, even in this low-melting point metal boundary displacements approaching equilibrium positions might be realized. With regard to the apparently marked drop in surface energy for orientation differences approaching zero degree, and orientation differences approaching those existing between twins, it seems of interest to remark that in aluminum a crystal growing at the expense of fine grained material cannot (or can only very reluctantly) absorb grains in either ap- proximately (within 5—10°) parallel or spinel twin orientation (May, Tiedema and Burgers, Nature (1948) 162, 740 and Cryst. Ada in press). Consequently with aluminum the method of preparing a crystal with a definite orientation does not succeed when the new crystal has to absorb its own texture; for example it is not possible to grow in a polycrystalline wire with a [lll]-texture a crystal with a [11 Indirection parallel to the wire axis (Tiedema: Cryst. Ada, in press). Finally I should like to mention the well-known fact (Burgers: Proc. Acad. Amsterdam (1947) 50, 723) that prolonged annealing of recrystallized nickel-iron sheet with cube-texture never succeeds in transforming this into one single crystal of the same orientation; if, by "secondary re-crystallization," large crystals are formed

Jan 1, 1950

By C. H. Li, S. H. Bendel, J. A. Sartell

Small additions of Mg to a 62 Cu-38 Ni alloy reduce the oxidation yates drastically between 500° and 850°C. Metallographic examination of the oxide scale disclosed a continuous network, identified by X-ray diffraction as (Ni, Mg)O solid solutions, located along the former alloy grain boundaries. This network acts as a barrier to diffusion. It is thought to result from the segregation of mg to the alloy grain boundaries. Oxidation occurs preferentially in these regions because of the presence of this more active element. To substantiate these ideas, homogenized alloys ulere oxidized. No oxide network was produced and oxidation rates were the same as for the parent 62 Cu-38 Ni alloy. An interesting aspect of the oxidation of the 62 Cu-38 Ni alloy previously described by the present authors, is the relationship between oxidation kinetics and changes in the microstructure of the oxide.&apos; The oxide scale on these alloys consists of two layers: a thin layer of CuO outside a much thicker layer of Cu20 in which particles of NiO are dispersed. In addition, immediately beneath the oxide-metal interface there is an internally oxidized zone in which NiO particles are dispersed in a copper-rich alloy matrix. Experimental observations on the growth of the individual layers under isothermal conditions have led to the conclusion that the rate-determining step in the oxidation of this alloy is the diffusion of anions through the Cu20 layer. It has been found that this diffusion rate is increased by the recrystallization of the outer CuO layer. Willardson and Gorton have reported that the addition of magnesium to the 62 Cu-38 Ni alloy causes a decrease in the oxidation rate.2 The present investigation was undertaken in order to determine the mechanism by which magnesium additions improve the oxidation resistance of the 62 Cu-38 Ni alloy. EXPERIMENTAL PROCEDURE Fifty-gram ingots of Cu-Ni alloys were prepared by vacuum melting materials of 99.999+ pct purity. These ingots were then remelted in a He atmos- phere and magnesium added in the form of a previously prepared and analyzed Cu-Mg master alloy. This procedure was necessitated by the high reactivity of pure magnesium at high temperatures. The proportion of the alloying elements was adjusted so as to obtain alloys with the desired magnesium content while maintaining a Cu-Ni ratio of 62 :38 by weight. (All alloy compositions will be given in weight percent.) Since it was considered desirable to study the oxidation of only single-phase, solid-solution alloys, it was necessary first to determine the approximate limit of solid solubility of magnesium in the 62 Cu-38 Ni alloy. A series of melts with various magnesium contents was made, homogenized by annealing for 48 hr at 975OC, then cooled in the furnace. Metallographic samples were prepared, etched in a potassium dichromate solution and examined at XI500 for the presence of a second phase. The alloys were then chemically analyzed and it was found that the approximate limit of solid solubility of magnesium in the 62 Cu-38 Ni alloy was 1 pct Mg. The ingots containing less than 1 pct Mg (0.19, 0.29, 0.58, and 0.87 pct Mg) were cold-rolled down to thicknesses suitable for oxidation experiments and specimens for gravimetric studies were cut to dimensions of 3.0 by 1.5 by 0.05 cm, specimens for inert marker studies, 0.6 by 0.6 by 0.17 cm. These were heat-treated in a protective atmosphere at a temperature (975" C) well above the oxidation temperatures and furnace-cooled to insure structural stability of the alloy during oxidation. Immediately prior to oxidation, the specimens were chemically cleaned by immersion for 1 min in a solution of 2 parts nitric acid, 1 part acetic

Jan 1, 1961

By N. A. D. Parlee, I. D. Shah, W. C. Phelps

THIS note reports on a continuation of a program on the thermodynamics of Fe-S-X systems in the "steel-burning" temperature range begun by Bock, Barloga, and parlee.&apos; Small coils of 0.039-in.-diameter pure iron (Ferrovac-E) wire were equilibrated with Fe-S-0 melts in ingot iron crucibles under argon at 1324°C in the assembly shown in Fig. 1, the lower part of which was heated in a large Globar furnace. Fig. 1 shows (R) the coiled iron wire sample, (M) the Fe-S-0 melt prepared from desired proportions of ferrous sulfide and ferric oxide, (K) the iron crucible, (I) a mullite guide tube, (J) an alumina crucible, (L) alundum sand, (N) crushed mullite, (Q) hollow cylinders of K30 brick, (C) a steel rod, (B), (El, (F), (G), (P), and (O), details of brass water-cooled head, and (H) a mullite tube 2-3/4 in. ID and 26 in. long. The rod (C) bearing the sample could be removed at will and be replaced by a tube for sampling the melt, or by a thermocouple for comparing the melt temperature with a control thermocouple not far from the 2-3/4-in. mullite tube. After equilibration the iron coils were treated with acid to remove the outer layer of metal and then they were analyzed for sulfur by a standard combustion method. The melt samples were analyzed for oxygen by a variation of Lander&apos;s2 hydrogen-reduction method for mattes, and for sulfur by the ASTM combustion-iodometric method NO. E 30-47. When the results of some forty-two runs were examined it was found that the sulfur and oxygen contents of the equilibrated melts showed good consistency, in that the plotted compositions fell along the smooth curve shown in Fig. 2. The points on this curve represent the experimental compositions of melts in equilibrium with ?-iron (Fe-S-0) solid solutions. These solid solutions are saturated with sulfur and oxygen with respect to the melt and therefore have the same sulfur and oxygen activities as the melt. The curve drawn through the points therefore delineates the ? liquidus. It falls in such a position as to roughly confirm the liquidus curves of Hilty and crafts3 at 1200" and 1300°C which are

Jan 1, 1965

By W. C. Winegard, C. Feng, C. Elbaum

SEVERAL investigations have been made concerning the effect of oxygen on the mechanical properties of titanium 1-6= In particular, the yield strength has received considerable attention. Finlay and snyder2 report a 0.2 pet strain offset yield strength if 49 kg per sq mm in titanium containing 0.1 pct 0 and 61 kg per sq mm in titanium with 0.2 Pct 0. These results are in good agreement with those of Jaffee, Odgen, and Maykuth3 who report values of yield strength

Jan 1, 1960

By I. E. Campbell, R. I. Jaffe

Oxygen, nitrogen, and hydrogen are known to be absorbed by titanium at elevated temperatures. Ehrlichl reports that about 30 at. pct oxygen can be dissolved in solid solution by alpha-titanium. Nitrogen also has a solid solubility in alpha-titanium, but there is no information as to its extent. The solid solubility of hydrogen in titanium also is high. Kirshfeld and Sieverts2 report 50 at. pct soluble, while Hägg3 reports about 33 at. pct hydrogen to be soluble in alpha-titanium. General statements are made in the literature that oxygen, nitrogen, and hydrogen embrittle titanium, but no quantitative measurements have been made of the effect of these gases on the mechanical properties of the metal. One reason for this is the lack of a source of titanium pure enough to be considered a suitable starting material. Iodide-refined titanium, made by thermal decomposition of titanium iodide vapor on an incandescent wire,4 contains small amounts of carbon, silicon, iron, and aluminum, but is very low in oxygen, nitrogen, and hydrogen content, and, therefore, was used in this work. A further reason for the lack of quantitative information on the effect of these gases, particularly oxygen, is the difficulty of carrying out accurate analytical determinations at the low concentrations of interest in this work. For this reason, the oxygen, nitrogen, and hydrogen were added in measured amounts as gases, and diffused into the titanium, to avoid the necessity of chemical analysis. The purpose of the work reported here was to isolate and measure the effects of oxygen, nitrogen, and hydrogen on titanium of the highest purity available at the time. The concentrations studied were 0.25, 0.5, and 1 at. pct in each case. Experimental Work One-half of a 24-in. hairpin of iodide-refined titanium was available for this work. The rod was approximately 0.25-in. in diam and had a 0.003-in.tung sten core. From chemical and spectro-graphic analyses, the purity of the sample was estimated to be between 99.80 and 99.95 wt pct. The chief impurities (aside from the tungsten core) were iron (0.04 pct), silicon (0.01-0.1 pct), aluminum (0.05 pct), carbon (0.03 pct). The tungsten core constituted 0.05 pct by weight of the sample. Although some alloying undoubtedly took place between the tungsten and the titanium during the deposition reaction, the core remained substantially intact in the deposited metal. The initial average hardness of the titanium as deposited was 105 Vickers (10-kg load). The maximum hardness was 116 Vickers and the minimum 91 Vickers. The metal was somewhat harder than that currently being obtained by the iodide process, that is, 75-90 Vickers. The rod was cold swaged to ¼-in. diam and then cold rolled in diamond shaped rolls to about 0.080-in. square, using reductions of 15 pct in area per pass. The 0.080-in.-square wire was cut into 6-in. lengths for the preparation of the alloys by the gaseous absorption and diffusion method. ADDITION OF OXYGEN, NITROGEN, AND HYDROGEN TO TITANIUM A modified Sieverts&apos; absorption apparatus, shown in Fig 1, was used in

Jan 1, 1950

By H. R. Peiffer

The increase in electrical resistivity, ?pT,at 78°K was measured as a function of elongation, E, at 78°K for a 2 pct (approximately) by weight finely divided alumina in silver material. The amount of increase in electrical resistivity (?pT) is a function of the amount of alumina present and can be represented by: ?pT = cen where c and n are constants. The constant c increases and the exponent n decreases with increasing alumina content. Approximately 33 pct of the resistivity increase is recovered upon annealing at room temperature. RECENTLY, dispersed phase alloys&apos; have shown promise for use at elevated temperatures. These materials have a high creep resistance, a high-temperature strength considerably above that of the pure matrix, and a high electrical conductivity. These materials also show other properties such as retardation of re crystallization and resistance to flow even above the melting point of the matrix.&apos; It is believed that high-temperature creep is retarded in these materials because the dispersed phase blocks the motion of dislocations. According to schoeck3 and also Weertman,4 the rate controlling process is the climb of dislocations around the dispersed phase particles. Any mechanical property of these materials, or any other material for that matter, can be explained on the basis of defect structures and their interrelations. It would certainly be interesting to learn something about the effect of a dispersed phase on dislocation densities and also their effect on point defect concentrations following cold work. This is the purpose of the research discussed herein. The method used was the measurement of the electrical resistivity as a function of elongation at low temperatures. This scheme has already been applied to the studies of pure metals.5 Electrical resistivity measurements conducted on pure metals such as copper, silver, gold, and so forth, have indicated that defects such as vacancies and dislocations are formed during deformation.5 It has been shown by van Bueren6 that the resistivity change, ?p, should increase with elongation, E, according to the following relation: Ap=Al/2 + B£3/2 where A and B are constants of the system; ?p is in µ? cm. The first term refers to the amount of resistivity change associated with line defects and the second term with the change associated with point defects. A later calculation yielded exponents of 3/4 and 5/4, respectively.6 Manintveld7 has shown that the resistivity of copper increases with strain according to a 3/2 power law, whereas van Bueren has shown that the resistivity of silver increases according to a 5/4 power law. Assuming then that van Bueren&apos;s calculations are correct, it appears that line defects contribute very little to the electrical resistivity. There is some doubt, however, as to the validity of van Bueren&apos;s expressions for all cubic metals.&apos; In fact, the data on copper and silver are not conclusive. In this in-

Jan 1, 1962

By B. Hyatt, E. Klokholm

The reesistivity of Cu-Pd alloys of 9.6 to 29 pct Pd alloys was measured after plastic deformzation in tension. For all compositions a continzting decrease in resistivity with increasing plastic strain was observed. By comparison with the results of Damask on a brass ad Cu3Au, it was deduced that these anonzalous decreases in resistivity are due to the decrease in short-vunge order caused by cold work. An anomalous decrease in the resistivity of cold-worked CU-Pd alloys was first reported by Jaumot and Sawatzky.&apos; They observed decreases in the electrical resistivity when disordered Cu-Pd alloys drawing at room temperature. Recently, a similar anomaly was reported by Aarts and Houston-Mac-Mi1lan2 in Ag-Pd alloys containing 10 to 45 pct Pd. The plastic deformation in this case was produced by tensile strain at liquid-nitrogen temperatures. For AE-Pd alloys the relative resistivity change becomes positive for tensile strains of about 20 pct.

Jan 1, 1960

By Irving B. Cadoff, Ernest Levine

The fracture path in a Cu-4 pct Ag alloy wet with mercury was found to he dependent on the heat treatment used prior to tensile testing. Both quenched and slow-cooled alloys were embrittled by the mercury.. For quenched alloys, which were single -phase, the crack path was intergranular. Slowly cooled alloys, which contained precipitate platelets, exhibited transgranular fracture. By comparing stress-strain data for these alloys with similar data on mercury -embyittled solid-solution alloys, it was found that the role of the precipitate and that of the grain boundary in the fracture process were equivalent . THE fracture path which results when metals are strained in a liquid environment appears to be dependent upon the nature of the specific system. Mixed transgranular and intergranular cracking has been observed in the 2024 T4 aluminum alloy when wet with a Hg-Zn amalgam.&apos; Transgranular fracture was induced in an A1-4 pct Cu alloy by masking off the grain boundaries from the liquid Hg-Zn amalgam.&apos; The embrittlement of solid-solution alloys of copper in mercury results in intergranular fracture.&apos; The effect of a precipitated phase on the fracture path in copper alloys is the subject of the present investigation. Cu-4 pct Ag was chosen so that its behavior could be compared with previous work on embrittlement of copper alloys. PROCEDURE High-purity copper (99.999 pct) was used as a base metal, along with 99.999 pct purity silver. Melting was carried out in graphite crucibles with manual agitation to get adequate mixing. The ingots were homogenized by means of vacuum annealing, chemically cleaned, and cold-rolled with intermediate vacuum anneals, to the desired thickness of 0.025 in. The rolled sheets were sheared to the final specimen size of 1 by 0.025 by 0.1 in. The specimens were then electropolished in phosphoric acid (concentrated) and heat-treated in an evacuated capsule at the solution temperature of 770°C. One batch was slow-cooled and the other quenched in water. The thermal etching which occurred during heat treatment was sufficient to permit grain boundary and precipitate delineation. Tensile tests were carried out in air and in mercury on a Table-Model Instron at a pulling speed of 0.2 in. per min. Wetting was accomplished by electro-polishing in phosphoric acid, rinsing in alcohol, and immersing in a pool of mercury. Once wet the coating was stable throughout the mechanical tests. In our studies it was found that wetting the surface or total immersion in mercury produced identical results. For convenience, the wetting technique was used for the experiments described. The crack pattern was observed directly on the surface by removing the mercury after testing. De-wetting was accomplished by flame heating the samples in a vacuum after testing and before observation of the surface. No etchant or polishing was used so as not to obscure the crack pattern on the surface. The mercury removal, however, resulted in a pitted surface but otherwise left the pertinent features visible. Photomicrographs were taken in this condition so as not to disturb the structure associated with the crack pattern. The average precipitate spacing was measured previous to coating the sample with mercury by use of an optical eyepiece micrometer. RESULTS The microstructure of the quenched specimens was single-phase while that of the slow-cooled specimens contained thin platelets of a second

Jan 1, 1964

By Nicholas J. Grant, W. Michael Yim

The creep-rupture properties of nickel, in as-prestrained or prestrain-polygonized condition, were studied at 1300°F and 4000 psi, and also at 700°F and 26,000 psi. An improvement of strength was noted in both the as -prestrained and the prestrain-polygonized tests at each temperature. The as-prestrained tests, however, showed superior creep resistance to the prestrain-polygonized ones. From the results of X-ray and etch-pit studies, the strengthc gain was interpreted in terms of dislocation density and the stability of preformed substructures. COLD work is known to improve the strength properties of metals at low temperatures. At high temperatures, however, the strength improvement is often lost if gross structural changes, such as re-crystallization, take place prior to or during the test. Even in the absence of recrystallization, a prestrained metal may undergo structural changes— polygonization and the formation of well-defined subgrains—which importantly effect the resultant properties. The relationship between substructure and creep properties has received considerable attention in recent years. The work of wood1 indicated that the creep strength of aluminum and its alloys was closely related to the subgrain size. Hazlett and Hansen,2 and Ancker, Hazlett, and parker,3 working with nickel and nickel alloys, had shown that small amounts of prestrain at room temperature followed by a recovery anneal at 800°C (1470°F) improved the strength at both low and high temperatures. The strength gain was attributed to an increase in the number of subgrain boundaries as a result of the prestrain-polygonization treatment. More recently Coldren and Freeman4 studied the effect of substructures on the creep rate of nickel at 1550°F. Their conclusions indicated that the substructure size as measured by the number of boundaries was the factor that controlled the creep rate. In addition, the perfection of the subgrain boundary has been indicated to have an important role on the strength.&apos; On the other hand, there are data which disagree with the above observations. Grant, Chaudhuri, Silver, and Ganow6 found no creep strength improvement by a prestraining treatment. In reviewing the role of subgrains on high-temperature creep, Shepard and Dorn7 concluded that the contribution of the subgrains to high-temperature creep strength was a minor one. Guard,8 in a recent study on poly-gonized nickel, has cast doubt on the validity of the postulate that subgrain size controls the creep rate. In the majority of the previous studies, the subgrain boundaries have been singled out as the most important factor in determining creep strength; however, there is no firm theoretical ground for the postulate that the subgrain boundaries act as effective barriers to dislocation motion.B910 Little effort has been directed toward the study of the relationship between creep strength and other structural variables, such as dislocation density, lattice strain,

Jan 1, 1963

By John W. Cahn, John E. Hilliard

Single crystals of copper and silicon-iron were cold rolled in orientations chosen to produce individually the major components of the poly crystalline deformation texture. The orientation dependence of the recrystallization kinetics was studied relative to the primary recrystallization textures of these specimens. It is not possible to rationalize the poly crystalline re crystallized textures on this basis. The results suggest an important role of the interaction of adjacent crystals during the deformation of aggregates. BRICK and Williamson1 first noted evidence that the recrystallization temperature was different for straight-rolled and cross-rolled copper given comparable reductions. Michalak and Hibbard2 investigated quantitatively the effect of rolling procedure on the kinetics of recrystallization of cold-rolled copper and found that material cold-rolled the same amount by straight-pass, cross-pass, and compression-pass techniques developed different deformation and recrystallization textures, different 1-hr recrystallization temperatures, and different recrystallization kinetics. However, the temperature dependence of the rate of recrystallization was essentially the same for all techniques. Similar results were obtained on iron. Dunn and Koh3 in studying the recrystallization textures of cold-rolled silicon-iron single crystals reported large differences in the annealing temperatures and times required to recrystallize specimens of different orientations cold-rolled the same amount. Liu4 and Liu and Hibbard5 utilized the concept of different recrystallization temperatures for different orientations of cold-rolled crystals to rationalize the difference in recrystallization textures found in various face-centered-cubic metals. Their explanation predicted a significant difference in the recrystallization kinetics of deformed (110) [112] crystals as compared to (358) [352] crystals, and, in fact, Liu4 reported evidence that this difference existed at least qualitatively. Verbraak6 who rolled and recrystallized a series of copper single crystals found that the double (112) [111] rolled orientation is related to recrystallized cube texture formation. The effect of rolling intensity on the relative amount of cube component suggests an important role of recrystallization kinetics. Walter and Hibbard7 while trying to relate the behavior of rolled and recrystallized single crystals of silicon-iron to the behavior of polycrystal-line silicon-iron again noted that differences in recrystallization kinetics were necessary to rationalize their results. The purpose of the present investigation was to obtain quantitative kinetic data on the recrystallization of single crystals of both copper and silicon-iron rolled to initial isolated individual orientations corresponding to those found in the polycrystalline deformation textures. These data might indicate the importance of the deformation orientation, i.e. the range of available nuclei, the deformed matrix orientation into which these nuclei grow, and the orientation dependence of their growth rate during primary recrystallization on this texture. I. COPPER Experimental Procedure—A single crystal of 99.98 pet purity copper, grown by the Bridgman technique, was purchased in the form of a bar 1 1/2

Jan 1, 1962

By T. A. El-Bassyouni, Paul Gordon

Grain-gvowth data in zone-refined aluminum and in dilute alloys of copper with this aluminum have been obtained. The amounts of copper added were from 4 to 400 at. ppm. It was found that in both the unalloyed aluminum and the alloys grain growth was characterized by a high value of n in the isothermal growth equation 6n = Kt The inadvertent presence of 1 at. ppm Fe in the alloys was found to he more potent in slowing growth than the purposely added copper. Possible rationalizations of these observations and their general relevance to the theoretical use of gvain-grozvth data have been discussed. Grain growth data of Winegard and his co-workers&apos; on zone-refined tin and dilute tin alloys were analyzed with some success2 in terms of approximate theoretical equations for boundary migration.2-4 In view of this success, experiments were carried out in an effort to obtain similar data on zone-refined aluminum and on dilute copper-in-aluminum alloys. The results obtained were anomalous in several respects and could not be used to test theory. A discussion of these anomalies is presented here; they have been attributed to impurity effects and serve to emphasize the sensitivity of grain growth in general—and the particularly high sensitivity in aluminum—to impurities. The resulting difficulties in the theoretical use of grain-growth data are also discussed. EXPERIMENTAL DETAILS An aluminum bar was zone-refined and leveled by methods similar to those described previously.&apos; The degree of purity obtained is indicated in Table The data in Table I were determined by mass-spectrographic methods through the courtesy of Mr. Thomas A. Johnson of AIAG Metals, Inc.* Three dilute copper alloys with this aluminum were prepared also by methods described previously.&apos; The alloys contained nominally 4, 40, and 400 at. ppm of Cu, respectively (0.001, 0.01, and 0.1 wt pct). Each material was fabricated by swaging and rolling into a round bar about 1/4 in. in diameter with an annealed penultimate grain size of approximately 0.003 to 0.007 cm. In order to minimize preferred orientation the fabrication was carried out in several steps, each consisting of a reduction of about 40 pct followed by a recrystallization anneal. Annealing temperatures for the grain-growth studies were attained by the use of boiling liquids up to 213°C and molten metal baths at higher temperatures. Temperatures were controlled to within 1°C. Samples for measurements were cylinders about 3/4 in. long and 1/4 in. in diameter cut from the fabricated rods. In the interests of sample economy a single sample was used for the grain-growth measurements at each temperature. Each sample was, thus, annealed for several successive periods of time, the grain size being measured at each annealing period on a transverse surface exposed by

Jan 1, 1965