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By H. E. Cline

Solidification of Pb-Sn alloys ranging in composition from 1.2 to 56 at. pct Pb ws observed with polarized light. Lamellar structures were observed over a larger range of compositions in alloys containing excess tin than excess lead, as expected from constitutional supercooling. The occurrence of pools of supercooled liquid surrounded by lead is explained by the difficulty in nucleating tin. Cells and dendrites weve observed in tin-rich alloys. Evidence was found that the degenerate structure formed at low growth rates, the formation of faults, and abrupt changes in composition and structure can be attributed to non-steady-state growth. The apparent interface shape was observed to have deep grooves at the interphase boundaries. HUNT and Jackson have observed the shape of the interface during growth of organic eutectics. They observed the formation of lamellar faults and shape instabilities upon changes in growth rate. The lamellar structure in these organic eutectics was not restricted to the eutectic composition. Recent work by Mollard and Flemings2 indicated that Pb-Sn alloys from 12 to 26 at. pct Pb could be solidified with a lamellar or rodlike structure if a sufficiently steep temperature gradient was used at a slow growth rate. Observations of the solid liquid interface of the Pb-Sn eutectic were made by Davies3 using polarized light. Photographs were at too low a magnification to determine the interface shape, but he has concluded that tin was the leading phase. In the following experiments, solidification of a range of Pb-Sn alloys from 1.2 to 56 at. pct Pb was observed using polarized light, to determine the factors controlling stability of the lamellar structure. EXPERIMENTAL Procedure. One hundred-gram ingots of alloys prepared from 99.999 pct pure Pb and Sn were cast into graphite molds under argon. The compositions of the alloys were 1.2, 6, 12, 26, 36, 46, and 56 at. pct Pb. Two-gram pieces were melted between two cover glass slides which were squeezed into a 1-mm separation. Samples were then observed under polarized light in a hot stage shown in Fig. 1. A long working distance objective designed for viewing at 500 times was used. Photography was made difficult by the lack of illumination and contrast at these high magnifications. By using an elliptical polarization compensator, as suggested by A. Holik, the contrast and illumination could be optimized. Photographs could be taken only at slow growth rates to avoid excessive interface motion during the 15-sec exposure used. The solidification rate was varied by increasing or decreasing the power to the heater. It was found that insulation was necessary to avoid undesired growth rate fluctuations. The temperature gradient, as measured with two thermocouples 1 cm apart, was 80" ± 20°C per cm during all the experiments reported here. The advantage of this procedure is in being able to observe solidification while it is occurring. However, the observations are restricted to the glass-metal surface and may be influenced by this surface. Also, one has no knowledge of the interior of the sample, in contrast to studies of the freezing of transparent organic eutectics.' Observations. The alloy near the eutectic composition (26 at. pct Pb) solidified in a lamellar structure when the growth rate was uniform. If the growth

Jan 1, 1968

By Peter R. Morris

The effecl of preferred orienlation on X-vay dzffvaction measurements of retained austenzte was investigated for four precipitation-hardening staznless steels in sheet form. A method is preserzted for estimating the ervor in measurement associated with a given samplirig direction. The method was used to select an "optimum" sampling direclion in order to minimize errors in measurement due to preferred orientation. hleasuremenls of retained austenite content employing lhe proposed sampling direction are conzpaved to measuretnents enzploying the more commonly used normal direclion for a series of sawzples. THE first application of X-ray diffraction to the measurement of retained austenite in steels is due to Sekito, 1 who employed a photographic technique in which the (111) reflection from a thin strip of gold affixed to a cylindrical sample was employed as a standard. Averbach 2 introduced the "direct comparison" method in which the ratios of observed to calculated random intensity are assumed proportional to the austenite and/or martensite contents. Averbach's work forms the basis of most subsequent X-ray diffraction methods for the determination of retained austenite. Subsequent improvements are due to: Averbach and Cohen,3 who employed a sodium chloride crystal to monochromate cobalt radiation; Averbach et a1.,4 who introduced a bent sodium chloride monochromator; Mager,' who used a bent quartz crystal to monochromate chromium radiation ; Littmam, who first used a geiger counter diffractometer for this purpose; Beu and Beu and Koistinen, 11,12 who studied effects of absorption factor, surface preparation, sample geometry, integrated intensity vs peak height, choice of radiation, monochromator, and filter. The possibility of errors in measured values due to orientation effects was noted by Miller,13 who suggested examination of a surface other than the plane of rolling. Lopata and Kula 14 have developed an experimental technique in which the preferred orientation is measured in each sample. They illustrated the method for a sample containing 42 pct retained austenite. Application of their technique to the 1 to 15 pct range typical for the precipitation-hardening stainless steels does not appear feasible. EXPERIMENTAL PROCEDURE The nominal compositions of the precipitation-hardening stainless steels investigated are listed in Table I. Ingots were solution-treated, hot-rolled to approximately 0.2 in., and reduced to 0.050 in. by a suc- cession of cold rolling and annealing operations. After this treatment the 17-4PH sample was in the marten-sitic condition, while the 17-7PH, PH 14-8Mo, and PH 15-7Mo samples were in the austenitic condition. Samples of 17-7PH and PH 15-7Mo steels in the mar-tensitic condition were obtained by heating to 1750'F for 10 min and holding at -100°F for 8 hr. A sample of PH 14-8Mo steel in the martensitic condition was obtained by heating to 1700°F for 1 hr and holding at -100°F for 8 hr, followed by aging at 950" for 1 hr. POLE FIGURE DETERMINATIONS Samples were thinned to 0.003 to 0.005 in. by etching in a solution containing 250 ml reagent-grade phosphoric acid (85 to 87 pct H3PO4), 250 ml technical-grade hydrogen peroxide (30 to 35 pct H 2 O 2), and 50 to 100 ml reagent-grade hydrochloric acid (37 to 38 pct HCl). The specimens were placed in an "integrating" sample holder which provided a 1-in. oscillation in the plane of the sample. The diffractometer was aligned to measure the intensity diffracted by planes of the particular {hkl} type being studied. The sample was Set for a given latitude angle, a, measured from the plane of the sheet, and diffracted intensity recorded as the longitude angle, 0, measured in the plane of the sheet from the rolling direction, was increased from 0 to 360 deg. After a 360-deg scan of B, a was incremented by 5 deg, and the process repeated. Random standards obtained by spraying suspensions of powdered iron (bcc structure) and nickel (fcc structure) in lacquer were used to correct observed intensities for absorption and geometrical effects. Zirconium-filtered molybdenum radiation was used to determine the transmission regions of the (111) (0to 45 deg), (200) (0 to 60 deg), and (220) (0 to 45 deg) austenite and (110) (0 to 45 deg), (200) (0 to 50 deg), and (211) (0 to 35 deg) martensite pole figures. Vanadium-filtered chromium radiation was used to

Jan 1, 1968

By G. Kimmel, A. Bar-Or

The rate of nucleation and the rates of both lateral and longitudinal growth of martensite plates (needles) in b—a transformation were determined as a function of temperature, in various U-Cr alloys. The activation energies for nucleation and both modes of growth were calculated from the experimental results. The identical values for lateral and longitudinal growth clearly indicate that both are controlled by the WHITE,' Mott and Hines and Holdeen3 showed that characteristic martensite plates (needles) appear in U-Cr alloys during the transformation 8 —0 in the lower temperature range (up to -300°C). Holden pointed out that the rate of growth of the individual martensite plates under isothermal conditions is same mechanism. Lomer's suggestion that single-atom movement over subatomic distances controls the specially slow growth of martensite receives further support from the present kinetic study, which shows that the growth rate can be described quantitatively by known formulas for the growth rate in processes involving single-atom movement. very slow, and suggested that this is due to the slowness of the relief of the stresses engendered during the growth of the individual plates. lomer4 attributed the slow growth to the complexity of the atomic adjustment at the growing interface b/(u. In the present work the rates of nucleation and growth of martensite plates in U-Cr alloys were studied by direct observation, in order to elucidate the mechanism which controls their characteristic slow growth.

Jan 1, 1968

By David Kramer, Cecil G. Rhodes

Critical transport currents were measured as a function of perpendicular external magnetic field in Ti-22 at. pct Nb wire samples. These samples were heat-treated to yield w Phase precipitates at denslties ranging from 10 to 10 17cm-3. The Precipitates are ellipsoids of revolution with major axes of 50 to 1300A. Flux-Pinning by w precipitates is responsible for the high critical transport currents that were ob- ThE ability of a type II superconductor to sustain a zero-resistance transport current (Jc) in an external magnetic field (H) is due to the presence of micro-structural features which can impede the motion of magnetic flux penetrating the superconductor under the influence of a Lorentz force. Such features are referred to as pinning sites. The pinning strength is tained. A sample cooled from 800°C and annealed 1 hr at 450°C carried a critical tramport current of 10 amp per sq cm at 30 kG. Variations in the current-carrying ability of this alloy are due to changes in its pinning strength which is a function of precipitate density and composition and of the composition of the matrix. the reaction of the bulk superconductor to the Lorentz force and depends on the efficiency of the individual pinning sites and on their volume density. The super -current density increases with pinning strength, other things being equal. The above concepts are discussed in detail in a comprehensive review by Livingston and Schadler.' In Ti-Nb alloys, as in other binary titanium alloys, the metastable hexagonal w phase usually forms below the p/a + p phase boundary near the titanium side of the phase diagram. Stiegler et a1.' have summarized much of what is known about w phase in titanium and zirconium binary alloys. The present work deals with

Jan 1, 1968

By H. C. Brassfield, R. E. Fryxell, E. C. Duderstadt, E. A. Aitken, P. K. Conn

Permeation rates of hydrogen through are-cast tungsten were measured at temperatures from 1300" to 2600°C with hydrogen pressure differentials of 1 and 0.1 atm across isothermal membranes. Rates were nearly Proportional to square root of pressure, were inversely ProPortional to membrane thickness, and were temperature-dependent according to the equation: p = permeation coefficient in cu cm (stp)-mm per sq cm-min-atmlr2, R = gas constant in cal per mole-OK, T = absolute temperature in OK. Permeation rates of oxygen through tungsten were deternlined in the range 1965" to 2300°C and at calculated oxygen (02) pressures of 3.3 x 10-4 to 2.2 x at?n using sealed capsules containing Kmown quantities of tungsten oxide. Permeation coefficients obtained in this manner had a temperature dependency in the range of 40 to 45 kcal per mole of permeating species. Permeation coefficients for oxygen were higher than those for hydrogen in the temperature range studied. This is probably the result of oxygen solubility being much greater than hydrogen solubility at these temperatures at a gzven pressure. The purpose of this investigation was to determine experimentally the permeabilities of hydrogen and oxygen through polycrystalline tungsten at temperatures ranging from 1300° to 2600°C. Permeation rates of hydrogen through tungsten have been measured at temperatures up to 925°C,but no previous measurements have been reported for the temperature range covered in this investigation. Some diffusion measurements3&apos;&apos; and solubility measurements3 have been made for hydrogen at temperatures below 2200°C. No previous permeability studies of oxygen through tungsten are known to the authors; however, efforts have been made to determine diffusion rates5-&apos; and solubilities PERMEATION THEQRY Permeation has been defined by ortton" as the overall steady-state flow process from the gas phase on one side of a membrane or wall to the gas phase on the other side and includes the steps of adsorption, solution, diffusion, exsolution, and desorption; in a given temperature range, any of these processes may be rate-controlling. For diatomic gases, which dissociate prior to diffusion, the quantity of gas which permeates through a membrane or wall at a given temperature is directly proportional to the surface area of the membrane, the length of time of permeation, and the difference between the square roots of the pressures on each side of the membrane, and it is inversely proportional to the thickness of the membrane when diffusion-controlled, thus: q = total amount of gas permeating a membrane, p = temperature-de pendent permeation coefficient, A = area of membrane exposed, / = time, p i = gas pressure of high-pressure side, p2 = gas pressure of low-pressure side, d = thickness of membrane. When the surface reactions are not rate-controlling steps and the solution of the gas in the metal follows Henry&apos;s law, the permeation coefficient, P, is equal to the product of diffusivity and solubility. The permeation coefficient is also temperature-dependent according to the equation: Po = permeation constant, Q = activation energy, R = gas constant, T = absolute temperature. MATERIALS The tungsten materials used in this investigation were greater than 99.9 pct pure. The interstitial impurities ranged from < 1 to 50 pprn C, 7 to 35 ppm O, less than 15 pprn N, and undetectable quantities of hydrogen. Previous high-temperature studies of are-cast tungsten have shown that thermal treatment similar to that which the hydrogen permeation cells experienced reduces the carbon content from starting levels of 50 to 60 ppm to about 30 ppm. Metallic impurities were in the low (1 to 50) ppm range. The argon gas used in this investigation contained about 8 ppm N. None of the following gases were

Jan 1, 1968

By C. Altstetter, Y. Huang, E. de Lamotte

Nitrogen was introduced into pure niobium (colutn-bium) and dilute Nb- Zr alloy wires by equilibration with pure nitrogen gas at high temperatures. Room-temperature hardness was correlated with the alloy composition, heat treatment, and microstructure. Hardness was found to be most sensitive to the amount of nitrogen in solution; however, a significant hardening up to 500 Dph look place upon aging of quenched alloys. A coarse dispersion of nitride did not significantly increase the hardness of the material though the nitride was found to have a hardness of 1400 Khn. BY now the marked effect of nitrogen on the properties of bcc refractorv metals is we ll-documented. There are few studies, however, in which the state of the solute has been carefully controlled. Indeed, the composition-temperature-pressure relationships in nitrogen-refractory metal systems have been determined precisely for only niobium and tantalum.&apos;-4 Most investigations on niobium have dealt with alloys High-nitrogen alloys cleaved on (100) planes and had negligible ductility. Precipitation was found to occur in either a discontinuous or a continuous fashion, depending on the composition and cooling rates. Upon cooling, the precipitation first proceeded discontinu-ously by the nucleation of nilride needles at subbound-aries and subsequent growth of a two-phase microcon-stituent. At lower temperatures continuous precipitation occurred in the subgrain interior ahead of the discontinuous precipitation interface. containing nitrogen, carbon, and oxygen in significant but uncontrolled and, in several instances, undetermined amounts. Thus, there has been some uncertainty regarding the presence and the distribution of precipitates. This paper presents results which relate the hardness and microstructure to the heat treatment and nitrogen content of niobium and Nb-Zr alloys. Niobium rod* produced by the Wah Chang Corp.

Jan 1, 1968

By P. R. Sahm, T. V. Pruss

Mixtures of fine GaSb and Gds as well as preal-loyed GaSbl,As, powders were hot-pressed at 690°C and 25,000 psi. Dense alloys with compositional gradients of less than 5 pct were obtained from mixtures containing about 20 mol pct GaAs. For x < 0.2, there were increasing compositional gradients, and for x > 0.2 a GaAs-rich second phase appeared in the microstructure. Densification as well as alloying wlechanisms were enhanced by dissociation and, possibly, oxidation reactions of the powders. Densification of coarse prealloyed material, however, primarily depended on plastic flow phenomena and required temperatures just below solidus and pressures of 50,000 psi Thermal and electrical properties were measured. Although in no case was the figure of merit of melt growth materials approached closer than to within 25 pct, the better overall thermoelectric properties were found in coarse-grained, prealloyed materzals which had been compacted to near theoretical density and where grain regrowth had been induced. Similar results are believed to hold in other binary 111-V compound systems if processed under similar conditions. The densification of unalloyed GaSb powders during pressure sintering (= hot pressing) was shown to depend strongly on powder particle size.&apos; Fine powders displayed a "liquid skin effect" that enhanced compaction through the presence of liquid gallium, whereas coarse powders compacted predominantly by plastic flow. The liquid skin effect, in particular, appeared attractive for alloying GaSb with other, higher-melting, III-V compounds, and to densify these in a one-step operation. This is of special interest in the case of III-V compound alloys as the conventional techniques of melt growth or long-time annealing of powders2 is very time-consuming, especially in cases where a large separation of liquidus and solidus can be expected, such as in GaSbl alloys.2 It was felt that experimentation with this system, a particularly unfavorable example, would allow us to extrapolate to several other, more favorable, cases. Uses of Ill-V alloys are most evident in thermoelectric energy conversion devices.&apos; For this reason certain thermal and electrical properties were measured and compared to those of melt-grown material and to hot-pressed prealloyed powders. EXPERIMENTAL PROCEDURE The pressure-sintering apparatus has been previously described.&apos; Using this equipment, both powder mixtures of GaSb with GaAs and prealloyed GaSbl-,As, powders were hot-pressed. The mixtures were pre- pared from cast GaSb and melt-grown GaAs. The prealloyed material was obtained from stoichiometric melts, initially heated to 1200°C in an evacuated quartz ampoule, and then annealed in the solidus-liquidus interval. A typical annealing cycle consisted of a heating to 850°C (1 hr), extended successive annealing at 750°C (65 hr), and slow stepwise cooling (25 hr) to below solidus. The GaSb, GaAs, and GaSbl-,As, materials were ground in a vibrational mill to particle sizes below 500 . A jet mill reduced these further where necessary. Fine powders were analyzed by Coulter counting for their size distribution. Average sizes by volume were calculated from the data. Mixing of the powders, where necessary, was carried out through rapid vibrational motion. The hot-pressing operation consisted of a degassing period of 15 hr, in most cases at 690°C, followed by several hours of compression, normally 25,000 psi at 690°C for powder mixtures and 50,000 psi at 710°C for prealloyed powders. The chemical compositions were confirmed by X-ray fluorescence analysis. To estimate the degree of solid solution achieved, lattice parameters were determined and interpreted according to Vegard&apos;s rule. In addition, optical microscopy helped to correlate the relative amounts of the phases present as well as the degree of porosity to the measured density. To reveal grain boundaries, polished surfaces were etched4 with H 2 O:H 2 O:HCl = 2:l:l. In several cases microscopic concentration gradients were monitored by electron-probe analysis-. RESULTS AND DISCUSSION Alloying and Densification of GaSn-GaAs Powder Mixtures. After preliminary experiments showed that no appreciable alloying took place in mixtures of coarse GaSb (22.5 p) and fine GaAs (2.5 p) powders, hot pressing of mixtures was confined to fine powders only (3.1 and 2.4 p, respectively). Alloying and densification apparently occurred simultaneously with a grain regrowth mechanism which depended on the presence of a liquid phase.&apos; The liquid phase was provided by the dissociation of GasbS particles into liquid gallium and antimony above 555°C. This not only enhanced grain regrowth and densification, as in unalloyed GaSb,&apos; but took on additional importance here for the alloying process. Alloying was speeded up by the resulting liquid-solid interaction as compared to the very slow solid-state diffusion process normally expected at these temperatures.&apos; The results obtained with a series of powder mixtures have been compiled in Table I. It is seen that for mixtures with less than 20 mol pct GaAs, x < 0.2, the compositional ranges increased and for x > 0.2 a GaAs-rich phase and free antimony appeared in the microstructure in sizable amounts.

Jan 1, 1968

By P. L. Weston, S. E. Khalafalla

A systematic study was made by the Bureau of Mines on the effect of so me hypothesized accelerators for the process of wustite reduction in carbon monoxide. When small concentrations of promoter materials in the order of 0.69 at. pct were added to the reducible charge, the rate of reduction to iron was increased. Promotion phenomenon prediction was made in light of a suyface reduction mechanism with the aid of Vol&apos;kenshtein&apos;s effect regarding the propagation of crystal lattice disturbances by small amounts of relatively larger interstitial ions. The acceleration produced by a typical promotor, such as potassiunl, increases with protnoter concentration up to a maximum, beyond which the reduction rate decreases. Concentration for maximum promotion depends on the nature and physicochemical properties of the promoter. The extent of reduction rate enhancement is found to be directly proportional to the atomic volume and electronic charge of the additive. DESPITE the enormous volume of literature on iron oxide reduction, very little is reported concerning additive or impurity effects on this important metallurgical process. The beneficial effect bf calcium compound additions on the reducibility of iron oxide sinters has been reported by Tigerschiold,1 vor dem Esche,2 and Edstrom. Doi and Kasai~ found that the addition of lime or limestone to iron ores helps to break up any unreducible compounds, such as fayalite or ilmen-ite. and thus free the combined iron for reduction. Schenck et al. 5 suggested that the increased reduction rate obtained when adding lime could be accounted for by the instability of wustite in the presence of lime. Acid-base slagging reactions resulted in wustite disproportionation according to The dicalcium ferrite formed will yield iron and calcium oxide during reduction. Regenerated calcium oxide dissociates more wustite. This mechanism has been used by Seths and white7 to explain their experimental results. Recently, Strangway and ROSS&apos; attributed the calcium carbonate acceleration of iron oxide agglomerate reduction to increased porosity, both initial as well as that developed during reduction. Aside from calcium carbonate, or oxide, no other promoter was noted in the literature, except for a brief mention by Barrett and woodg on the effect of sodium carbonate and aluminate as activators for the hydrogen reduction of magnetite at 600°C. The present investigation systematically studied a host of other promoters, including calcium and sodium, in an attempt to elucidate the mechanism by which promotion takes place and to fit the results into a simple chemical model. To attain this goal, the effect of promoter physical properties, such as atomic volume, electronic charge, and concentration are related to wustite reduction kinetics in this paper. Wustite reduction to iron, rather than the overall hematite reduction, was chosen since this reaction is known to be the slowest, and hence the rate-deter mining step for the overall iron oxide reduction process. EXPERIMENTAL PROCEDURE Raw Materials and Their Preparation. The pure or impregnated wustite pellets were prepared from minus 400-mesh chemically pure hematite powders. A known weight of hematite was thoroughly and uniformly mixed with a calculated weight of the additive. The mixed paste containing 35 wt pct water was gradually heated from 400" to 1200° C and fired at 1200°C for approximately 4 hr in an air atmosphere. After cooling, the sinter was pulverized to minus 100 mesh and pelletized into minus 4- plus 5-mesh spheres. Pellets were fired, similarly to the paste mix, air-cooled, sized, and stored. An appropriate weight of the charge (20 g) was placed in a zirconia reduction tube maintaining a uniform oxide bed height of 1 cm and a cross section of 7.1 sq cm for all of the test runs. The samples were supported in the vertical reaction tube by a bed of fragmented insulating firebrick plus 3- to 6-mesh alumina beads. The hematite was then transformed to wustite by reduction with a 30 pct CO2-70 pct CO gas mixture at 1000°C in a globar furnace. Complete conversion to wustite was ascertained by a continuous infrared gas analyzer recording the CO-CO2 content of the effluent gas until no carbon monoxide was absorbed from the inlet gas, and inlet-outlet gas analysis remained constant for 30 min. The wustite sample was then reduced with 100 pct CO at 100WC. From the recorded data, an initial rate of reduction was determined by the initial slope of the graph percent reduction vs time. In order to estimate the accuracy of the data, five separate determinations of the reduction curve of pure wustite, under otherwise identical conditions, were performed. The maximum deviation from the average reduction at 14 min amounted to 2 2 pct reduction. This deviation corresponds to 3.8 pct variation based on the percent reduction of the sample. Aiiy impurity effect below the limits of this maximum deviation was considered a spurious result. If the effect exceeded + 4 pct, then it was considered as a positive one. Considerable care was exercised in determining the initial rate from the slope of the initial segments of the curve. Each reduction curve was examined separately on large graph paper and the best tangent to the curve at zero time was drawn. The slope of this tangent was taken as a measure of the initial fractional reduction per minute. Although the time required to reach 50 pct reduction may be of special practical significance, initial rate measurements are invaluable in fundamental studies. These rates provide a measure of the process kinetics on the initial

Jan 1, 1968

By S. Lipson, H. W. Antes, H. Rosenthal

A study was made of the effect of ingot structure on the strength and ductility of high-strength wrought-aluminum alloys. It was found that a fine-cast structure facilitated complete homogenization which, in turn, resulted in significant increases in ductility and strength. A completely homogenized 7075-T6 alloy developed tensile properties of 85,000 psi UTS, 75,000 psi YS, with 40 pct RA. Completely homogenized 7001-T6 alloy tensile properties were 102,000 psi UTS, 99,000 psi YS, with 19 pct Ra. A method was devised for making small ingots having secondary dendrite arm spacing of less than 10 u. This method involved multiple-pass arc melting of commercial rolled plate with a tungsten electvode. This material could be completely homogenized after 3 hr at 900°F; homogenization of the original plate material was not complete after 120 hv at 900°F. Degree of homogeneity was determined by use of metallographic and electron-microprobe analyses. The electron-micro-probe study also showed the preferential segregation of solutes in the microstructure. HIGH-strength aluminum alloys, such as those of the 7000 series, usually freeze by the formation and growth of dendrites. The dendrite arm spacing (DAS) depends on the rate of solidification.&apos; Commercial ingots are usually direct chill-cast to promote more rapid solidification, but, due to the large mass of the ingot, localized solidification times are long and a large DAS results. During solidification, solute elements are rejected by the solid as it forms, causing enrichment of the liquid and ultimately solute-rich interdendritic regions. In order to attain a homogeneous ingot, the segregated solutes must diffuse across the dendrite arms. The larger the DM, the longer the time for complete homogenization. In the case of commercial ingots, the DAS is so large that the time for complete homogenization is prohibitively long and, therefore, second phases or compounds are always present. These un-dissolved phases are carried over to the wrought material during processing, resulting in an impairment of strength and ductility. In addition, the mechanical fibering of the undissolved second phases or compounds during working results in mechanical property anisotropy. If complete homogenization could be attained, higher ductility could be expected. The realization of higher ductility at current strength levels is a desirable objective; however, if higher-strength alloys were wanted, it might be possible to sacrifice some of this ductility by adding more solute elements and produce even higher-strength alloys than are currently available. Further, if complete homogenization leads to more efficient utilization of solute elements, then more dilute alloys should have relatively high strengths with very high ductility. In all instances, it would be expected that the degree of mechanical property anisotropy due to mechanical fibering would be reduced. Therefore, it was the purpose of this investigation to produce cast structures that would facilitate homogenization and to determine the effect of homogenization on the properties of high-strength, wrought-aluminum alloys. MATERIAL CLASSIFICATION Commercial Alloys. In order to illustrate the non-homogeneous condition that exists in commercial high-strength, wrought-aluminum alloys, typical micro-structures of 7001, 7075, and 7178 are shown in Fig. 1. The chemical compositional specifications of these alloys are given in Table I. It can be seen in Fig. 1 that a considerable amount of undissolved second-phase material is present in each of these alloys. The solute elements associated with the undissolved phases were identified by electron microanalyses. Back-scattered electron images and characteristic X-ray images of the three commercial alloys are shown in Figs. 2, 3, and 4. These data indicate that the second phases are regions of high copper and high iron-copper concentrations. The second-phase material also was analyzed for magnesium, zinc, manganese, chromium, and silicon, but no significant enrichment above that of the matrix was found. Therefore, the problem of homogenization resolved itself into one of dissolving the copper-rich and the iron-copper-rich second phases. In order to accomplish this objective, two approaches were made. The first was to reduce the iron as low as possible since this element has a maximum solid solubility of 0.03 pct in aluminum. The second was to produce cast structures with finer DAS to facilitate dissolving the second phases. Commercially Produced High-Purity Alloys. A special high-purity, 2000-lb ingot of 7075 alloy was made by a commercial producer. This alloy contained the following weight percentages of solutes: 5.63 Zn, 2.48 Mg, 1.49 Cu, and 0.21 Cr. All other elements combined were less than 0.02 pct by wt including iron and silicon at less than 0.01 pct each. The ingot was cast and processed into rolled plate using standard commercial techniques. Microstructures of standard commercial 7075 and the special high-purity 7075 are shown in Fig. 5. It can be seen from this figure that the high-purity alloy has less undissolved second-phase material, but a significant amount was still present. The second phase in the high-purity material did not contain iron but it was found to be enriched with copper. The slight effects of the increased purity and de-

Jan 1, 1968

By T. F. Bower, M. C. Flemings

Results are reported of a study of surface dendrilic structure of an Al- Cu alloy solidified against a chill wall. Most primary and secondary "arms " in the surface dendritic structure are arranged orthogonally, giving the impression of strong preferred orientalion on the surface. However, no such preferred orientation exists and it is therefore evident the arms do not represent (100) directions. The primary arms are shown to be interseclions of a (100) plane wilh the chill plane, or, equally often. the projeclion of a (100) direction on the chill plane. Secondary dendrite arms are usually within a few degrees of 90 deg to the primary arm, independent of grain orientalion. Prirary, secondary, and higher-order surface dendrite arms almost always represenl intersections of (100) platzes with the chill surace, or pvojections of (100) direclions. Growlh of secondary arms is favored on the side of the primary arm where a (100) direclion points toward the chill surfAce a1 a Lou, angle. Surface dendrile arms are often observed to be bent. In these cases, the crystal lallice changes orientation; bending is concave to the chill surface. In a previous paper,&apos; a technique was discussed whereby large grains can be obtained at a chill surface. The technique used involves quickly drawing superheated liquid A1-4.5 pct Cu alloy into a thin copper mold, so that the mold is full well before solidification begins. The chill surfaces employed are polished copper blocks coated with amorphous carbon. Shrinkage during solidification between dendrite arms and grains delineates both, without the need for polishing or etching of the cast surface. The grain structure of the chill surface was discussed in a previous paper;&apos; in this paper, the dendrite arms within each grain are examined. Previous work on surface dendrites includes that of Edmunds, who studied the development of preferred orientation in zinc, cadmium, and magnesium.&apos; In zinc and cadmium, he found that the surface region has a (0001) texture (parallel to the chill surface). Walton and Chalmers reasoned that, since the fast growth (1010) directions are in the basal plane, nuclei which have this plane parallel to the mold wall would produce larger grains than nuclei with other orientations. Hence, the texture observed is as expected.3 The same authors, in measurements on aluminum ingots, found no preferred orientation at the mold wall. However, the X-ray technique they used measured the preferred orientation in terms of grain numbers, not grain areas; larger grains were weighted equally with small ones. No preferred orientation is expected on this basis at the chill surface. In a later paper,&apos; Edmunds stated that experiments show a random grain orientation at the surface in die cast aluminum; his technique, also used in his earlier paper, takes account of grain area. Little work has been published on the dendritic structure of metal chill grains. Recent work of Biloni and Chalmers on "predendritic growth" shows the change in morphology from spherical to dendritic during the initial stages of freezing, 5 but this work did not include detailed examination of the fully developed dendrites. Other pertinent work includes that of Lin-denmeyer, who investigated the growth of ice dendrites. 6 When growth was on a substrate, the dendrite axes were bent. The bend corresponded to a change in orientation of the crystal lattice and occurred in such a way as to align the basal plane to the substrate. DENDRITE STRUCTURE Fig. 1 shows the chill surface of a typical casting poured above the critical temperature necessary to produce coarse grains. A cursory examination of these grains shows that the surface dendrite arms within most of the grains are oriented roughly perpendicular to each other. One is tempted to assume that these are (100) directions and that, therefore, marked preferred orientation exists at the chill face. This, however, is not the case. Each of the grains in the casting of Fig. 1 was separately identified, Fig. 2, and its orientation determined by the Laue back-reflect ion method. Results are given in Fig. 3 and it is seen there that no preferred orientation exists. Even when grain area is accounted for, there is no significant preferred orientation. The relationship between surface grain structure and crystal orientation was then obtained by assigning X and Y axes to the casting surface, Fig. 1, and assigning the same axes to the stereographic projections of each grain. Thus, the visible surface structure could be compared readily with grain orientation. This was done for fifty-five of the grains of Fig. 1. Results of this study on three typical grains are described below, and some general observations given subsequently. Fig. 4 shows the structure and stereographic projection of a grain which lies near the (100) zone (with respect to the casting surface). The X and Y directions are marked on the projection, and the photomicrograph mounted with the same orientation. Poles of the stereographic projection represent crys-tallographic directions in the grain which point out of the casting, toward the chill. Two (100) directions are shown in Fig. 4. A line joining the center of the projection and a pole represents the projection of the pole onto the X-Y plane (chill surface). Two such lines are shown in Fig. 4 (solid lines). A line joining the intersection of a great circle with the circumference of the projection gives the trace of a crystallo-graphic plane in the chill surface; two such traces are shown (dashed lines).

Jan 1, 1968

By R. E. Reed-Hill, W. H. Hartt

The "(3034) " twin lamellae in magnesium have been reexamined using electron microscope replicas. The double twinning sequence (1011)- (1012) for these lamellae has been reconfirmed. Evidence is presented showing that the irrational habit of these twins is probably the direct result of a need to accommodate the second-order twinning shear. This accommodation vesults in both an external shear in the matrix and an internal shear in the lamella. A model is presented which accounts for the experimental obseruations. HCP metals are generally characterized by strong textures in which the basal planes of the grains tend to be aligned parallel to the rolling direction in sheet or plate and to the axis of wires and rods. Since these directions are normally those in which finished products may be subjected to uniaxial tensile stress, these textures effectively place the crystals of magnesium objects in orientations unfavorable to both basal slip and {1012) twinning, the easily activated deformation systems of this metal. However, when magnesium crystals are deformed near room temperature by a tensile stress nearly parallel to the basal plane, another mode of deformation can occur.&apos;,2 This is _a double twin which forms first by twinning on {loll), followed by retwinning on (1012). The resulting twin lamellae are of considerable interest. First, they can be responsible for "brittle fracture&apos;&apos;; when a tensile stress axis lies in the basal plane, because the reoriented crystal structure of a lamella is well-aligned for slip while the parent crystal is not. Extensive internal deformation may thus occur while the matrix is still almost undeformed. This deformation can produce a ductile rupture running the length of the twin.3 Complete failure of the specimen may then oc-cure by the spreading of cracks from one twin lamella to another, or by the movement of a crack into a grain boundary and then along grain boundaries. Since the the volume fraction of these doubly twinned elements is normally very small, the fracture may be classed as brittle, although the fracture mechanism is, of itself, essentially ductile. It is quite probable that the ductility transition, normally observed4 in magnesium at or slightly Obove room temperature, is closely associated with these second-order twins. The detailed relationship of these twins to fracture in single crystals will be the topic of another paper. The present paper is concerned with a second important aspect: the irrational habit of these double twins that falls close to {3034), or approximately 7 deg away from the primary (10il) twin habit. There is good reason to believe that this habit results directly

Jan 1, 1968

By N. Christensen, B. Augland, T. H. Johansen

Samples of an Fe-Nb alloy were brought to equilibriurtr with hydrogen-methane mixtures in the temperature range from 950° to 1050°C, and subsequently analyzed on their carbon contents. The solubility pvoduct L = [%Nb] [%C] may be represented by the equation Approximate solubilities indirectly assessed through hardness measurements have been included from a previous report. These data are shown to be in a fair agreement with the present solubility measurements. IN an investigation based on hardness measurements by de Kazinczy, Ms, and pachleitnerl the molal heat of solution of NbC was estimated to 11.5 kcal per mole. This value was considered rather small, and an investigation using a similar technique was carried out. The results indicated a heat of solution about 35 kcal per mole.2 At this stage it was decided to determine the solubility under conditions of true equilibrium . During the course of this work a similar investigation was published by Smith. 3 His heat of solution, 41.6 kcal per mole, is not very different from the value resulting from the present work (42.5 kcal per mole). Our solubility product, on the other hand, is at considerable variance with that reported by Smith. Possible reasons for these differences are discussed below. Mori, Tokizane, and saheki 7 have studied the behavior of niobium in commercial steels, with special attention to the formation of niobium carbide, nitride, and sulfide. Assuming a carbide composition Nbco.87 based on X-ray diffraction and chemical analysis of residues extracted from Fe-Nb-C-S alloys, the molal heat of solution of niobium carbide was estimated to 35.2 kcal per mole. MATERIALS AND EQUIPMENT The chemical analysis of the materials is given in Table I. Electrolytic iron* was used in the preparation of

Jan 1, 1968

By A. J. Ardell, O. D. Sherby

The elevated-temperature steady-state creep behavior of polycrystalline a Zr was studied in vacuo under constant tensile stress. The experiments were conducted from 660° to 845°C over the stress range 870 to 5400 psi. The steady-state creep rate, is, of a Zr was found to be related to the applied stress, a, and temperature, T, by the equation where C is a constant. Two interpretations of the data are considered, each requiring different values of the parameters ß, Q, and . It is shown that this formula can be derived using Gilman&apos;s phenomeno logical equation relating dislocation velocity to the shear stress for the case where dislocation mobility is limited by the nucleation of kink motion. From the fundamental dependence of strain rate on dislocation velocity and the density of mobile dislocations, the factor exp(ßo) can be related to the stress dependence of the dislocation density, and Q to the energy of kink formation. The two interpretations considered are as follows: Case I—the parameters are adjusted so that the equation above describes the data over the entire range of stress and temperature, implying that creep is controlled exclusively by dislocation glide; Case IIthe parameters are adjusted to allow for the possibility that creep is diffusion-controlled at high stresses but glide-controlled at low stresses. For both cases the values of the parameters are within the spread permitted by the data. Factors favorable to the observation of the unusual stress -dependence of i, for a Zr are discussed and it is shown that the anomalously rapid rates of self-diffusion and the low modulus on the principal glide system are primarily responsible for the anomalous creep behavior. Metal-lograflhic observations are presented and discussed with reference to the overall creep behavior. PREVIOUS investigations of the creep behavior of a Zr have been conducted from room temperature to about 500C The results of these investigations are primarily of engineering significance because of the variety of conditions under which they were carried out, and the low testing temperatures employed. Little information is available concerning the fundamental nature of the elevated-temperature creep behavior of a Zr. This investigation of the creep behavior of a Zr above half the melting temperature (the melting temperature, T,, of a Zr is estimated to be about 1860"K was initiated because there are two significant anomalies of the physical properties of a Zr: a) the rate of self-diffusion in polycrystalline a Zr is anomalously rapid: b) both Young&apos;s modulus for polycrystalline a Zr and the shear modylus as-sociated with the prismatic slip system { 1010)( 1120) (the principal slip system in a Zr 7) have anomalously large temperature variations The importance of these quantities to the understanding of creep behavior has been demonstrated, and it was hoped that this investigation would provide a critical test of the predictions based upon the analysis of creep data for other pure metals. However, as the investigation progressed it became increasingly clear that the unusual creep behavior of a Zr could not be analyzed in a conventional manner. 1) EXPERIMENTAL EQUIPMENT AND PROCEDURES Two grades of zirconium, designated A and B, were used in this investigation. The analyses, as supplied by the vendors, are presented in Table I. Material A, with a nominal purity of 99.84 pct, was supplied by the Wah Chang Corp. in the form of cold-rolled sheet from which specimens were machined without further fabrication. Material B, with a nominal purity of 99.95 pct, was purchased from the Nuclear Materials and Equipment Corp. in the form of iodide crystal bar.

Jan 1, 1968

By C. H. P. Lupis, R. Hocine, G. Bernard

The necessary and sufficient conditions for the stability of a multicomponent phase with respect to infinitesinzal fluctuations are derived and transformed to be written in terms of activity coeffcients and mole fractions rather than in terms of the customary second deritlatives of the free energy. NECESSARY conditions for the stability of a multi-component system were derived by Gibbs as early as 1876.&apos; However, as the usefulness of these conditions is greatly enhanced by the simplicity of their translation in terms of functions of common usage, the present contribution establishes these conditions in terms of activities or activity coefficients-and mole fractions. It was shown in another article2 that not only may these conditions be used for the prediction of the appearance of new phases, but they may also provide a check on the orders of magnitude of the interaction coefficients involved. "Spinodal" decomposition is said to occur when, at constant temperature and pressure, the system is unstable with respect to infinitesimal fluctuations in composition. As a result, the "phases" which appear may be attained through continuous changes in the system rather than discontinuous ones, and, consequently, the free energy of these phases may be described by a unique continuous free-energy function. For a binary system, the familiar curve of Fig. 1 illustrates the case we wish to extend to a multicom-ponent system. The conditions to be written pertain to the decomposition of a system of n moles into moles of phase moles of phase v, ...hen moles of phase 9, where the phases a, ...v, ...9 are—at least initially-arbitrarily close in composition to that of the original phase. Each A, is positive and since the total number of moles n in the system remains constant: Each phase v contains hv(nl +dnY) moles of component (I), ...xV(ni +dny) of component + dnk) moles of component (m). The total number of moles ni in the system remaining also constant, it is clear that:

Jan 1, 1968

By J. Larsen-Badse

The resistance to dry sliding abrasion us been measured for some hardened and tempered carbon steels. The wear resistance, defined as the reciprocal of the volume loss per unit sliding distance, is found to vary linearly with the hardness of the abraded surface. The data fit two lines, one, of high slope, for the pure metals and for the annealed steels and another, of smaller slope, for the hardened and tempered carbon steels. A relationship is developed showing the alwasion resistance to be proportional to the hardness of the material and to en, where n is the exponent of work hardening. The values of n and of the hardness FOR most materials a high resistance to abrasion is generally associated with a high value of indentation hardness. Brine11 even used the abrasion resistance as a measure of hardness in an attempt at expanding the hardness range covered by his indentation-hardness test.&apos; When comparing different types of materials there is, however, only a very general relation between abrasion resistance and hardness. Sample brittleness seems to contribute to the deviation from a direct relationship. In general, increased brittle- are those relating to the heavily deformed abraded surface. However, for materials having n constant or varying m a regular manner over a wide range of strailts, the wear resistance will also be a linear function of the bulk hardness of the material. For tempered steels containing a dispersion of cementite in ferrite the increase in wear resistance due to the dispersion is found to be a linear function of the volume fraction of Fe3C and of the reciprocal of the mean free ferrite path. This indicates indirectly that the yielding of this material, when it is already heavily deformed, follows the Orowan criterion. ness leads to decreased abrasion resistance.&apos; When comparing materials in the same group, e.g., the metals, the spread is less. Kruschov found that the abrasion resistance of pure metals and of annealed steels is directly proportional to the hardness of the metal. For hardened and tempered steels he obtained another linear relationship, one of smaller slope and intersecting the line for the pure metals at the location of the data for the annealed steels. He also found that the abrasion resistance of cold-worked metals is independent of the degree of cold working. This shows, as he concluded, that the process of abrasion work hardens the metal in the surface region to a very high degree.

Jan 1, 1967

By A. H. Larson, L. G. Twidwell

The influence which Au, Ag, Sb, Bi, Sn, and Cu have, both individually and collectively, on the activity coefficient of sulfur in liquid lead at 600"C zuas studied by circulating a H2S-Hz gas wlixture over a specific lead alloy until equilibrium was attained. Subsequently, the H2S concentration in the equilibrium gas mixture and sulfur concentration in the condensed phase were deterruined. The elements gold, silver, and antinzony (above 8 at. pct) increased the activity coefficient of sulfur. Bismuth had no apparent effect. Tin (above 3 at. pct) and copper decreased the coefficient. The influence of an individual element, i, on sulfur is best reported as the interaction parameter, riS, which is defined as The values o these first-order interaction zus are: ESzu = —55.0. These interaction parameters are used to predict the activity coefficient of sulfur in six fouv-component alloys and one seven-component alloy. Comparisons are made with direct experimental determinations. INTERACTIONS in dilute solution have been studied by many investigators. Most of the experimental work has been confined to solute-solvent interactions in simple binary systems and solute-solute interactions in ternary systems. Dealy and pehlke"~ have summarized the available literature on activity coefficients at infinite dilution in nonferrous binary alloys and have calculated from published data the values for interaction parameters in dilute nonferrous alloys. Interaction parameters are a convenient means of summarizing the effect of one solute species on another in a given solvent. Only a few investigators have studied interactions of the nonmetallic element sulfur in a metallic solvent. They are as follows: Rosenqvist,~ sulfur in silver; Rosenqvist and Cox,4 sulfur in steel; chipman, sulfur in alloy steels; Alcock and Richardson,% ulfur in copper alloys; Cheng and Alcock,&apos; sulfur in iron, cobalt, and nickel; Cheng and ~lcock,&apos; sulfur in lead and tin. The only reported work on the Pb-S system in the dilute-solution region is that of Cheng and Alcock.&apos; Their investigation involved a study of the solubility of sulfur in liquid lead over the temperature range 500" to 680°C. The results may be summarized by the following relationship: S (dissolved in lead) + Pb(1) = PbS(s) log at. %S = -3388/T + 3.511 Experimentally, it was found that Henry&apos;s law was valid up to the solubility limit of sulfur in lead, i.e., at 600°C up to 0.43 pct. Their investigation did not include the study of sulfur in lead alloys. More accurate calculations could be made in smelting and refining systems if activity coefficients of solute species could be accurately predicted in complex solutions. One of the objectives of this study was to compare the experimental data with the values calculated from the equations derived from models for dilute solutions proposed by wagner9 and Alcock and Richardson. A temperature of 600°C was chosen as the experimental temperature to attain reasonable reaction rates and to minimize volatilization of the condensed phase. EXPERIMENTAL Materials. The Pb, Au, Ag, Sb, Bi, Sn, and Cu used for preparation of the alloys were American Smelting and Refining Co. research-grade materials. All were 99.999+ pct purity except the antimony and tin which were 99.99+ pct. The initial alloys prepared for this study consisted of twenty-one binary alloys, eleven ternary alloys, and one six-component alloy. The constituent elements were mixed for each desired alloy and were placed in a crucible machined from spectrographically pure graphite. The crucible was placed in a vycor tube which was evacuated with a vacuum pump and gettered by titanium sponge at 800°C for 8 to 12 hr. After the gettering was completed, the chamber containing the titanium was sealed and removed. The remaining sample chamber was placed in a tube furnace at 800°C for 2 hr and quenched in cold water. The final operation consisted of homogenization of the alloy for 1 to 2 weeks at a temperature just below the solidus for the individual system. The resulting master alloys were sectioned into small pieces and a random choice made for individual equilibrations. Cobalt sulfide (Cogs8) used to control the gas atmosphere in the circulation system was prepared by passing dried HzS for 24 hr over a Co-S mixture heated to 700°C in a tube furnace. This material was then mixed with cobalt metal to give a two-phase mixture which, when heated in hydrogen to a particular temperature, produced a desired H2S/H2 gas atmosphere in the circulation system. A Cu2S-Cu mixture also used in this study was prepared in a comparable manner. Apparatus for Equilibrium Measurements. The experimental technique of this study required apparatus

Jan 1, 1967

By D. T. Peters, C. R. Cupp

Aging of commercial 18 pct Ni maraging steel and of related binary, ternary, and quaternary alloys has been studied by electrical resistivity, X-ray diffrac-tion, and hardness measurements. The aging process is in three stages: 1) recovery of martensite; 2) two precipitation reactions; 3) formation of nickel- rich austenite. The main objective of this work was to discover the nature of the Co-Mu interaction. Addition of cobalt to the Fe-18 pct Ni-5pct Mo alloy results in acceleration of the pvecipitation reaction by increasing the super-sat~lration 0f molybdenum. The cobalt-containing al- loys show no incubation period for the precipitation reaction, but the alloy without cobalt shows an initial slow reaction. These results are interpreted in terms of precipitation on dislocations. At low aging temperatures, the presence of cobalt leads to the appearance of a second type of precipitate which is a particularly effective hardener. Cobalt was found to retard the formation of austenite. Overaging is a combination of classical overaging and the formation of austenite in the structure. he- activation energy for the precipitation reaction determined from resistivity ,measurements is 42.8 kcal per mole and the growth of the precipitate is found to obey at law at high tenzperatures and a tU3 law at low temperatures. HE mechanism of strengthening of the 18 pct Ni maraging steels has been studied extensively since 1962.&apos;-? The strengthening is due to precipitation hardening of the martensitic matrix. The main precipitate is an inter metallic compound involving molybdenum, but there is disagreement about its identity.

Jan 1, 1967

By S. Floreen

Seven iron alloys ranging from 5 to 12 pct Ni and 5 to 14 pct Cr were studied. All alloys transformed to bcc massive martensites. Tempering increased the strengths , probably because of relief of residual stresses generated by the martensite transformation. The major strengthening mechanism appeared to be solid-solution hardening by nickel and chromium. Studies of the work-hardening behaviw, of the effects of prior austenite grain size, and of the effects of changing strain rate and test temperature gaue results very similar to iron or low-alloy steels. Increasing nickel contents markedly improved the toughness at subzero temperatures. Studies of the flow properties did not, however, indicate the reason for the beneficial effect of nickel on toughness. The marine atmosphere corrosion resistance of the alloys was improved primarily by chromium additions, but increasing nickel contents were also beneficial at low levels of chromium. J\ number of maraging and PH stainless steels are strengthened by precipitation hardening in a low-carbon Fe-Ni-Cr martensite matrix. To some extent the resultant properties of these steels must depend upon the properties of this matrix. The present study therefore was conducted to evaluate the transformation characteristics and mechanical properties of a series of Fe-Ni-Cr martensitic ternary alloys. A limited evaluation of the corrosion resistance of the alloys in marine atmosphere was also made. ALLOY PREPARATION Seven 100-lb air induction melts were prepared using electrolytic iron, nickel, and chromium metal additions. The initial Fe-Ni charge also contained 0.05 wt pct graphite to produce a carbon boil during melt down. After melting of the base charge, the heats were refined with 0.1 wt pct additions of manganese, silicon, aluminum and titanium and poured into cast-iron molds. The ingots were homogenized at 1250°C and uni-directionally hot-rolled to 2-in. plate. They were then homogenized another hour at 1250°C, and unidirection-ally hot-rolled to %-in. plate at a finishing temperature of approximately 1050°C. The compositions of the heats are given in Table I. Two additional heats were prepared as 40-lb vacuum-induction melts using electrolytic iron, nickel, and chromium metals, and commercially pure molybdenum chips. A carbon boil, and 0.1 wt pct additions of aluminum and titanium were again employed, but manganese and silicon were not added. The heats were converted to %-in. plate using the procedure described above. The compositions of these heats are included in Table I.

Jan 1, 1967

By Jerome J. English, Gordon W. Powell

An experimental investigation and mathematical analysis of the thermal-dilation behavior of the titanium alloy Ti-7Al-3Cb have shown that the linear dimensional changes associated with the polymorphic transformation need not be isotropic. The absolute magnitude of the linear dimensional change, which may be either positiue or negative, associated with the cr-p transformation is dependent upon the relutzve volumes of different orientations of the transformation product. It is hypothesized that the dilation irregulati-ties that have been observed during the polymorphic transformation of pure, coarse-grained titanium and other titanium-base alloys can be explained in the same manner. When titanium is heated above about 165O°F, the hcp a structure transforms to bcc 0. Thermal-dilatioh measurements have shown that the transformation is accompanied by a decrease in length of 0.16 pct.&apos; Such dilation behavior would be expected because the volume of the hcp unit cell is about 0.3 to 0.4 pct greater than that of the bcc unit cell. A recent investigation2 of the thermal-dilation behavior of an experimental a-p* titanium alloy, Ti- 7A1-3Cb, containing 0.06 wt pct 0 showed that its dilation behavior during the polymorphic transformation differed substantially from that reported for unalloyed titanium. The first time the alloy was cycled through the transformation, the dilation curve closely duplicated that of unalloyed titanium. However, upon repeated cycling through the transformation temperature range, both the magnitude and the sign of the dimensional change associated with the transformation were observed to vary with each cycle. This investigation was undertaken to obtain additional data on the dimensional changes associated with the polymorphic transformation in the Ti-7A1-3Cb alloy and to determine the cause of the dimensional irregularities. After testing, the specimens were examined metallo-graphically. In addition, Laue back-reflection patterns were obtained from selected sections taken perpendicular to the specimen axes to determine the a orientations present in these sections. White radiation from a tungsten target and a 0.1-mm-diam collimator were used to produce the diffraction patterns. RESULTS Dilation Curves. Three types of thermal-dilation curves were obtained when the a-8 titanium alloy was heated and cooled through the transformation temperature range. These three types of curves are illustrated in Fig. 1. The type I curve represents what is considered normal behavior, because the dilation change is what would be expected on the basis of the volumes of the unit cells of a and p. The Type I1 curve is the inverse of Type I. Normal behavior is characterized by an expansion on cooling through the transformation, whereas a contraction takes place in the Type 11 curve. With Type ni behavior, no clearly distinguishable length change occurs during the transformation. No other anomalies that might be indicative of other phase transformations were observed in the dilation curves at lower temperatures. Apparently, the cooling rate was low enough for equilibrium to be reached during the 0 to a transformation. Table I lists the types of dilation curves observed during the polymorphic transformation as a function of the direction of measurement and cycle number. The A1 value was determined by extrapolating the low-temperature (a + 5 pct p) and high-temperature (100 pct p) segments of the dilation curves to a common temperature and measuring the difference in the or-dinates at that temperature, see Fig. 1. The transformation occurs over a temperature range in this alloy, so the magnitude of A1 is not an absolute value but depends on the choice of temperature. A mean temperature, T,, within the transformation temperature range was selected for the measurement. T, on cooling occurred about 100°C lower than T, on heating. The first time each of the three dilation specimens was heated to above the temperature, that is, Cycle 2, normal Type I behavior was observed. In Cycle 3, two deviations from normal behavior occurred. First, during cooling of the longitudinal specimen, a substantially larger expansion, +0.21 pct, was measured as 0 transformed to a compared with +0.03 pct in Cycle 2. Second, the thickness specimen was observed to undergo a contraction instead of the anticipated expansion on cooling. Continued cycling of the three specimens from room temperature to 2500°F produced additional changes in the dilation behavior. These changes did not seem to be related to the fabrication direction of the alloy because the values of a1 for the longitudinal, transverse, and thickness specimens varied unpredictably in magnitude and sign. Furthermore, both the longitudinal and transverse specimens showed all three types of dilation curves at least once during the six cycles that they received. Fig. 2 is a sketch of the transverse specimen after

Jan 1, 1967

By R. Lagneborg, R. Gullberg

An X-ray method for determinig volume fractions of phases in textured materials has been developed. The method involves measurements of the integrated intensities of reflections of each phase for one single orientation of the sample. The method was checked by evaluating the phase contents in samples from two stainless Cr-Ni steels containing austenite and ferrite in known amounts. In the present case measurements of about five reflections from each phase were required. The agreement between calculated and known volume fractions was found to be very close. AN X-ray diffraction method is often employed for determining the amounts of two or more phases in a material. The details of the method have been described at several instances.&apos;" In short, the method is based upon the fact that the integrated intensity of a reflection is directly proportional to the volume fraction of the phase considered. In principle, the method only requires the measurement of the intensity of one reflection for each phase. The most severe shortcoming with this method is that it disregards influences from preferred orientation in the material. In a diffractometer, where this type of analysis is most conveniently carried out, the geometry is such that the diffracting planes for a specific Bragg peak are all parallel to the surface of the specimen. This implies that it must be required that the occurrence of the diffracting planes parallel to the specimen surface must be as frequent as for any arbitrarily oriented physical plane of the sample. This requirement will generally only be fulfilled for a material free of texture. Since all materials in reality always exhibit a preferred orientation to some extent. the deficiency of the method is quite serious. In cold-deformed material the texture is appreciable, but also annealed material will in many cases display a considerable texture. The problem of quantitative phase analysis in textured material is one of obtaining the integrated intensity averaged over all orientations of the specimen with respect to the X-ray beam. Lopata and ~ula~ have shown that this can be accomplished by integration of intensities over the whole pole figure, or by random rotation of the specimen in the X-ray beam, or by a combination of both. Hence, in this method the average integrated intensity for a specific reflection is obtained by directly determining the intensity for a sufficient number of physical orientations of the sample. However, since an excess of diffracting planes in a certain surface plane necessarily must be accompanied by a deficiency of another type of diffracting plane, it appears to be possible to obtain the correct average intensity for a specific diffracting plane by performing an appropriate averaging of intensities belonging to a large number of diffraction planes of different hkl when all intensities have been produced from one single orientation of the specimen surface. In the present work such a method has been attempted and tested experimentally for two stainless Cr-Ni steels containing austenite and ferrite. 1) THEORY The expression for the integrated intensity of a Bragg reflection diffracted from a phase in a polycrys-talline sample in a diffractometer is: where C is a constant only dependent on the incident X-ray power and the diffractometer geometry, v the volume of the unit cell, F the structure factor, m multiplicity of the diffracting plane, L Lorentz factor, P polarization factor, e-2 temperature factor, p average linear absorption coefficient of the irradiated vO1umej and V volume fraction of the phase &apos;Onsidered. Hence, the factor R in the abbreviated form of Eq. [I] can be calculated and depends only on 0 and the diffracting plane {hkl}. For an alloy containing two phases, a and y, we can write

Jan 1, 1967