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By George Hallerman, R. J. Gray

In the customary method of studying age hardening, the process of aging is interrupted by cooling the specimen and measuring its room-temperature hardness. However, the aging process may be conveniently measured while it is occurring at an elevated temperature by a series of hardness measurements at suitable time intervals. The latter method gives data void of complications that might result from processes occurring during the quench, and the data may be more indicative of the alloy's properties at elevated temperatures. The elevated-temperature hardness tester1 used in the present study employed a dead-weight loading system with a synthetic sapphire Vickers-type in-denter mounted in a molybdenum holder. The tests were performed in a vacuum of l0 to 10 torr. Hardness impressions were made by applying a 2-kg load for 15 sec. Although the hardness impressions made in the tester at elevated temperatures were measured at room temperature, the correction for thermal contraction during cooling was insignificant and therefore neglected. The two methods of obtaining age-hardening data were compared using eighteen samples of Haynes alloy No. 25* which had been annealed for 2 hr at 2250°F (1232°C). The test surfaces of the 1 by 1 by 1/4-in. samples were ground and then polished on vibratory polishers2 prior to testing. Three groups of five samples were aged at 1400°, 1650°, and 1800°F (760°, 899", and 982°C) for 4, 16, 32, 64, and 100 hr and then water-quenched. Room-temperature hardness as a function of aging time for these samples is shown in the broken lines of Fig. 1. Only one sample for each of the three temperatures was necessary to determine the hardness of the alloy at the aging temperatures with the elevated hardness tester. The specimens were heated isothermally and hardness impressions were made after various time intervals up to 100 hr. The results of these determinations were represented by solid lines in Fig. 1. Comparison of the two sets of curves shows, as expected, the hardness values determined at the aging temperatures are lower than the room-temperature hardness of the quenched specimens and the hot-hardness values reflect a strong tempera-

Jan 1, 1964

By N. Brown, H. Green

The effect of quenching temperature and of aging temperature and time on compression stress-strain curves of ß brass was investigated. Age softening occurs at a rate which decreases with decrease of quenching temperature below the critical temperature for ordering. The activation energy for softening is 15,400 cal per mol. No matter how rapidly brass is quenched or what the temperature from which it is quenched, practically complete order is obtained at room temperature. It has been demonstrated that with respect to the specific heat,',' electrical resistivity," X-ray diffraction, and microstructure, the slowly cooled and rapidly quenched specimens are the same and that complete long range order exists in both cases. However, Smith" showed that the hardness of ß brass depended upon the cooling rate and the temperature from which brass is quenched. Smith showed that the hardness was a maximum for specimens quenched from about 445 °C and that the as-quenched structure softened at room temperature at a rate depending upon the temperature prior to quenching. This softening after quenching is in this paper referred to as age softening. The results of this investigation are qualitatively the same as the findings of Smith. However, a more detailed analysis of these phenomena has been possible since the stress-strain curve offers a more sensitive index of the state of the metal than hardness. It is the purpose of this paper to show how the mechanical properties are related to the ordering of ß brass. A 200-lb ingot made from electrolytic copper and electrolytic zinc was extruded to 1/2in. rod. Chemical analyses at frequent intervals along the rod showed that the alloy contained 51.5 pct Cu with the greatest impurity being iron, at 0.01 to 0.001 pct. To obtain a constant test material, the 1/2in. extruded rod was warm-rolled to % in. diameter at 200°C and then recrystallized to a grain size of 2.0 mm. The specimens for the compression test were % in. high and % in. in diameter. The specimen ends were polished on 600 metallographic paper and coated with Molykote for a lubricant. The compression rig consisted of an anvil resting on the machined table of the Baldwin Southwark testing machine and a plunger fixed to the movable cross

Jan 1, 1954

By G. R. Speich

The age-hardening of Fe-18 to 21 pct Ni marten-sites containing small amounts of titanium, aluminum, copper, or molybdenum has been studied by hardness measurements, transmission electron microscopy, extraction replicas, and X-ray and electron diffraction. Electyon-probe microanaly-sis of the extracted precipitates was also performed. The effects of temperature and composition on the aging kinetics have been studied in detail for Fe-20 pctNi-Ti martensites. All the martensites hardened on aging at 400" to 500 "C with a single aging peak. In the Fe-20 pct Ni-Ti martensites hardening was associated with the formation of a fine dispersion of NisTi. No precipitation was observed in an Fe-21 pct Ni-2.6 pct A1 alloy, although the hardness increased from 327 to 545 Dph during aging at 500°C. Copper was precgitated from an Fe-20 pct Ni-10.7pct Cu alloy, at least during the later stages of age-hardening. Hardening in an Fe-18 pctNi-5pct Mo alloy was associated with the precipitation of an intemzetallic compound tentatively identified as NisMo. The formation of austenite and the recovery of the defect structure of the martensite occur simultaneously with the normal precipitation processes &ring aging of these alloys. THE age-hardening of substitutional iron-base martensites is an important subject for study since age-hardening is one of the principal means of strengthening the substitutional iron-base martensites in precipitation-hardening stainless steels1 and maraging steels.a~4 In contrast to Fe-C martensites, these martensites are relatively soft and ductile in the as-quenched condition, due to the low solid-solution hardening effect of the substitutional elements as compared to carbon. Also, these martensites are hardened by aging at low temperatures in contrast to Fe-C martensites which generally soften on tempering. Titanium and aluminum, singly or in combination, as well as copper and molybdenum, have been the principal alloying additions to stainless steels to obtain an age-hardening reaction.' Ti-A1 or Co-Mo-Ti combinations have been used in the case of maraging steels.3"4 The present work has been confined to a study of the age-hardening characteristics of an Fe-18 to 21 pct Ni martensite to which small amounts of titanium, aluminum, copper, and molybdenum were added in order to study the effects of each alloying element separately. The age-hardening characteristics of these alloys were studied by hardness measurements, transmission electron microscopy, extraction replicas, and X-ray and electron diffraction. Electron-probe micro-analysis of the extracted precipitates was also performed. The types and dispersion of precipitates, the formation of austenite, and the recovery of the defect structure of the martensite all were studied. EXPERIMENTAL PROCEDURE Alloys. The compositions of the alloys studied are listed in Table I. The level of 18 to 21 pct Ni was chosen to assure complete transformation to martensite on quenching and is the same nickel level used in maraging steels. The concentrations of titanium, aluminum, copper, and molybdenum were chosen after a study of the and Fe-Ni-MO' ternary diagrams indicated how much of each alloying element could be dissolved in austenite. Alloys with 2 and 4 pct Cu were also studied, but these did not show precipitation hardening at the nickel levels studied and will not be discussed further. The alloys were prepared from electrolytic iron and high-purity* nickel, titanium, aluminum, copper, and molybdenum by vacuum melting of 20-lb heats. These were vacuum-cast into two 8-lb ingots. The ingots were hot-rolled at 1100°C to 1/2-in. plate and subsequently cut into 3/8-in. cubes. The cubes were sealed in evacuated quartz capsules and solution-treated for 16 hr at 1100°C, except for the Fe-20 pct Ni-10.7 pct Cu alloy and Fe-21 pct Ni-2.6 pct A1 alloys which were solution-treated for 16 hr at 1300" and at 1250"C, respectively. Metallographic examina-

Jan 1, 1963

By P. W. Ramsey, G. L. Werley

THERE have been numerous examples in recent years of the similarity between aging behavior and diffusion behavior, where a plot of the logarithm of the aging rate versus the reciprocal of the absolute temperature yields an approximate straight line, analogous to a similar plot of the diffusion coefficient D (log D vs. 1/T). Austin and Rickettl have pointed out that this linear relationship holds empirically for the de- composition of austenite into pearlite and bainite in carbon steels, and Robertson' has shown similar trends in the aging of 24S-type aluminum alloys. Jenkins and Bucknall³ have also demonstrated the association between aging and diffusion rates for nickel-silicon-copper alloys. Jetter and Mehl,4 however, have shown that the maximum rate of dilation of a series of aluminum-silicon alloys does not show this linear relation and Mehl5 has pointed out that careful study of available knowledge indicates that "aging rates increase with temperature approximately exponentially, whereas D increases precisely exponentially." He further notes that "the rate of aging at a given temperature is the greater the lower the melting point of the alloy, which is also true for D." This paper describes the aging changes occurring in a zinc-25 pct manganese-15 pct copper-0.1 pct aluminum die casting alloy. It was found that this alloy does show this linear relationship and use was made of this relationship to estimate aging rates at low temperatures from data acquired at elevated temperatures. It should be noted that the aging reaction is being studied only indirectly, using changes in certain properties as criteria of the progress of the phenomenon. This alloy is purely an experimental one and is not available commercially. Zinc-Manganese-Copper System: The zinc-rich portion of the zinc-manganese-copper diagram which is of significance in the present work is quite uncertain. X ray examination of the alloy as die cast shows a phase similar to the epsilon phase (hexagonal close packed) of the copper-zinc system. All of the data accumulated indicate that the epsilon phase of the zinc-manganese-copper alloy is stable at high temperatures; that is, 500°C or above. Below this temperature a new phase is precipitated on annealing, and a decrease in specific volume occurs. At elevated temperatures this phase change occurs quite rapidly, while at room temperature the alloy has shown no change after several years. According to X ray data, this precipitated phase resembles the gamma phase (cubic) of the copper-zinc system, a hard and brittle structure. From examination of the microstructure and from X ray examination of the alloys annealed at

Jan 1, 1951

By J. G. Kura, P. D. Frost, L. W. Eastwood

THE preparation and general properties of mag-nesium-lithium base alloys have been described in earlier papers.l,2 Lithium forms solid solutions with pure magnesium, lowers its density, and improves its formability. The improved isotropy and better formability of these alloys are attributed to the ability of lithium to convert the magnesium lattice from hexagonal (alpha phase) to body-centered-cubic (beta phase) structure. This change in structure is, however, accompanied by some limitations which make it difficult, if not impossible, to combine all the desirable properties in one composition. The most important of these limitations is the tendency of the high-strength alloys to overage and lose strength at temperatures of the order of 150" to 200°F. A study was made of the effects of composition and heat treatment on the age-hardening character- istics of the alloys. Stability of properties was determined by hardness and tensile testing of the alloys at room temperature after various periods of exposure to elevated temperatures. Precipitation-hardening curves are shown for a number of magnesium-lithium-zinc alloys in fig. 1. All the alloys were solution treated at 700°F and aged at 200°F. The reason for using the drastic quench, toluene at —105°F, was to reduce the rapid precipitation of the hardening phase which takes place at room temperature. Previous experience has shown that a hardness of about 90 to 95 Rockwell E is indicative of yield strengths in the range of 35,000 to 40,000 psi. This is a desirable strength level for magnesium-lithium base alloys with specific gravities of the order of 1.65 or less. Although the hardness level is raised by large zinc contents, a corresponding decrease in the cold formability of these alloys occurs with increasing zinc content. Thus, alloys containing up to about 10 pct Zn and having hardnesses of the order of 70 to 75 Rockwell E may be bent over a very small radius; however, the 16 pct Zn alloy requires a bend radius of more than 8T. The hardness relationships illustrated in fig. 1 can be explained by the partial phase diagram shown in fig. 2. The zinc-free magnesium-lithium alloys are entirely body-centered cubic (100 pct beta phase) when the lithium content of the binary is 10.3 pct or higher. When zinc is added, the boundary between the beta and alpha-plus-beta fields at 700°F is shifted to lower lithium contents. In addition, the solubility of zinc at 700°F decreases with decreasing lithium content. It is shown by a study of micro-structures that the limit of solid solubility of zinc in the 6Mg/Li* matrix at 700°F is about 19 pct. It is believed from a study of the aging curves that this limit is about 2 to 3 pct at 200°F. Zinc additions up to about 2 pct increase the hardness and strength of the magnesium-lithium base solid solution. Larger additions of zinc effect further hardness increases, but precipitate during prolonged aging at 200°F. Alloys having 14 to 20 pct Zn precipitation harden extremely rapidly during quenching, even when quenched in toluene at —105° F. The high-zinc alloys overage at 200°F but are capable of maintaining reasonably high hardnesses for periods up to 1000 hr.

Jan 1, 1951

By N. J. Grant, R. Nordheim

An extensive study was made of the aging characteristics of alloys based on the 80 pct Ni-20 pct Cr composition hardened with aluminum and/or titanium, each up to 4 pct. Aging was followed by means of hardness and hot electrical resistance measurements as well as by X-ray and microscopy. Stress rupture tests at 1500°F were utilized as a check on the predicted behavior. THE titanium and aluminum hardened Ni-Cr alloys, exemplified by Nimonic 80 and Inconel X, constitute one of the more important groups of alloys developed to meet the demand for materials retaining their strength at elevated temperatures. For service in the temperature range 1200" to 1500°F, these alloys offer high creep resistance. With increasing service temperature, however, the strength of the simpler Ni-Cr base alloys falls off rapidly so that above 1500°F there is a significant loss of strength. The present investigation was undertaken with the hope that a better understanding of the factors controlling the precipitation hardening of these alloys would make it possible to increase the useful service temperature range. Primarily this investigation involved the study of the effects of titanium and aluminum on the hardening and the subsequent softening at elevated temperatures. The titanium and aluminum contents were each varied between 0 and 4 pct by weight at a constant nickel to chromium weight ratio of about 4:1. (Except when otherwise stated, all compositions are expressed on a weight basis.) The major part of the investigation was confined to alloys with less than 0.06 pct C. Recently several papers dealing with the identity of the microconstituents in the titanium and aluminum hardened Ni-Cr alloys have been published. Using X-ray analysis of the residues from anodic dissolution, Rosenbauml was only able to identify carbides and nitrides in Nimonic 80 and Inconel X. However, since Rosenbaum worked with alloys in the hot rolled rather than in the aged condition, his results are inconclusive. Recently Hignett' reported that the hardening of Nimonic 80 was due to the controlled precipitation of Ni,(TiAl) having the cubic Ni3A1 structure. Taylor and Floydv-" published the results of an investigation of the nickel-rich corner of the Ni-Cr-Ti, Ni-Cr-Al, and Ni-Ti-A1 systems. In the Ni-Ti and the Ni-A1 systems the hexagonal Ni,Ti phase, 7, and the cubic Ni3A1 phase, -y', respectively, exist in equilibrium with the nickel-rich solid solution. The interatomic distances in the basal plane of Ni,Ti and the octahedral planes of the matrix are almost equal, thus explaining the Wid-manstaetten type structure formed when Ni,Ti precipitates from solid solution. When Ni:,Al precipitates from solid solution, it appears usually in globular form, often dispersed along rows corresponding to definite crystallographic directions. The 7 and phases are also the only intermetallic compounds which occur in the nickel ternary alloys with up to 25 pct Cr and 10 pct Ti or Al. Taylor and Floyd found that Ni,Ti takes practically no nickel, chromium, or aluminum into solution. Nial, on the other hand, dissolves a considerable amount of chromium and titanium and some nickel. Up to three out of every five aluminum atoms could be replaced by titanium in Ni,Al. This substitution caused a slight increase (less than 1 pct) in the lattice parameter. With respect to the effect of variation in the titanium and aluminum contents on the high temperature strength of Nimonic 80 type alloys, Pfeil, Allen, and Conway" reported that an 80 pct Ni-20 pct Cr alloy containing 0.20 to 0.30 pct A1 had the highest creep resistance when the titanium content was kept between 1.65 and 2.75 pct. Experimental Procedure The materials used for this investigation were electrolytic nickel, electrolytic or low carbon chromium, sponge titanium and 2s aluminum. The alloys were melted in an indirect carbon arc furnace under

Jan 1, 1955

By D. R. Mash

A strong yield point with attendant enhanced mechanical properties was found in commercially pure beryllium under certain conditions of heat treatment. Beryllium specimens also responded to both quench and strain aging treatments. Based on these results, a possible means of obtaining increased normal temperature mechanical properties is suggested. COMMERCIALLY pure beryllium has been found to exhibit the yield point phenomenon and several other aging manifestations under certain conditions of heat treatment. This behavior is not surprising in view of the present accumulation of experience regarding such effects in numerous metals; but in addition to extending this experience to include beryllium, the present study is of interest because aging effects are generally associated with the presence of small amounts of solute elements. The well known lack of tensile ductility in beryllium at normal temperatures is also considered to be due to impurities in some way. In the present investigation, the view was taken that beryllium of commercial purity (greater than 98 pct) should be considered as a dilute alloy and that precipitation phenomena may well exist which could lead to enhanced mechanical properties. In connection with this possibility, published data on the variation of mechanical properties with temperature are of interest. For example, Fig. 1 illustrates the variation of ductility (percentage of elongation) and ultimate strength as a function of temperature for beryllium of various histories.* Although these curves are somewhat schematic in nature, they clearly indicate the possibility that precipitation of an unstable phase and/or aging effects occur during tests in the region 400" to 700°C. The existence of such behavior should be recognized as affecting the properties of the commercial material and perhaps can be employed advantageously. Experimental Method All testing was done at room temperature using a Baldwin universal testing machine. A microformer extensometer was used in conjunction with a micro-former-type stress-strain recorder. All tests were conducted at constant loading rate, the slowest rates being used. This corresponded to 120 lb per min in the 1200 lb full scale range and 300 lb per min in the 6000 lb full scale range. After the rate of loading was set in the elastic range of the material during the early part of the test, no further adjustments were made, allowing the test to proceed at that setting. In the plastic region of the curve above the yield region, strain rates of from 0.002 to 0.006 in. per min were regularly obtained. All experimentation was carried out on specimens machined from the same lot of beryllium, lot No. Y5036BP. Table I shows the chemical analysis as furnished by the supplier, Brush Beryllium Co., as well as the standard specifications to which commercial beryllium is produced. Both 1/4 in. thick hot pressed plate and ½ in. round hot pressed and warm extruded rods were obtained. The history of the material is reported to be as follows: 1—Beryllium metal plates, produced from a standard hot pressed QMV beryllium metal block 4x15x40 in., were cut off and finished machined to 1/4x6x12 in. flat plates. The original hot pressed block was made by hot pressing —200 mesh vacuum cast attri-tioned powder at about 1050°C under vacuum. 2—Beryllium rod was hot pressed and warm extruded. Extrusion billets were machined from the regular hot pressed blocks followed by extrusion at 425°C. The extrusion was done without jacketing, and graphite was used as a lubricant. The rods were then straightened at 720 °C, after which they were annealed at 800°C for 15 min. Both flat tensile specimens and round tensile specimens were tested. The former were machined from the plate stock into standard specimens according to specifications shown in ASTM E8-52T. The nominal cross-section was 0.25x0.500 in. and the gage length was 2 in. The round specimens were

Jan 1, 1956

By Nicholas J. Grant, Robert F. Wilde

TAYLOR and Floyd's"" work in establishing phase diagrams based on the elements Ni-Cr-Ti-A1 has led to an understanding of the precipitation hardening mechanism in alloys based on these elements. Nordheim and Grant4 concluded that in simple alloys, and where the aluminum to titanium atomic ratio was such that less than three out of five aluminum atoms were replaced by titanium, the precipitate on aging is the face-centered-cubic Ni 3A 1 phase, called They further found that increasing amounts of hexagonal ? phase, Ni3Ti, precipitated from these alloys when the titanium content exceeded the solid solubility of both matrix and Ni3A1. For alloys of Ni-Cr-Ti-Al, in which the titanium and aluminum contents each ranged from 0 to 4 wt pct, the titanium-rich was superior for strengthening to either pure ?' or 7. It was also noted that the combined titanium plus aluminum content (atomic pct) was a direct measure of the high temperature strength and overaging temperatures for these alloys.4 The present investigation was undertaken to extend existing data on precipitation hardening in the more complex commercial alloys containing higher titanium plus aluminum, and with significant quantities of cobalt, molybdenum, and carbon. Experimental Procedure Reforging of As-Received Bar Stock—The alloys were received as ground, forged bar stock. Chemical analyses and the as-received bar diameters are shown in Table I along with the ASTM grain size after the various treatments. All stock except the Waspaloy was reforged to % in. diam to gain material and to facilitate machining of stress-rupture specimens. Forging was carried out at 2100°F, and discontinued when the bar temperature fell to 1800°F. Heat Treatments—For experixental simplicity it was desirable to heat treat all of the alloys at, the

Jan 1, 1958

By R. O. Williams

It is shown that Ni3Al precipitates homogeneously from nickel-rich alwminum alloys as plates on the (100) planes. Prior to actual precipitation a process occurs which is believed to be one of increasing short-range order. After precipitating the Ni3Al plates enlarge through competitive growth. Discontinuous precipitation can occur simultaneously with the above processes. Recent ideas of the origin of precipitation strengthening appear adequate to explain the hardness changes. REMARKABLY little appears to be known about the precipitation process in Ni-Al alloys in spite of their technical importance. This investigation originated to supply additional information about precipitation in general, this system in particular. Information on the structures and kinetics have been obtained through the use of hardness, X-rays, microscopy, calorimetry, and resistivity on high-purity alloys. PROCEDURES Six alloys, Table I, were prepared by melting carbonyl nickel and high-purity aluminum in alumina crucibles in vacuum and casting into 1-in. graphite molds. All rods were homogenized at least once at 1300°C for 24 hr prior to swaging and this was repeated on the first three alloys after 75 pct reduction. Alloy 4 could be reduced only 10 pct at 1000°C (probably in two-phase field) prior to fracture but 1/4-in. samples quenched from 1100°C were readily reduced cold. Alloy 5 was reduced 15 pct cold but failed on the next pass while alloy 6 of essentially the same aluminum content failed inter-granularly without apparent flow up to 1000°C. The alloys were heated in hydrogen at the elevated temperatures and formed thin, coherent aluminum oxide coatings which provided excellent oxidation resistance at lower temperatures. However, freshly prepared surfaces showed considerably less resistance at 500"to 700°C in air and apparently resulted in internal oxidation. As a consequence, low-temperature agings were carried out in evacuated tubes. RESULTS The isothermal hardening behavior of these alloys at 500"and 565C is given in Figs. 1 and 2. These results were obtained from samples cold worked 75 pct, recrystallized at 1000°C (1100°C for the 7.8 pct Al) and quenched in water. This recrystallization was used to give smaller grain sizes so as to obtain more uniform hardness values and the points represent an average of five readings. The electrical resistivity was measured on 1/16-in. wires quenched from 1000°C during aging at 495°C to give Fig. 3. The energy release and its rate are given in Fig. 4 for the 6.9 pct Al alloy during aging around 500°C. Inasmuch as this was a single run, its accuracy is not known but certainly the general shape and magnitudes are correct. The method used to obtain these results is described elsewhere.' Data for the aging at 600°, 700°, and 800°C of these alloys cold worked 50 pct are given in Fig. 5. Supplementary information from microscopy and X-ray diffraction have been included to indicate recrystallization, discontinuous precipitation and the appearance of superlattice lines from the Ni3Al. The hardness of these alloys as annealed, aged, cold worked, and cold worked and aged is given vs composition in Fig. 6. Those samples which were isothermally aged, Figs. 1 and 2, were reaged at 532°C and at successively higher temperatures for the indicated times to give the data of Fig. 7. These results as well as certain others, support the idea that the level of hardness reached for temperatures above 600°C are equilibrium values more or less independent of path. This being the case, the breaks in the curves would be the complete solution of the Ni,Al. The electrical resistivity versus temperatures for some of these alloys, both aged and unaged, is given in Fig. 8 along with those data from heating slowly (10 deg per day) to high temperatures. Interesting points include the lowering of the Curie temperature (the change in slope), the lack of any indications of a solubility limit and the large temperature coefficient for the Ni3Al. A slight break for Ni3Al around 100C shows up but this is not a Curie temperature as Ni3Al is not ferromagnetic down to -190°C. Metallographically both the nickel-rich solid solution and the Ni3Al appear very much like pure nickel. Profuse twin boundaries are present both

Jan 1, 1960

By C. E. Nelson, T. E. Leontis

THE properties and casting characteristics of sand-cast Mg-Al-Zn alloys, used commercially in this country and abroad, have been discussed in a number of articles during the past few years.'-" In addition, broad surveys of many compositions in the magnesium corner of the Mg-Al-Zn diagram between 0 and 12 pct A1 and 0 and 6 pct Zn have been presented by Busk and Marande7 and by Fox." The purpose of this paper is to furnish a comprehensive survey of the changes in tensile properties, micro-structure, and dimensional stability of two magnesium alloys, AZ92A and AZ63A,+ as a function of aging time and temperature after solution heat treatment. Rates of precipitation in Mg-Al-Zn alloys are slow enough so that a substantially homogeneous, supersaturated solid solution can be maintained even when these alloys are air-cooled from the heat-treating temperature. Consequently, even though it has been demonstrated9 10 that significantly higher strengths can be developed in some alloys in the aged condition by quenching rather than air cooling from the heat-treating temperature, general practice is to air-cool magnesium alloys. All the work discussed in this paper is based, therefore, on aging studies performed on material air-cooled from the heat-treating temperature. This investigation was intended to be a study of commercially practical aging cycles; the tensile properties were determined, therefore, up to aging times of 25-hr duration. The alloys, used in this investigation were prepared in the laboratory by remelting commercial ingots of the appropriate composition according to the procedures described in a previous paper" as the "crucible method." All melts were given the standard superheating treatment in order to insure the maintenance of a uniform grain size of 0.003 to 0.004 in. Standard test bars, 61/2 in. long with a 2½ in. long reduced section having a diameter of Y2 in., were cast from these melts in green-sand molds using a four-bar pattern. The alloys were heat treated according to the following schedules: AZ92A alloy: 500" to 780°F in 2 hr + 780°F (24 hr) AZ63Aalloy: 500" to740°Fin2 hr + 740°F (16hr) In commercial practice," AZ92A alloy is heat treated at 770°F for 18 hr and AZ63A alloy is heat treated at 730°F for 10 hr. The slightly higher temperatures and longer periods of heat treatment were used in order to obtain as homogeneous a solid solution as possible and thus to minimize inconsistencies in the

Jan 1, 1952

By D. H. Polonis, Gary A. Dreyer

This investigation involved a study of the reactions occurring during aging of supersaturated a phase in a CIL-Si alloy. The aging processes at temperatures below 552°C were studied by means of metallography, microhardness, and electrical resistivity measurements. During the initial stage of aging in the temperature range 275o to 525oC an anisotropic phase, which is visible in the form of striations in the micro-structure formed prior to the appearance of the -phase. This transition phase has been designated k' due to its structural similarity to the k phase. The rate of K' formation during aging increased with aging temperature. At 450o and 525°C the reaction appeared to reach completion before significant amounts of precipitation were observed. The overall precipitation reaction in this system involved four stages: formation of formation of at a grain boundaries, growth of particles in 7-egions, and coagulation of into large particles. The relative role of each of these processes is dependent on the temperature of aging. The formation of phase from supersaturated a during aging increases the electrical resistivity and slightly increases the hardness of a 4.9 pct silicon alloy. The formation of during aging decreases the electrical resistivity and increases the hardness until coalescence of particles begins during the final stages of aging. The coalescence of results in a decrease of both electvical resistivity and hardness. THE available literature does not record a detailed analysis of the aging processes in Cu-Si alloys. Such an analysis has been difficult due to both the limited data available and misleading microstructural observations which have been reported. Previous work suggests that a rather complicated series of processes may be involved in the aging of supersaturated a. The present investigation is concerned with an analysis of the sequence of these aging processes in a 4.9 pct Si alloy. The currently accepted version of the Cu-Si equilibrium diagram, Fig. 1, was published by C. S. Smith in 1940.' This diagram shows a eutectoid at 5.2 pct Si with the high temperature phase, having its composition range entirely to the right of this value. By quenching alloys in the composition range 4.6 to 5.2 pct Si from the region, Smith was able to retain the phase. However, this phase exhibited a striated microstructure which was anisotropic to polarized light. These striations were suggested by Smith to be duplex twins. Using an oscillating crystal X-ray method Barrett2 studied alloys containing 4.0 to 5.4 pct Si quenched from the and regions. The striations observed in quenched specimens were attributed by Barrett to quenching stresses. He found that striations could also be formed by deformation after quenching and identified them as stacking faults in alloys containing 4.0 to 5.0 pct Si. Barrett related the striations in alloys containing 5.0 to 5.4 pct Si both to stacking faults and to a metastable phase which he called The striated structure reported by smith' was also obtained by Hoffmann, et al. 3 By deeply etching their specimens the anisotropic phase on the surface was removed, leaving a structure which was microscopically similar to pure copper. By means of X-ray analysis before and after deformation at room temperature it was concluded that the anisotropic phase was metastable This conclusion has been questioned by Barrett who attributes the discrepancy to superposition of k and lines on the powder patterns of Hoffmann, et alm3 The decomposition of supersaturated according to smith' and Anderson,4 is very sluggish. However, Nony and Dreyer,5 and Hoffmann, et al.' found that deformation increases the rate of decomposition. X-ray studies by Hoffmann, et al on

Jan 1, 1962

By J. H. Westbrook, R. W. Guard

The influence of a number of alloying additions on the structure and hardness of Ni3Al (?') has been studied. Three general effects have been observed.. solid-solution hardening, strain aging, and defect hardening arising from deviations from stoichiometry. The solid-solution hardening phenomena are complicated relative to binary terminal solid solutions due to the possibility of virtually independent substitution for the component elements and to the concomitant effects of strain aging. In many superior nickel-base high-temperature alloys the elevated temperature strength is attributable to the presence of a dispersion of Ni3A1 (?') in a solid-solution matrix. Examples of such alloys are Inconel X-550, Inco 713, Waspalloy, and Nimonic 80. It is, therefore, appropriate to seek a further understanding of the properties and alloying behavior of this compound. Ni3Al, the compound most rich in nickel in the nickel-aluminum binary system, was first detected by litakal but not established with certainty until the much later studies of Bradley and Taylor' and Alexander and Vaughan.3 More recently the mechanism of formation was clarified by Floyd4 who showed that Ni3Al is the product of a peritectic reaction at 1395°C between the melt and the compound NiAl in agreement with the original suggestion of Alexander and Vaughan.3 Ni3Al has the ordered face-centered-cubic or Cu3Au structure in which the nickel atoms occupy the face centers and the aluminum atoms the cube corners, a0 = 3.570A. Despite earlier reports to the contrary. the compound apparently remains ordered at least to 1000oC.5 It exists over a narrow range of compositions (-3 pct wide) whose limits and temperature dependencies thereof have been reviewed recently by Taylor and Floyd.' Most previous workers have found Ni3Al to be both hard and brittle7,8 although Maxwell and Grala8 obtained 2.5 to 6 pct tensile elongation at room temperature and Alexander and vaughan3 described the material as "hard and tough" on the basis of observations made while preparing metallographic specimens. In a recent study one of the present authors found that although considerable intergranu-lar brittleness was evident: individual grains of a coarse-grained inert atmosphere arc-melted specimen were readily deformable.l0 The same study also showed Ni3Al to have an anomalous temperature dependence of hardness in that such a curve exhibits a number of peaks between room temperature and 800°C which could not be associated with any microscopically observable precipitation reactions or polymorphic transformations. It was, therefore, proposed in the present study to elucidate the anomalous high-temperature strength behavior and to examine the solid-solution alloying of this compound and the effects of such alloying on hardness. Sample Preparation and Experimental Procedure-Samples, both of pure Ni,Al and of various alloyed solid solutions based on Ni3Al, were prepared by arc melting 100-g buttons in an inert atmosphere arc furnace. All buttons were heat treated for 4 hr at 1275oC and examined metallographically for homogeneity. Microstructures were typically homogeneous and single phase with ASTM grain size about 1 and unusually clean grain boundaries. Chemical analyses showed good correspondence (within a few tenths of a percent) with intended compositions. Microindentation hardness data were obtained from room temperature to 800°C in vacuo using a balanced-beam type loading system in an instrument to be described in detail elsewhere." In general a 100-g load, a loading rate of 1 mm per min and an indentation time of 15 sec were used. Various indenter materials were used according to the materials bein tested because of specimen-indenter interaction. Fl Measurements of the Vickers-type indentations were made at room temperature. Hardness-temperature curves were run at least twice on each sample to ensure that surface work-hardening effects had been eliminated." Precision lattice-parameter measurements were made on powder samples using a back-reflection

Jan 1, 1960

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

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

Jan 1, 1951

By C. S. Smith

The solubility of tantalum at 1100°C is 0.025 pct in pure copper, 1.2 pct with 20 pct Ni, and 2.7 pct with -30 pct Ni. The solubility decreases with temperature, and the alloys are precipitation hardenable. A 79/20/1 Cu-Ni-Ta alloy reaches maximum hardness after aging at about 750°C and, if cold worked, does not recrystal-lize below that temperature. The alloys have good tensile properties at moderately elevated temperatures and, since they can be hot and cold worked nearly as easily as cupronickel, they are suggested for service at temperatures above the usual limits for copper alloys. MASSIVE tantalum dissolves extremely slowly in copper-rich alloys, and tantalum powder forms refractory surface layers which prevent its solution unless special precautions are taken. After many trials, an 80 pit recovery was consistently obtained by using a mixture of a finely divided tantalum powder with two or three times its volume of potassium tantalum fluoride (K2TaF1,-melting point about 750°C) poured in a slow stream directly on to the surface of the molten copper alloy, so that each particle would remain coated with flux and be immediately and individually wetted by the molten metal. A 50-50 nickel-tantalum alloy has a melting point of about 1400°C and small lumps of it slowly but satisfactorily dissolve in molten copper-nickel alloys as does commerical "ferro-tantalum." The high affinity of tantalum for carbon makes it necessary to avoid carbonaceous crucibles. COPPER-TANTALUM ALLOYS Castings with good shrinkage resulted when 0.1 pct Ta or more was added to copper melted under charcoal and cast in air. Copper in two-pound melts to which 0.1, 0.15, and 0.2 pct Ta had been added retained residual amounts, by analysis, of 0.025, 0.023 and 0.026 pct, respectively. The solubility of tantalum in molten copper at about 1200 °C is therefore about 0.025 pct. The electrical conductivity of these three samples was 100.48, 100.00 and 100.20 pct IACS in the annealed condition, and 98.24, 97.98 and 98.08 in the cold-drawn condition. Wires 0.080 in. in diam withstood from thirteen to nineteen reversed bends after annealing for 30 min in hydrogen at 850°C and the metal was therefore completely deoxidized. The annealing temperature corresponding to 50 pct loss of work hardness in 1 hr in a strip cold rolled 77 pct reduction was 175C, compared to 230°C for equivalent undeoxidized material. It is unusual for a decrease of recrystallization temperature to result from an alloying addition, and the tantalum probably combines with and removes some minor impurity in the original copper that restrained its recrystalliza- tion. No difficulty whatever was encountered in hot or cold rolling or drawing these ingots, and were tantalum not so expensive it would make an excellent deoxidizer for copper. COPPER-NIcKEL-TANTALUM ALLOYS Studies were made of the solubility of tantalum in a large number of copper-rich alloys, but of these significant solubilities were found only in the case of an iron alloy (which, however, separated into two immiscible liquid layers) and alloys of copper and nickel, in which tantalum is freely soluble and which were found to have interesting properties. The latter alloys are the subject of U. S. Patent No. 2,430,306 (1947). They are not at present available commercially. The Ternary Constitution Diagram—The copper-rich corner of the constitution diagram was constructed on the basis of microscopic examination of samples of various composition and treatments. The alloys were hot rolled to 0.25 in. from castings 0.625 in. thick, then annealed for 1 hr at 1000°C, quenched, cold rolled to 0.10 in. and finally annealed for various periods of time at temperatures between 800" and 1100°C in a nonoxidizing atmosphere and quenched. When the solid-solubility limit had been transgressed, particles of a compound believed to be Ni2Ta*were

Jan 1, 1960

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

IN THE past year, Jaffee and Campbell&apos; and Finlay and Snyder2 reported on the mechanical properties of titanium-base alloys, some of which were in the same ranges of composition as are covered in this paper. In this paper, evidence confirming that given by Finlay and Snyder on the effects of carbon, oxygen, and nitrogen on titanium will be presented; and, in addition, new data will be given on the effects of these elements on the flow properties and phase transformation of titanium. Materials and Preparation of Alloys The preparation and general properties of iodide titanium have been adequately described elsewhere.&apos; , As-deposited iodide titanium rod, prepared at Battelle, of Vickers hardness less than 90 was employed as the base metal in the present work. This was the same material as that used by Finlay and Snyder.2 The probable analysis reported by them for standard quality metal holds here also: N 0.005 pct, 0 0.01 pct, C 0.03 pct, Fe <0.04 pct, A1 <0.05 pct, Si <0.03 pct, and Ti 99.85 pct. Carbon was added in the form of flake graphite supplied by the Joseph Dixon Crucible Co. Oxygen was added in the form of c.p. grade TiO, powder, produced by J. T. Baker Chemical Co. Nitrogen was added in Ti3N4 powder, supplied by the Remington Arms Co. Individual ingots weighed 7 or 8 g. Carbon, oxygen, or nitrogen was added by placing the corresponding powder in a capsule made from as-deposited iodide titanium rods and melting the capsule with the balance of the charge. The charge was are-melted with a tungsten electrode on a water-cooled copper hearth under a partial vacuum of very pure argon (99.92 pct minimum). Melting was practically contamination free. Vick-ers hardness increases of less than 10 points were normal for unalloyed iodide titanium control melts. Nitrogen analyses of are-melted iodide titanium showed a nitrogen content of 0.005 pct, about the same as is present in the as-deposited rod. No tungsten pickup was found in a melt of iodide titanium analyzed for tungsten. Weight losses in melting nitrogen-free alloys were very small and varied consistently from nil to 0.015 g (0 to 0.2 pct). This permitted the use of nominal composition for these alloys. Chemical analyses made for carbon, which can be analyzed conveniently by combustion methods, justified this procedure. Where nitrogen was added, considerable splattering took place. Here it was necessary to analyze for nitrogen by the Kjeldahl method. The ingots were hot rolled at 850°C to about 0.045 in. thick. After hot rolling, the strips were descaled by mechanical grinding, and then given a cold reduction of 5 to 10 pct to insure a uniform thickness throughout the length of the specimen. The edge strips and the tensile strips were annealed in a vacuum of 1x10-4 mm Hg pressure for 3 1/2 hr at 850°C and furnace cooled. Methods of Investigation Hardness Measurements: At least five Vickers hardness measurements were taken using a 10-kg load on each sample in the following conditions: (1) top and bottom of each ingot, (2) top and bottom surface of as-rolled and annealed sheet, and (3) on cross-section of annealed sheet and all quenched specimens. Tensile Tests: Tensile tests were conducted on Baldwin-Southwark testing machines having load ranges of 600 or 2000 lb. Tests were made on 1-in. gauge-length specimens, 3 1/4-in. overall length, 1/2 in. wide, 0.040 in. thick, with a reduced section 1 1/4 in. long and 0.250 in. wide. Two SR-4, A-7 strain gauges, one mounted on each side of the specimen, were used to measure the strain over a limited range to determine the modulus of elasticity. After the modulus of elasticity readings had been taken, load vs. strain readings were taken, using only one strain gauge, at increments of 0.0001 in. until the yield points were passed and then at 0.001-in. increments to the limit of the strain-gauge indicator (0.02 in.). Strain readings above 0.02 in. per in. were taken every 0.01 in., using dividers to measure the strain between the 1-in. gauge marks until the maximum load had been reached. Crosshead speed, when using the SR-4 gauges, was 0.005 in. per min, and, when using dividers, 0.01 in. per min. Flow Curves: Flow curves were determined using the true stress-true strain data obtained during the tension test. The usefulness of this type of information has been dealt with very adequately elsewhere by L. R. Jackson,&apos; J. H. Hollomon,6 and many others. Flow curves of true stress vs. true strain could be converted to the more conventional cold-work curve of 0.2 pct offset yield strength vs. percentage of cold reduction by means of the transformation, 1/1 = 1/1-R, where R is the fraction reduction in cold working. Thus, the true strains corresponding to percentage reduction can be calculated, and the 0.2 pct offset yield strengths scaled off the — 6 curve by taking the true stresses corresponding to the values of 6 + 0.002 strain. Heat Treatment: For the transformation studies, the alloys were heat treated in a horizontal-tube furnace using a dried 99.92 pct argon atmosphere, and quenched into water. Essentially no contamination was found after several hours of heat treatment at temperatures up to 1050°C. Metallography: Specimens were prepared in the

Jan 1, 1951

By J. A. Rowland, C. W. Funk

THIS investigation is a part of the United States Bureau of Mines work in conserving the Nation&apos;s resources. The isothermal sections presented were developed as a guide to a comprehensive investigation of the properties and fabricating characteristics of copper-base alloys containing manganese and tin. These alloys are being investigated as possible replacements for the commercial bronzes containing substantial quantities of tin. Development of the isothermal sections has, therefore, been limited to the area between 0 to 20 pct Mn and 0 to 25 pct Sn. Since Heusler1 reported the ferromagnetic properties of the Cu-Mn-Sn alloys in 1903, the system has been the subject of several investigations. These studies were largely concerned with correlation of magnetic properties and crystal structure.2-6 Vero,&apos; however, established the solidus surface of the system, between 20 pct Mn and 40 pct Sn, by thermal and microscopic methods. The a, ß, and y solid solutions were also observed by Vero and reported to extend into the interior of the ternary system. For the present study, the annotated diagram of the Cu-Sn system prepared by Raynor&apos; and the Cu-Mn diagram by Dean and coworkers9 were used as the binary borders of the ternary system. Procedure The metals used in this investigation were electrolytic manganese, washed cathode copper, and three-star tin. The manganese, produced at the Boulder City pilot plant of the Bureau of Mines, had a purity of 99.9 pct; the copper contained less than 0.004 pct Bi and 0.001 pct S; the tin contained 0.070 pct Pb, 0.070 pct Sb, 0.050 pct Fe, and 0.065 pct Si. Heats of 1 lb were melted in alundum crucibles with a 3-kw induction furnace. The heats were chill-cast in iron or copper molds to form 6-in. ingots 3/4 in. in diameter. Molds were washed with graphite or zirconia, depending on the manganese content, and preheated to 150°C. The maximum impurity content of any alloy was 0.03 pct Fe, 0.02 pct Si, and 0.02 pct Al; in most cases, they contained less than half this quantity of any of these impurities. Composition of the alloys and their treatment prior to homogenizing are shown in Fig. 1. Designations adjacent to each composition refer to the heat numbers. With a few exceptions, ingots containing 20 pct Sn or less were hot-swaged. These ingots were swaged, after a 24-hr preheat at 650°C, to obtain a total reduction of 70 pct in cross section. Intermittent reheating was necessary, and reductions were limited to either 0.025 or 0.050 in. in diameter per pass. Selection of a 200-hr homogenizing treatment was based on extensive experiments which indicated that virtual equilibrium was reached after 150 hr. Structures were retained by quenching in water. Grain sizes in the specimens homogenized at 350" and 450°C were generally small. These homogenizing treatments were preceded by a 50-hr anneal at 650°C to facilitate phase identification by increasing the grain size in these specimens. The specimens were furnace-cooled from this temperature to the homogenizing temperature, and the heat treatment was continued for the standard 200-hr period. The homogenized samples were bisected to provide an internal section for metallographic examination. Optimum definition of the microstructure was obtained by successive polishing and etching. Quarter-strength ASTM copper reagent No. 13 gave the most satisfactory results.10 Filings from interior sections of the samples were used for diffraction studies. These filings were annealed in evacuated glass tubes at homogenizing temperatures for periods exceeding 50 hr and quenched in water. During this treatment the manganese content was reduced by significant amounts, probably by vaporization. This change in composition was considered in applying the diffraction data, which were used only as a means of identifying phases where the data were consistent with the metallographic evidence. Phase Identification The a solid solution is readily distinguished by the copper-colored, twinned, polyhedral grains, as shown in Fig. 2, and a face-centered cubic X-ray pattern. Tukon indentations, using a 25-g load, indicate a Knoop hardness of 155 for a quenched from 650°C. Using white light developed by a Wratten 78 A filter, the ß grains in etched specimens have a dark brown tint in contrast to the lighter copper-colored grains of the a phase. Knoop hardness values of 284 were obtained for the ß structure in specimens quenched from 650°C. The ß structure was also distinguished from the a phase by its body-centered cubic lattice. The acicular structure appearing in Fig. 3 was evident in several alloys of higher tin content after quenching from either 750&apos; or 650°C. Since a trans-

Jan 1, 1954

By Nicholas J. Grant, Michio Yamazaki

Cast copper alloys containing 10, 20, and 30 pct Ni and 0.75 to 0.80 pct Al were machine-milled into chips, then comminuted in a rod mill to fine flake powder utilizing a number of processing variables. The powders here internally oxidized, mostly at 800°C, in a low-pressure oxygen atmosphere. The consolidated powders were hot-extruded into bar stock. Room-tenmperature tension tests, stress-rupture tests mostly at 650°C, but also at 450° and 850°C, and hardness measurements after various annealing temperature treatments to study alloy stability were perfomted. Excellent room-temperature strength, high rupture strength at 650°C, and resistance to recrystallization at 1050°C were obtained. Problems in optimizing conditions for internal oxidation of Cu-Ni base alloys are discussed. THE interesting high-temperature properties of SAP&apos; have stimulated considerable effort in the study of more refractory alloy systems where the potential for high-strength alloys at high temperature is great.2-13 A number of methods have been utilized to produce the desired fine, hard particle dispersions, of which internal oxidation2,9,7 of dilute solid-solution systems offers considerable promise by virtue of the potential for producing ultrafine, well-dispersed oxides. While most of the published works are concerned with pure metal matrices, a number of investigators have studied the effects of solid-solution strengthening.10,19 Use of more complex alloy matrices (for example, aging systems) has been unsuccessful because overaging still occurs at high temperatures in the oxide-containing alloys.14.15 Solid-solution strengthening is, however, effective at very high temperatures9,10 and might be expected to contribute importantly to the strength of oxide-dispersion strengthened alloys. For this study, internal oxidation of solid-solution alloys of copper and nickel, containing small amounts of aluminum, was chosen as the method of alloy preparation. PREPARATION OF ALLOYS Three copper alloys containing about 10, 20, and 30 pct Ni and each containing 0.75 to 0.80 pct A1 (enough to yield about 3.5 vol pct alumina) were prepared as air-cast ingots measuring 2.5 in. diameter by 6 in. high (see Table I for the analyses). Processing steps for all the alloys were as follows (also see Table 11): 1) Homogenization of the ingot at 982°C (1800°F) for 45 hr in an argon atmosphere. 2) Machine milling of ingots into fine chips. Average thickness was about 0.1 to 0.2 mm. 3) Hydrogen reduction of chips at 593°C (1100° F) for 1 hr to reduce copper and nickel oxides. 4) Rod milling of chips to finer powders. 5) Hydrogen treatment of powders as in step 3. 6) Internal oxidation of the powders. 7) Hydrogen treatment of oxidized powders as in step 3. 8) Hydrostatic compression of evacuated powders. 9) Sintering of compacts in hydrogen. 10) Hot extrusion. Variations in processing among the alloys were made in steps 4, 5, and 10 (see Table 11). In the past, two methods were utilized to internally oxidize alloy powders. Preston and Grant3 surface-oxidized dilute Cu-Al powders to obtain the necessary amount of oxygen to oxidize the solute metal (aluminum and silicon), and then permitted the formed copper oxide to diffuse and react with the solute in an argon atmosphere. Bonis and Grant4 exposed Ni-A1 and other nickel alloys to an oxygen pressure derived from the decomposition of nickel oxide at a preselected temperature, in an argon atmosphere. Both methods are applicable and can be modified to generate a range of oxygen pressures for oxidation of the solute but not the solvent metals. Procedure I: Surface Oxidation of Alloy A3, Cu-10Ni-0.76A1. Powders of -20 to +28 mesh were surface-oxidized at 500°C (932°F) to obtain the desired amount of oxygen for oxidation of the aluminum to alumina; the powder was then sealed in Vycor and heated at 900°C (1652°F) for various times up to

Jan 1, 1965

By W. L. Phillips

Aluminum and copper single crystals were strained in shear, unloaded and rotated 60, 120, and 180 deg. The magnitude of the Bauschinger strain increased rapidly during the easy glide region and became constant as the easy glide limit was reached. An increment in stress was not required to continue slip in any close-packed plane or in the reverse direction during easy glide. A qualitative theory is proposed to explain the present results. FOLLOWING the initial work on tin by Bausch,&apos; there have been several investigatorsB7 who have employed the shear test to study the deformation of aluminum. In all cases the shear technique was employed in an attempt to obtain a more homogeneous shear than in the conventional tension test The direct shear technique has the obvious advantage, relative to the tension test, that a crystal may be stressed in any predetermined plane and direction, including the reversal of strain sense. In the present investigation the shear technique was employed with aluminum and copper single crystals and their behavior was studied with respect to deformation in all close-packed directions in the octahedral plane. In contrast to previous investigations, the shear technique was used in an attempt to obtain a stress-strain curve in shear which is identical with the corresponding tension curve and then to use the additional degree of freedom of the shear test to study the mechanical behavior of crystals in all close-packed directions in the octahedral plane. PREPARATION OF CRYSTALS Single crystals 1/2 in. in diam and 6 to 7 in. long, were prepared from aluminum containing 0.001 pct Si, 0.001 pct Fe, and 0.001 pct Zn, by spectro-graphic ana1ysis and from OFHC copper. Crystals were grown from the melt in graphite at a rate of 1 5 in. per hr. The copper crystals were grown under an argon atmosphere. No lineage structure was observed in Laue patterns, though small angle boundaries were present in the crystals. The aluminum and copper crystals were annealed at 640" and 900°C, respectively, for 24 hr and furnace-

Jan 1, 1962

By C. Elbaum

If a thin layer of liquid gallium is spread on a surface of solid aluminum, the gallium penetrates high-angle grain boundaries at a very rapid rate and separation along these boundaries follows. An experiment was carried out to investigate this phenomenon. A well-annealed specimen of aluminum 99.994 pct pure, consisting of several large grains was used, Fig. 1. The dimensions of the sample were 25 mm wide by 2.5 mm thick and all the grain boundaries extended through the entire thickness of the plate. This sample was prepared by strain-annealing and, as can be seen in Fig. 1, contained one long, straight boundary. An examination of the crystal orientations showed this boundary to be a coherent twin boundary. The angular misorientations between the grains forming the other boundaries were all in excess of 20 deg. A thin layer of liquid gallium was spread on one side of the specimen at about 30°C (the melting point of gallium is 29.7"C). After the application of the liquid the temperature was lowered to about 27°C. The gallium remained liquid at this temperature and it can be seen from the A1-Ga phase diagram1 that the liquid was probably saturated with aluminum.

Jan 1, 1960

By S. Weissmann, P. R. Swann, D. F. Wriedt

The sizes and density of precipitates in an intemally oxidized 0.19 wt pct Al-Ag single crystal have been determined by low-angle X-ray scattering and by transmission electron microscopy . The correlation in particle sizes measured by the two techniques is reasonably good. For an oxidizing temperature of 800°C the particles were found to INTERNAL oxidation of dilute alloys of aluminum in silver produces an oxide which has an excess of oxygen compared to Al2O3.&apos; It is believed that the excess oxygen is an indication of the small sizes of the oxide particles. Depending upon the particular model chosen for the oxide structure, the size of the o-A1 particles can be calculated as a function of the oxygen-to-aluminum ratio. These calculations pre- have diameters in the range 30 to 140A, with a mean size of about 50.4 as observed by electron microscopy. At lower oxidizing temperatures, less than 600°C, no clearly resolved particles are formed, and it is suspected that if A1-0 clusters exist they must be exceedingly small, i.e., 10A or less in diameter. dicto that the particles would vary in size from 15 to 100A. This range of sizes is amenable to detection by both small-angle X-ray scattering and transmission electron microscopy. This paper compares the cluster sizes in such internally oxidized A1-Ag alloys determined by transmission electron microscopy and small-angle X-ray scattering. SPECIMEN PREPARATION Single crystals were prepared from 99.9999 pct Ag, obtained from Cominco Products, and 99.99 pct Al, obtained from Aluminum Co. of America. All melting operations were carried out in graphite molds under flowing purified hydrogen in a horizontal zone refiner. The silver was first degassed,

Jan 1, 1964