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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.' 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.' 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'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' 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' 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.' 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'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's expressions for all cubic metals.' 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.' 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.' Transgranular fracture was induced in an A1-4 pct Cu alloy by masking off the grain boundaries from the liquid Hg-Zn amalgam.' The embrittlement of solid-solution alloys of copper in mercury results in intergranular fracture.' 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.' 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' 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.' 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.' 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

By N. S. Kenny, A. A. Burr

THE purpose of this note is to present evidence that vacancies, which have been produced by quenching from a high temperature, alter the rate of strain-hardening of an hep single crystal. The majority of investigations of the effects of quenched-in vacancies on the yield stress of metals have been made using fee samples in the form of thin wires. However, there is an inherent disadvantage in using such wires to study the effects of vacancies on the rate of strain-hardening of metals because fee wires begin stage II slip either immediately upon yielding or very shortly thereafter. When stage II slip occurs, very rapid strain hardening also occurs, masking the effects of vacancies on the rate of hardening. In this investigation single crystals of magnesium hep were studied since magnesium has only one slip plane at low temperatures and has, therefore, an extensive easy glide region. In addition, the effect of both static and dynamic recovery on the rate of hardening were eliminated by testing in liquid nitrogen. Both forms of recovery occur in hep metals by dislocation climb, which is a diffusion controlled mechanism and is negligible at liquid nitrogen temperatures. Finally, the dependence of the strain-hardening rate on the crystal orientation was eliminated by using the equations of Schmid and Boas.' Variations in the strain-hardening rate could, therefore, be attributed to the presence of vacancies. Single crystals in the form of rods approximately 5 mm in diam and 6 cm long were grown by a modified Bridgman technique from commercial high-purity magnesium (99.97 pet) supplied by the Dow Chemical

Jan 1, 1962

By R. D. Barer, M. B. Bever

Age hardening alloys are quenched from the solution treatment to room temperature in order to retain a supersaturated solid solution. Some alloys age "naturally" in this condition but in most alloys aging is induced "artificially" by heating to intermediate temperatures. Cold working of the supersaturated solid solution accelerates the aging process and quenching strains have the same effect. The investigation reported here is a study of the progress of aging in specimens quenched directly from the solution treatment to various aging temperatures. This procedure reduces the temperature interval of quenching and the resulting quenching stresses. It also eliminates any changes which would take place in the undercooled sample at room temperature prior to aging at an elevated temperature. Isothermal aging is thus approached and its kinetics may be studied. An aluminum-copper and an aluminum-silicon alloy were chosen for this investigation. The aging mechanism of aluminum-copper alloys is complex while the aging of aluminum-silicon alloys is nearly ideal. As standards of comparison for the samples directly quenched to the aging temperature, specimens were also age hardened by the usual procedure in which solution treated samples are first quenched to room temperature and then reheated to the aging temperature. Review of Previous Work The mechanism of age hardening has been the subject of a controversy which has ranged from the theory of outright precipitation of an equilibrium phase to theories based on subtle changes occurring in the matrix prior to precipitation. A detailed critical review of the literature up to 1939 is available1 and contributions to the general theory of age hardening continue to be made.2,3 Age hardening, whatever its mechanism, involves the nucleation of a second phase within a supersaturated solid solution. Theoretical considerations4,5 indicate that the rate of nucleation reaches a maximum at an intermediate temperature below the temperature at which supersaturation sets in. Studies of precipitation at various subcritical temperatures have demonstrated that the largest property changes in a given time occur at such intermediate temperatures.6,7,8 The precipitation of a phase from supersaturated solid solution is accelerated by strains which may result from quenching or cold work. Phillips and Brick9 established that quenching strains are an essential condition for the age hardening of aluminum-copper alloys at room temperature, at least for aging periods of less than 30 days. They also found that on aging at 300°C the hardness increased faster and reached a higher maximum after quenching into water than after quenching directly to the aging temperatures. Fink and Smith10 observed preferential precipitation on slip bands and grain boundaries in aluminum-

Jan 1, 1950

By R. E. Ogilvie, N. L. Peterson

DURING the past few years there has been considerable effort devoted to the understanding of radiation effects on materials. The concept of the Frenkel defect and other lattice defects suggests that radiation may alter the rate of many metallurgical phenomena, especially those which are diffusion controlled. In 1953 R. R. Coltman and T. H. ~lewitt' found an appreciable effect on the ordering rate of Cu,Au due to fast neutron bombardment. Since then several rather comprehensive theories have been proposed on radiation enhanced diffusion in solids.2"4 If the energy of the radiation is above the threshold energy for the removal of atoms from their lattice sites, Frenkel defects will be produced. These defects can be produced uniformly throughout a relatively thick specimen by high-energy X-rays permitting bulk property studies without the limitation of sample dimensions. In this work high-purity arsenic containing 30 ppm of impurities was allowed to diffuse from the gase- ous phase at 700°C into single crystals of p-type germanium containing 0.1 ppm of indium. As the arsenic diffuses into the P-type germanium, an n-type layer will form in the diffusion zone. At the p-n junction the concentration ratio of the arsenic to the indium is constant. Experimental Procedures—The germanium specimens, 10 mm by 10 mm by 5 mm, were polished and etched to a mirror finish. The specimens were then sealed off in a vycor glass capsule at 3 x 10"5 mm Hg pressure with a sufficient amount of arsenic powder to produce a one-half atm pressure of arsenic at 700°C. Specimens were annealed at 700°C without radiation. The diffusion coefficient determined from these samples agrees within 8 pct of previous work done by Fuller.' Three specimens were given diffusion anneals at 700°C in a small tube furnace centered beneath the target of a 2-mev Van de Graaff generator. The specimens when in the furnace were 10 cm directly below the target of the generator. These specimens were irradiated continuously during the diffusion run with the Van de Graaff operating at 2 mev with a tube current of 225 to 250 pamp. The intensity of the x-radiation at the surface of the specimen inside the furnace was approximately 4.5 x l05 roentgens per hr. The temperature was controlled within m2°C by a chromel-alumel thermocouple throughout this work with no observed temperature change due to the radiation. By careful lapping, the samples were polished at an angle of 5 deg to the diffusion zone, giving a XI0 increase in the visible diffusion zone. The location

Jan 1, 1960

By E. F. Koch, J. L. Walter

oriented crystals of iron and iron with 3, 5, and 6.25 pct Si were rolled to reductions of 10 and 70 to 97 pct at room temperature. Similarly oriented crystals were deformed in tension. Dislocation substructures of the deformed crystals were observed by transmission electron microscopy to determine the effect of silicon on the formation of substructures. Pole figures were obtained to relate orientation changes to substructure. When rolled 10 pct, the iron crystals and the 3 pct Si-Fe crystals formed cells, 1 and 0.2 u in diameter, respecliuely. Cells were absent in the higher-silicon crystals. Extended dislocations and possible stacking faults were observed in the 6.25 pct Si-Fe crystal rolled 10 pct and annealed at 650°C. The stacking-fault energy was estimated to be 20 ergs per sq cm. Rolling to 70 pct resulted in the formation of sub-bands (0.9 µ wide) ill the iron crystals and transition bands (containing 0.2-µ-wide subbands) in the 3 pct Si crystals. No subbands formed in the 5 pct Si-Fe crystal until it was ankzealed. SliP occurred on (112) planes ill tension. The slip traces on the 3 pct Si crystal were wary while those on the 5 pct Si crystal wvere straight. The strain-hardening coefficient for the 5 pct Si crystal was nearly zero. Cells did not form, at least at elongations up to 10 pet. The results suggest that cross slip of iron is restricted by additions of silicon beyond about 3 pct possibly by formation of immobile extended dislocations. IN a previous paper' the authors described the substructures developed in (100)[001]-oriented crystals of 3 pct Si-Fe which were rolled to reductions of 10 to 90 pct at room temperature. At low reductions (10 to 20 pct) cells, approximately 0.2 to 0.3 ja in diameter, were formed. The cell walls consisted mainly of edge dislocations. With increasing reduction (up to 50 pct) the cells were seen to elongate in the rolling direction. In certain regions of the crystal there were significant reorientations which were characterized as rotations about an axis normal to the (100) or rolling plane. These regions were called "transition bands". The regions in which there were no reorientations were called ('deformation bands". At reductions of 60 to 70 pct the elongated cells in the transition bands became sub-bands separated by low-angle tilt boundaries with angles of disorientation of about 2 deg. The elongated cell structure in the deformation band was replaced by a general distribution of dislocations. It was noted that the width of the subbands in the transition bands remained 0.2 to 0.3 µ; i .e., the width of the subbands was the same as the initial cell diameter for reductions up to at least 70 pct. From this, and from considerations of the mechanism of formation of the transition bands,' it was concluded that the subbands evolved directly from the initial cells. In order to check this conclusion, it was decided to examine the relationship between initial cell diameter and width of subbands produced by large rolling reductions. Cell size is known to be dependent upon the temperature of deformation.2,3 However, preliminary experiments with 3 pct Si-Fe crystals indicated that the change in cell size with increasing temperature of deform,ation was not sufficient for the present purpose. On the other hand, cell diameters generally reported for iron deformed at room temperature2'3 range from 1 to 2 p, a factor of 3 to 10 larger than the cells in 3 pct Si-Fe rolled to 10 pct reduction,' indicating the possibility of a marked dependence of substructure (at least in terms of cell size) on the amount of silicon in iron. Thus, the investigation was enlarged to include the study of the effects of varying silicon content on substructure in lightly rolled as well as in heavily rolled crystals of iron and iron with 3, 5, and 6.25 pct Si. The crystals used in this study all had the same orientation, (100)[001], with respect to rolling plane and rolling direction. These were rolled to reductions of from 10 to 97 pct and the substructures determined by electron transmission microscopy in both the rolled state and after annealing. In addition, stress-strain curves were obtained from (100)[001]-oriented crystals of iron and 3 and 5 pct Si-Fe to determine the effect of silicon on tensile properties. The dislocation substructure of the tensile specimens was also determined for Samples pulled to 2 and 10 pct elongation at room temperature for comparison with the substructures produced by rolling. 1) EXPERIMENTAL PROCEDURE Crystals with 3, 5, and 6.25 pct Si were prepared by annealing 0.012-in.-thick sheets of high-purity Si-Fe in purified argon at 1200°C to effect growth

Jan 1, 1965

By J. H. Jackson, P. D. Frost, C. H. Lorig, A. C. Loonam

THIS paper describes (1) the effect of sodium on the tensile ductility of magnesium-lithium base alloys, and (2) the precautions necessary to avoid sodium contamination. Effect of Sodium on Properties The harmful effect of sodium in magnesium-lithium base alloys has been recognized by other investigators.1,2 However, quantitative data on its effect have not hitherto been published. The effect of sodium on the ductility of an 87 pct Mg-9 pct Li-4 pct Zn alloy is shown in fig. 1. The sodium was introduced by adding sodium chloride to the flux, which consisted of 50 pct LiC1-50 pct KC1. Moderately high ductility was obtained at an indicated sodium content of about 0.05 pct. Actually, the value probably was less than 0.05 pct, be-cause analyses of the lithium, which were more accurate than those of the alloy, indicated that the highest ductility was obtained when its sodium content was 0.02 pct or less. In fact, in alloys having somewhat greater strength than this particular composition, the sodium content of the lithium must be under 0.01 pct to avoid embrittlement. The effect of sodium on the ductility of several alloys having fairly low strength levels is shown in fig. 2. These alloys were melted with a flux containing 75 pct LiC1-25 pct LiF, to which various quantities of sodium chloride had been added. Sodium had no significant effect in pure magnesium but markedly decreased the ductility of the magnesium-lithium-zinc alloy, even though the alloy contained only 3 pct Li. As the lithium content of the binary alloys was increased, the ductility of the sodium-free alloys also increased. However, the effect of sodium on ductility became progressively more pronounced. Sodium raised the minimum hot-rolling temperatures, particularly those of the high-strength alloys, but its effect, in this respect, was less critical than its effect on tensile ductility. For optimum cold roll-ability, a low-sodium content was required. No deleterious effect of sodium on the stability of properties at slightly elevated temperatures was found. Control of Sodium in the Alloys Optimum ductility is obtained in the magnesium-lithium base alloys when sodium-free materials are used. Commercial lithium was formerly the chief source of contamination. Now purified lithium is usually available. When lithium of ordinary purity is used, the effects of sodium can be minimized by using a flux consisting of 75 pct LiC1-25 pct LiF. Bubbling nitrogen through the melt also helps remove sodium. The damaging influence of sodium on the ductility of the magnesium-lithium base alloys was observed very early in the alloy development program. The discovery came about as a result of chemical analyses made on the lithium used in the alloys. Ductile alloys had been made from lithium containing about 0.2 pct Na, whereas the lithium used in the brittle alloys contained about 0.9 pct Na. The first magnesium-lithium alloys were melted under commercial fluxes ordinarily used in melting magnesium alloys. These fluxes were unsuited for scavenging the contaminating sodium, and the resulting alloys were not ductile. Next, a flux containing 50 pct KC1-50 pct LiCl was tried. This was somewhat more effective but still was not satisfactory. After a number of different experimental fluxes had been investigated, one containing 75 pct LiC1-25 pct LiF was adopted. This flux made it possible to obtain good ductility in the alloys. The

Jan 1, 1951

By W. C. Winegard, A. Galibois, C. J. Beingessner

The effects of solutes on the distribution of two-dimensional configurations of grains in zone-refined tin have been studied. When solutes with partition coefficients (ko) greater than unity are added, three-sided pains become more prevalent and the growth law changes. It is shown by electron-Probe micro-analysis that a solute buildup occurs ahead of a moving grain boundary when ko > 1. It has been found recently1, 2 that solutes with partition coefficients greater than unity have a larger retarding effect on grain growth than solutes with k, less than unity. ko is defined as the ratio of the concentration of solute in the solid to the concentration of solute in the liquid with which the solid is in equilibrium. Niessen and winegard2 have suggested that this effect is probably due to the complex shape changes which occur during the process of grain growth and that no theory based on single boundary motion3-5 can explain the results. They suggested that the dissociation of the unstable fourfold junction was delayed in alloys where ko was greater than 1 because the boundaries at the junction had to move into a region of high solute concentration. If indeed this mechanism were correct, it was felt that not only would the dissociation of fourfold junctions be affected by the solute buildup ahead of the boundaries, but the collapse of three-sided grains would be impaired. These combined effects would naturally lead to a modification in the distribution of the number of sides per grain seen on a two-dimensional section. The present investigation was undertaken to test these hypotheses by examining the grain-growth process in detail. EXPERIMENTS The Distribution of Grain Configurations in Zone-Refined Tin as Seen on a Two-Dimensional Section. Following the method of Bolling and Winegard,6 zone-refined tin was cast into button-shaped specimens and, subsequently, plastically deformed under a drop hammer at room temperature. The resulting flat coin-shaped samples were annealed at 200°C, some for 50 sec and others for 100 sec. The specimens were then examined to determine the distribution of the number of sides per grain, i.e., the num- ber of crystals adjacent to any particular grain in the section. For simplicity, the grains were classified as three-sided, four-sided, and so forth; this concept is schematically illustrated in Fig. 1. As indicated by smith,' it was necessary to examine every grain within an enclosed area to obtain a proper distribution of the relative frequency of each type. The distributions for the two annealing times are illustrated in Fig. 2. The total number of grains examined is also indicated on the figure. It is evi-

Jan 1, 1965

By G. Sachs, E. J. Riping

All ferrous alloys can be made brittle by straining at sufficiently low temperatures. However, the changes in mechanical properties for different ferrous materials with decreasing testing temperature do not appear to follow any universal law. In particular, complex effects of testing temperature have been observed if cold worked steels were subjected to tensile tests at low temperatures. EFFECTS OF PRESTRAINING AT A TEMPERATURE ABOVE THE TESTING TEMPERATURE ON THE FRACTURE CHARACTERISTICS‡ A considerable amount of data has been presented by a number of investigators on the fracture characteristics of various cold worked steels.' These data usually relate to a two-step procedure first used by Davidenkov,² consisting of stretching by tension to a certain strain or " prestraining" at room temperature and then completing the tensile test, or "testing" at the temperature of liquid air. On the basis of data of this type made available to date, ferrous alloys can be classified into two groups with respect to their fracture characteristics observed on testing at a low temperature after prestraining at room temperature. Very complex phenomena have been observed for all annealed steels. On the other hand, some observations indicate that steels in certain other conditions represent a fundamentally simpler relation. In considering the effect of prestraining at one temperature on the properties obtained at some lower temperature, it should be expected that any cold work reduces the ductility retained in proportion to the magnitude of the cold work. However, the test data presented to date indicate that only heat treated (quenched and tempered) steels appear to conform to this expectation, according to the very limited test data in Fig 1, presented by McAdam, Geil and Mebs. This series of tests, Fig 1, shows that the retained ductility became smaller the larger the prestrain. However, this decrease is less than the amount of prestrain or, in other words, less than the decrease in ductility at the prestraining temperature. These effects of prestraining are fundamentally identical with those observed by Bridgman3 when a steel was prestrained (in tension) under hydrostatic pressure and then subjected to a regular tension test. It appears, therefore, that the basic effect of prestraining under conditions which yield a higher ductility than the (subsequent) testing procedure, consists of gradually increasing the total ductility of the metal from the initial low value of testing to the higher value of prestraining. On the other hand, all annealed steels, if cold worked by tension at room temperature and then tested at a lower temperature, provided that some ductility is retained, showed a far more complex behavior than that discussed above. This relationship is exemplified by Fig 2, for three pearlitic steels.4,5 These particular steels were selected because of the various shapes of their ductility-prestrain curves. All three steels, and any other investigated so far, suffered a rapid decrease in retained (and consequently also in total) ductility when subjected to small pre-strains. Then, after exceeding a certain prestrain it was generally observed that the ductility recovered.* This rather complex behavior of annealed steels may be tentatively correlated with the presence of stretcher strains at small restrains. Heat treated steels do not exhibit stretcher strains. This fact might possibly explain their simpler prestrain-retained ductility relationship. The destructive effect of these stretcher strains may possibly be associated with the presence of triaxiality, which may occur in any highly non-uniform stress and strain state (and which is retained as residual stress after unloading). Even a small degree of triaxiality may then cause a reduction in ductility, or even embrittlement at a sufficiently low testing temperature. The discussion presented above deals with the effects of cold working at a high temperature on the fracturing

Jan 1, 1950

By J. O. Nelson, C. J. Altstetter

Single crystals of hcp cobalt, 3 mm in diameter and up to 35 cm long, were grown using an electron-beam, zone-melting technique. The martensitic-phase transformation was studied in single-crystalline and polycrystalline specimens by making length-change measurements as a function of temperature under various elastic compressive stresses. Upon thermal cycling, single-crystalline or polycrystalline specimens repeatedly transformed almost entirely on the same variant of close-packed plane provided the maximum temperature did not exceed 600°C. Cycling to 1000°C resulted in transformation on more than one {111} variant. This behavior is termed multivariance. The multivariant transformation occurred very rapidly at an M, temperature 2° to 6°C lower than the M, of a transformation which would result in a single-crystal product. Elastic compressive stresses (up to 253 g per sq mm) tended to lower the A, and raise the M, temperatures, decreasing the width of the temperature vs dilatation hysteresis loop. The transformation habit plane and transformation shear direction of an as-grown single crystal were not grossly affected by elastic compressi?ie stress. This was evidenced by similar dilatations on the temperature us dilatation loops joy specimens with and without compressive stress. A dislocation mechanism is proposed to explain the observed results. IT has been shown that, on heating, cobalt transforms martensitically from the hcp to the fcc phase.' The transformation habit plane is (0001)hcp || (lll)fcc and the transformation shear direction is (1010)hcp || (112)fcc. The transformation involves a shear of 1g°28', which may be achieved by a shearing of a/6(112) of every two planes with respect to the plane beneath, thus changing the ABABAB stacking of hcp to the ABCABC stacking of fcc. Associated with the phase change is a 0.3 x 10"3 contraction in the habit plane and a 4.2 X 10"3 expansion perpendicular to the habit plane resulting in a 3.6 x X volume increase on heating.' On cooling, an identical volume decrease takes place. The temperature at which the fcc phase begins to form on heating (A,) is reported as 430°C, and the temperature at which the hcp phase begins to form on cooling from an elevated temperature (A&) is reported as 390oC1,3 Consequently, temperature vs dilatation plots have the form of a hysteresis loop. If heating or cooling is reversed during a transformation, a smaller hysteresis loop results. Upon heating, the transformation is always complete; whereas, fcc is often retained at room temperature as a metastable phase entrapped in the polycrystal-line hexagonal matrix.1,4,5 Two obstacles in the theory of the allotropic-phase transformation of cobalt have been: 1) a detailed knowledge of the product nucleus, and 2) a plausible method of propagation of the transformation. Bilby,8 christian, 7 and seeger 8,9 have suggested a "pole mechanism" as a means of propagation of partiai dislocations from plane to plane. A pole dislocation and a Shockley partial come together at a node. The a/6(112) Shockley partial rotates about the pole dislocation effecting the transformation shear. The pole dislocation must have a 2a/3(111) screw component which causes extension of the transformed region by two atomic planes with each full rotation of the Shockley partial. Bollmannl0 suggested, on the other hand, that transformation propagation occurs due to the stress fields of intersecting (111)-type stacking faults. As faults intersect, a stress distribution is set up about their intersection which is in turn reduced by the emergence of another fault on the second nearest plane. This process continues with the final result of a complete phase transformation. In view of the similarities between deformation and transformation in cobalt, the effect of stress on the transformation would, hopefully, yield valuable information concerning nucleation and propagation. In the present work single-crystalline and polycrystalline specimen length changes were measured as a function of temperature at various compressive loads. PROCEDURE Several orientations of single crystals of hcp cobalt in lengths up to 25 cm were grown by electron-beam floating zone melting from 99.95 and 99.999 pct, 3-mm-diam cobalt rod as supplied by Johnson

Jan 1, 1964

By R. I. Garrod, R. A. Coyle

The shapes and positions of X-ray reflections from specimens of copper, steel, and aluminum alloy haue been examined in the elastic and plastic ranges both while the specimen was under stress and in the unloaded condition. For the aluminum alloy the shape was unaltered by the application of stress either within the elastic limit or in the plastic range provided that no additional plastic strain was induced. In copper the broadening accompanying plastic deformation was very slightly reduced when the specimen was unloaded. A similay but more marked elastic component of broadening was also found for steel, but in this case below the yield stress. Line profiles corrected for instrumental and particle-size broadening indicate very large internal stresses in local regions of the plastically deformed metals. The results are discussed in terms of a recent suggestion that the heterogeneous dislocation distribution between the cells and their boundary walls plays a major role in the peak shifts and broadening of the X-ray reflections. STUDIES of the X-ray line profiles from strained polycrystalline aggregates concentrate usually on one or the other of two main parameters: a) the displacement of the peak of the intensity contour from its position for a strain-free aggregate, or b) the shape of the profile. From peak shifts data can be obtained either on the relation in both the elastic and plastic ranges between applied external stress and average lattice strains in a given (hkl) direction, or, alternatively, on the residual lattice strains which are present after a plastically deformed specimen is unloaded.' On the other hand, the shapes of the broadened profiles from cold-worked metals can be analyzed to separate the broadening produced by small particle size and by heterogeneous lattice strains.' In this paper the terms "size broadening" and "strain broadening'' are used in the general sense adopted by warren.' In the past, apart from two early qualitative observation, it has been customary to examine only the movements of the peaks of the profiles while the specimen is actually under load, since the line broadening induced by plastic strain remains after removal of the external stress. Consideration of the implications of existing data of this type suggests, however, that fruitful additional information on a number of fundamental aspects might be gained by careful examination of whether the X-ray line profile is in fact different in the loaded and unloaded states of the specimen. By taking advantage of the sensitivity and convenience of modern diffractometer techniques it is possible to explore with relative ease the magnitude and importance of any elastic effects which may be superimposed upon the well-known permanent changes in profile. The main aim of the work to be described was thus to investigate this point for typical metals and alloys. For this purpose annealed specimens were extended first elastically and then plastically and the positions and shapes of X-ray reflections were recorded. Initially it was anticipated that prime interest would center on observations within the plastic range; it has been found, however, that small changes in profile sometimes occur both before and after the nominal elastic limit of the material is reached. It is shown that the results obtained have important implications in relation to the structural changes and processes associated with deformation. I) EXPERIMENTAL To enable the diffraction lines to be recorded while the specimen was under uniaxial-tensile stress, a small hydraulic testing machine was designed and constructed for direct attachment to the goniometer of a Philips diffractometer. The specimens, which were machined from 1/2-in.-diam rod and had a central rectangular section 3/8 by 1/16 in. over a gage length of 1 in., were held in the machine by split collets mounted in grooves in the cylindrical ends of each specimen. No special precautions were taken to ensure precise axiality of loading. Constant oil pressure was maintained by a lever and weights system and transmitted to the loading rig by flexible pipe. The actual load on the specimen was measured by a load cell in the machine to an accuracy of * 1 pct. To enable smooth X-ray profiles to be obtained the specimen and machine were oscillated continuously during recording through *7-1/2 deg about the normal half-angle position of the goniometer. The three materials chosen for the investigations were high-purity copper as representative of a ductile fcc metal, a low-carbon steel for a bcc metal, and an aluminum alloy as a material in which the proof stress/ultimate strength ratio is high. Details are as follows. a) Copper. 99.999 pct purity. After machining the specimen surface was polished mechanically and

Jan 1, 1964

By G. B. Craig, J. Rezek

The critical resolved shear stress of zone-refined zinc single crystals deformed in tension is found to increase with increasing amount of striation substructure. The increase in strength with numbers of striations can be accounted for by a dislocation pile-up mechanism. A somewhat different means of plotting stress-strain data is introduced which allows a more unambiguous choice of yield stress to be made. FEW systematic studies of the role played by mac-romosaic or striation-type substructure in the de- formation of high-purity metal single crystals grown from the melt have been reported. McGrath and Craig' found that striations increased the critical resolved shear stress of zone-refined aluminum crystals, postulating a dislocation blockage by the striations as the strengthening mechanism. Lauri-ente and Pond2 found that, as the etch pit density increased in aluminum crystals grown from the melt, the critical resolved shear stress also increased. Fleischer and Chalmers3 also found changes in the critical resolved shear stress of aluminum crystals grown from the melt at varying rates, but could not be certain whether an increase of strength with rate was due to a higher concentration of impurity in the gage length or to an increase in the number of small-angled boundaries. An early work by Hibbard4 indicated that copper crystals containing lineage boundaries were stronger than those free from this type of imperfection.

Jan 1, 1962