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By R. I. Jaffee, F. C. Holden, H. R. Ogden

Alpha solutes increase the strengths of Ti-Mn alloys through solid-solution strengthening. The substitutional a addition, aluminum, decreases, and the interstitial solutes, carbon and nitrogen, increase the rate of nucleation and growth of a from ß. The best combinations of properties of a-ß alloys are obtained when there is a sufficient quantity of a phase in the structure to dissolve the a solutes. OF the many different titanium-base alloy systems, the predominant alloy type is the a-ß alloy. The properties of the a-ß alloys are dependent on solid-solution strengthening and heat-treatment effects involving the a-ß ratio and transformation reactions. Another variable which influences the mechanical properties of a-ß alloys is the a-stabilizer content of the alloy. An a solute may be present as an intentional addition, such as aluminum, or as an impurity element, such as carbon, oxygen, or nitrogen. It is known that these a stabilizers, when added to titanium, form single-phase alloys which are not heat treatable but which obtain their strength from solid-solution strengthening. Thus, it would be expected that a additions to a-ß alloys would increase the strength of the alloys by solid-solution strengthening of the a phase. In addition, they would affect the transformation kinetics of the ß-to-a reactions and other processes based on the instability of the ß phase. The effects of heat treatment and structure on the mechanical properties of Ti-Mn alloys have been shown in a previous paper.6 This system offers a good base to demonstrate the effects of typical a solutes on the properties of a-ß alloys. The three a solutes described in this work are aluminum, representative of a substitutional a solute, nitrogen, representative of an interstitial a solute, and carbon, representative of an interstitial compound-forming element. The effects of heat treatment and microstructure on the properties of a alloys containing these three elements are described in concurrent publications. Some of these data are used for base-line points in several of the curves used for illustration herein. Experimental Procedures Iodide titanium was used as the base for all of the alloys studied in this work. The alloys were prepared as ½ lb ingots by double arc melting in an argon atmosphere. The ingots were forged to ¾ in. rounds, vacuum annealed for 6 hr at 900°C at a pressure of 10 ' to 10-5 mm of Hg to remove hydrogen, and hot swaged to 1/4 in. diam rod. After me- chanical descaling, test specimens were prepared for heat treatment. The alloys used in this study together with the fabrication temperatures are given in Table I. Heat treatments were done in argon. For the most part, the specimens were sealed in Vyeor capsules under a partial pressure of argon. Quenching was accomplished by breaking the capsule under water. Other cooling methods used included oil quench, argon cool (simulated air cool in an argon atmosphere), and furnace cool. The times for the various heat-treating temperatures are given in Table 11. The tests performed on the alloys consisted of tensile tests on ? in. diam specimens, hardness tests, and microimpact tests. Specimen sizes have been adequately described in a previous publication.' The micrographs presented in this paper were taken from specimens cut from the shoulders of broken tensile specimens. Final polishing was done with Linde B on a slow-speed wheel, and the specimens were etched with a 1½ HF — 3½ HNO, solution. Ti-N-Mn Alloys The transformation diagram and microstructures of the Ti-0.1 pct N-Mn alloys used in this investigation are given in Fig. 1. The effect of small nitrogen additions on the binary Ti-Mn diagram is to raise the ß-transus temperature with little effect on the a solubility of manganese. Also, as has been noted previously,' high manganese-content alloys containing nitrogen, when quenched from temperatures high in the ß field, contain a subgrain boundary phase which appears to be nitrogen-rich a. Marten-site is formed when alloys containing less than about

Jan 1, 1956

By H. T. Green, R. M. Brick

True stress-strain data on alloys of pure iron with up to 2.4 pct Al were obtained in the temperature range +100° to —185°C. Alumi-num was found to reduce yield and flow stresses of iron at low temperatures but to have little or no effect on ductility. The effects of temperature and composition on strain hardening are discussed. SEVERAL independent studies of the behavior of high purity iron binary alloys at low temperatures are now in progress in attempts to evaluate systematically the variables affecting the low temperature brittleness of ferritic steels. This paper reports the results of one such investigation in which the tensile properties of aluminum and aluminum plus silicon ferrites were measured from 100" to —192°C. True stress-natural strain data have been obtained in order to evaluate as many as possible of the parameters which describe the behavior of the materials involved. In comparable studies at the National Physical Laboratory in England, iron and iron alloys of high purity have been produced' and tested at subat-mospheric temperatures.' True stress-natural strain curves were obtained there also. The purest iron contained 0.0025 pct C and 0.001 pct O and N. Even this, as normalized at 950°C following hot rolling, showed little ductility at -196°C. The grain size was ASTM No. 3, and the room-temperature yield strength was 17,800 psi (which seems too high for pure iron). Some of the NPL irons contained considerably more oxygen and demonstrated intergran-ular fracture at —196°C. The authors2 carefully differentiated between intergranular fractures associated with excessive oxygen content and transcrys-talline cleavage with little ductility encountered at —196°C in the purer material. The cleavage stress was half again as great as that associated with inter-granular fracture. Test Material, Preparation, and Procedures Of a number of Fe-A1 alloys produced, eight were considered to be sufficiently pure for testing. Partial chemical analyses (Table I), low observed yield points, and high ductilities indicate these alloys to be comparatively pure for vacuum-melted irons of sizable ingots, 5 Ib or more. To produce the binary Fe-A1 alloys, electrolytic iron was melted in air, cast into slabs, and rolled to strips 0.010 in. thick. These strips, joined into a continuous ribbon and wound into 2 1/2 in. diameter spools, were subjected for four weeks to a moving atmosphere of purified dry hydrogen in a stainless-steel tube at 1050" to 1150°C. Charges of these spools were melted in beryllia crucibles under good vacuums (1 micron), and aluminum (99.97 pct Al) was added to the melts. Compositions of these alloys are recorded in Table I. The ingots were hot forged and then cold rolled at least 65 pct to 3/8 in. rods which were vacuum annealed to the desired grain size, approximately ASTM No. 4, prior to machining into tensile test bars. All tensile specimens had gage sections 1 in. long, with a fillet of 1.5 in. radius to the shoulder. Gage diameters were 0.250 in, except for a few rods where additional cold work required use of a 0.200 in. gage section. After machining, 0.002 in. was removed from the gage diameter using 240, 400, and 600-grit metallo-graphic papers. The final polish with 600 grit left the fine scratches running in the longitudinal direction. By this means, surface metal strained during machining was removed. A few specimens heat treated after machining were similarly reduced 0.004 in. to remove any material affected chemically by the atmosphere during heat treatments, as is discussed in a later section. Tensile tests of the eight alloys at constant temperatures from +100° to —185°C were performed in apparatus which has been described." The essentials include a double-walled insulated metal vessel which contained the liquid heat-transfer medium surrounding the test specimen. A constant temperature was maintained by means of a pyrometer which regulated the pressure of dry air driving liquid air through a copper coil. Temperature variation was less than ±2°C during a specific test. For axial straining, two lengths of case-hardened chain, terminating in simple shackles, loaded the specimen through threaded grips. The lower grip bar passed through a hole in the bottom of the test vessel to which it was joined by a thin-walled

Jan 1, 1955

By R. J. Franklin, G. W. Beckman, D. Warren, E. Both, J. F. Libsch

BINARY and ternary alloys of iron, nickel and cobalt respond to annealing in a magnetic field by a characteristic change in the shape of their hysteresis 100p.l,2 An increase in retentivity and a decrease in coercive force produced by the magnetic treatment cause the hysteresis loop to approach the appearance of a rectangle. Materials with a rectangular hysteresis loop have made possible the contact-rectifier³ and have greatly improved the performance of pulse transformers4 and magnetic amplifiers." In the best material presently available for these applications, a 50 pct nickel-iron alloy," the desired characteristics are achieved by aligning the preferred crystallographic directions of magnetization along the rolling direction of the tape. The objective of the present study has been to produce rectangular hysteresis characteristics in materials with inherently high saturation. Iron-cobalt alloys, exhibiting saturation values up to 24,000 gausses' appeared to offer promise for the magnetic annealing technique, because they remain magnetic to very high temperatures,8 exhibit favorable magnetostriction properties: and show zero crystal energy at 42 pct cobalt.10 Among the ternary iron-cobalt-nickel alloys,7,11 response to heat treatment in a magnetic field is unfortunately limited to alloys having rather low saturation values.' It appeared interesting nevertheless, to study a series of compositions connecting the optimum composition (50/50) of the binary iron-cobalt system with the "Perminvar" composition (30 pct Fe, 25 pct Co, and 45 pct Ni). Very recently, R. Smoluchowski and R. W. Turner," have shown that under certain circumstances magnetic annealing can produce oriented recrystallization. A combination of this technique with the domain orientation utilized in the present study might well result in further improvements. The advantages of the powder metallurgy technique in preparing magnetic alloys for study have

Jan 1, 1951

By B. L. Averbach, Morris Cohen, S. A. Kulin

The martensitic transformation can be initiated by elastic stresses at temperatures above M. in a steel containing 20 pct Ni and 0.5 pct C. Shear strains and normal tensile strains acting on a potential habit plane promote the transformation but compressive strains oppose it. THE strain sensitivity of the martensitic transformation has long been recognized. It is now well known that martensite formation can be induced by plastic deformation at temperatures below, and not too far above, the M, point.' However, the exact role of elastic vs. plastic strains and of the concomitant stresses has proved to be a very elusive matter. Many investigators2-' of the steel hardening reaction have made use of the stresses resulting from volume changes to account for such observations as the existence of retained austenite and its variation across the section of a bar, the change in the amount of retained austenite with quenching rate, and the self-stopping nature of the transformation when the cooling is stopped. The effect of applied strain as an independent variable has been studied in 70 pct Fe-30 pct Ni alloys by Scheil7 and McReynolds.8 Some data are also available for lithium and Li-Mg alloys,9 Cu-Zn,10 Cu-Sn and Cu-A1 alloys," and aus-tenitic stainless steels."-" It has been found that martensite formation can be induced isothermally, even at temperatures above M,, by mechanical deformation of the parent phase. The competitive nature of plastic yielding by slip and by the martensitic reaction has been depicted by Scheil.7 Basically, Scheil postulated that: 1—at temperatures not too far above M, (where austenite is less stable than martensite), a critical resolved shear stress (within the elastic range) is required to promote the transformation to martensite; 2—at and below M,, the austenite lattice becomes mechanically, as well as thermodynamically, unstable and shears over spontaneously into martensite without the application of external stress; and 3—at temperatures sufficiently far above M8, the critical resolved shear stress for martensite formation increases to a level above that required for slip, and plastic flow then supersedes the transformation when external stress is applied. Scheil's concepts were tested by McReyno1ds8 ho found no change in the elastic moduli (measured both statically and dynamically) of 71 pct Fe-29 pct Ni alloys in the vicinity of the M, temperature. Since the moduli did not approach zero or become negative on cooling to M,, it was concluded that the austenite lattice does not become mechanically unstable at M2, as postulated by Scheil. McReynolds also reported that M, is not raised by elastic stresses. Accordingly, plastic deformation was considered to stimulate the transformation by generating martensite nuclei in the distorted regions of the parent phase. The above issues with regard to the role of applied stress require clarification, if a basic understanding of the martensitic transformation is to be obtained. For example, in the reaction-path theory,'"," it is postulated that strain embryos exist in the austenite that provide part of the activation energy for the nucleation process. These embryos are visualized to be regions of localized strain in which the atoms in the austenite lattice are displaced part way along the path to their ultimate positions in the martensite. Consequently, it would

Jan 1, 1953

By W. H. Chang

The phase identification results on several Mg-base alloys are presented. These results have been correlated with strength data and microstructural studies to indicate that carbide dispersion may contribute significantly to raising the recrystallization temperature and strength of Mo alloys. Evidence is presented to show that the degree of carbide dispersion, and hence the extent of strengthening, is governed by the "metal/carbon" ratio which, in turn, depends on both the carbon content and the presence of stable -carbide-forming alloying elements. IN recent years, Mo-base alloys containing small additions of C, Ti, and/or Zr have been developed, which exhibit much higher recrystallization temperature and strength than those of unalloyed Mo. The superiority of these alloys undoubtedly results from simultaneous operation of more than one strengthening mechanism. In the present paper, the strengthening effect of carbide dispersion will be discussed. Although the role of carbide dispersion is being increasingly recognized, the nature of the carbides has, to the author's knowledge, not been well es- tablished. In Table I are presented some of the phase identification results on representative Mo alloys. These results have been obtained by X-ray diffraction of residues electrolytically extracted from an ethyl alcohol solution containing 7 pct HC1.

Jan 1, 1961

By W. Rostoker, D. W. Levinson, A. Yamamoto

The influence of carbon on tensile strength, tensile ductility, transformation kinetics, and grain growth characteristics of selected Ti-Mo base alloys was studied. No systematic influence of carbon in tensile strength or significant deleterious effect on tensile ductility was observed. There was a marked increase in transformation rate due to carbon. Dispersed carbides exert a marked inhibiting effect on grain boundary migration, and thus effectively prevent grain coarsening during solution treatment in the ß phase field. AS part of a research program directed toward the illumination of factors governing modes of transformation, transformation kinetics, and mechanical properties obtainable through these transformations by heat treatment, Ti-Mo base alloys were selected for study. The binary system is a characteristic phase diagram type which has been studied in some detail', ' in relation to transformation kinetics and mechanical properties. Although carbon bearing alloys have acquired a bad reputation, the possibilities of melting titanium under conditions which occasion some carbon pickup are very attractive. It is therefore of considerable importance to know whether carbon, present as a dispersed carbide phase, is actually deleterious when all other detrimental factors are minimized. Basic alloy compositions containing nominally 3, 5, 7, and 11 pet Mo were prepared with systematic carbon addition up to 1 pet by weight. Various of these alloys were subjected to a series of critical and definitive experiments to delineate the effect of carbon on the transformation behavior and associated mechanical properties. Experimental Procedure Alloys were prepared from 115 Bhn magnesium-reduced sponge titanium. This sponge analyzed ap- proximately 0.05 pet C. Ti-Mo and Ti-C master alloys were made by arc-melting the sponge with high purity (99.9 + pet) molybdenum and spectro-scopic grade graphite, respectively. Alloys were then prepared from the master alloys and sponge by double are-melting. One kg ingots were prepared by melting in a nonconsumable electrode furnace. These ingots were forged at 1000°C to '/z in. rods, and cleaned and processed into electrodes for the second melting operation. The final ingots were ground to remove surface defects, then forged again to 1/2 in. or 3/8 in. diam rods for processing to test samples. It is significant that all of the alloys at all carbon levels forged satisfactorily. For convenience, the alloys will be referred to throughout the text by their nominal analyses. Samples for the study of transformation rates were prepared from 1/2 in. diam round stock. They were then solution treated in a helium filled tube furnace at 1000°C for 30 min prior to the isothermal transformation treatments in lead bath furnaces. Temperature control in both cases was within ±3oC. Following the isothermal transformation treatments the samples were water quenched. These experiments were carried out before the general adoption of the resistometric procedure for kinetic studies. The data were therefore obtained entirely by metal-lographic analysis. M, temperature was also determined by the metallographic method. Shoulder-type tensile test pieces were machined from heat treated, 1/2 in. diam slugs to provide a 0.252 in. test diam and a 1 in. gage length. The isothermal-type heat treatments were chosen from previous data' to provide three levels of strength and ductility.

Jan 1, 1957

By H. Conrad

The strain hardening associated with the creep of magnesium single crystals at room temperatu.Je was investigated by shear tests in which the direction of stressing was reversed a number of times after creep in a <100> direction. The strain hardening was strongly anisotropic; the largest amount occurring in the direction of flow and the least 180 deg to this. The time law for creep changed from a parabolic type to logarithmic for the first and subsequent reversals of stress. For a given stress the creep strain decreased significantly for the first and second reversals and then only slightly for subsequent reversals. The logarithmic creep constant a changed in a similar manner. A linear relationship was observed between the creep strain for a given reversal and the stress. The slope for the third reversal yielded a strain hardening coefficient 12 to 16 times greater than that observed for unidirectional flow. Al-though no recovery was observed upon resting at room temperature, the hardening resulting from stress reversals could be completely removed by heating to 450" C. PREVIOUS work1.&apos; indicated that the creep rate of magnesium single crystals tested in the temperature range of 78" to 364°K decreased with time. This was attributed to an increase in internal stress resulting from an accumulation of dislocations at internal obstacles. The object of the present investigation was to further evaluate the nature of this hardening by conducting tests in which the direction of stressing is changed after previous creep in shear in a given slip direction. Previous to 1950 three investigations indicated that a Bauschinger effect3 occurred for single crystals as well as polycrystals brass in tension compression,

Jan 1, 1960

By E. J. Dulis, V. K. Chandhok, J. P. Hirth

Cobalt clearly increased the activity of carbon in austenite and in ferrite. This effect of cobalt on carbon activity Plausibly accounted for the effect of cobalt on accelerating the austenite to pearlite transformation. Cobalt was found to have only a slight effect on carbon diffisivity in various Fe-Co and Fe-Co-W-Mo austenites, but was found to decrease carbon diffusivity in Fe-Co ferrite. THE effect of cobalt in steel is unique in that it is the only element that reduces hardenability by accelerating the austenite to pearlite reaction. The results of several excellent investigations aimed at explaining the role of cobalt have been published,1"7 but a complete understanding is still lacking. In addition, cobalt significantly enhances the resistance to softening or tempering of highly alloyed highspeed and hot-work tool steels. The resistance to tempering is related to the secondary hardening reactions associated with the fourth stage of tempering during which carbides of molybdenum, tungsten, and/or vanadium form in a martensite matrix. The effect of cobalt on secondary hardening reactions in high-alloy tool steel has received considerable attention, but a full explanation of the reactions involved has not been developed. Inasmuch as austenite to pearlite transformation and secondary hardening involve carbide formation, the present authors believed that the role of cobalt in effecting carbon activity and diffusivity in austenite and in ferrite was important to a fuller understanding of the phenomena involved. TO investigate the effect of cobalt on the activity coefficient of carbon in austenite, an approach was used similar to that used by Darken17 in his experiments on the effect of silicon, manganese, and molybdenum on carbon activity and diffusivity in austenite. TO

Jan 1, 1962

By A. Boltax

The effect of cold work on the electrical and magnetic properties of solution-treated and aged Cu-Fe alloys was studied. The electrical resistivity of solution-treated and of aged Cu-1.7 wt pct Fe samples increased by up to 25 and 140 pct, respectively, follozcing a 55 pct reduction of area. The principle contributions to the increase of resistivity of the solution-treated and aged samfiles are examined. Measurements of the .saturation induction, coercive force, and stacking fault Probability are also reported. 1 HIS paper is the second in a series which examine the behavior of the electrical and magnetic prop- erties of Cu-Fe alloys. The first paper1 was primarily concerned with the effects of thermal treatment whereas the present paper examines the effects of cold work on solution-treated and aged Cu-Fe alloys. The effects of cold work on the transformation of the coherent fcc iron precipitate to the ferromagnetic form2 and the coercive force and remanence3 have already been described, but the unusually large increases in resistivity (up to 220 pct) which occlir with cold work have not been reported previously. EXPERIMENTAL METHOD The methods used for alloy preparation, heat treatment, and electrical and magnetic measurements are described elsewhere.1 The specimens, initially 4-in. lengths of 0.0625-in. diam wire, were cold worked by swaging in hardened steel dies. Following each reduction, the samples were etched lightly in hydrochloric acid to remove surface con-

Jan 1, 1962

By D. Walton

The effect of small solute additions of Cu on the activation energies for creep A1 single crystals were determined over the range from 78° to 850° K. Below 240°K and above 800°K activation energies were unchanged. Between 240°K and 400°K strain aging causes the creep rate to become vanishingly small and the flow stress was independent of the temperature. Between 500° and 50°K the activation energy was increased to 41,000 cal per mole. NUMEROUS investigationsL have shown that solid solution alloying invariably increases the flow stress. A typical example is documented in Fig. 1. Such increases in flow stress can arise from two general effects: Alloying can increase the long-range stress fields through which dislocations must move by causing appropriate clustering; modification of dislocation densities, and so forth. Alloying can also modify the short-range stress fields that determine the activation energies for thermally stimulated migration of dislocations, such as occurs in some solute atom pinning processes, and so forth. Actually both long- and short-range stress-field effects can occur simultaneously. It was the purpose of this investigation to evaluate the effect of alloying on the short-range stress fields by determining the effect of alloying on the activation energies for creep. The resulting observations also shed some light on the effect of long-range stress fields on dislocation processes. EXPERIMENTAL TECHNIQUE Single-crystal bars (6 in. long 3/8 in. wide and l/4 in. thick) of dilute solutions of Cu in A1 were seeded, so as to provide extensive single slip, with the pole of the tensile axis located in the standard stereographic projection as shown in Fig. 2. Each crystal was grown under an argon atmosphere in a graphite mold containing a large reservoir of molten alloy for the purpose of obtaining rather uniform composition of Cu along the length of the bar. The nominal compositions of the alloys which were produced from 99.99 pct Cu and high-purity A1 containing 0.001 pct Fe and 0.001 pct Si, are given in Table I. Strains, measured by linear variable transformers attached by quartz rods to a 3 in. gage section were sensitive to and the stresses were ap- plied by direct loading of the specimen. Temperatures were determined by thermocouples attached to the gage section of the specimens. Below 400°K the apparent activation energies for creep, Q, were determined by the effect of small, rapid changes in temperature of about + 10°K from T1 to T2 on the corresponding creep rates ?1 and ?2 during primary creep according to where R is the gas constant.&apos; Above 400°K, Q was evaluated from Eq. [1] for the secondary creep rate using temperature changes of about ±20K. A typical set of results is shown in Fig. 3. RESULTS AND DISCUSSION The previously obtained effect of temperature on the apparent activation energy for creep of single crystals of high-purity A12 is shown by the broken curve of Fig. 4. The datum points on the same graph illustrate the effect of dilute a solid solution alloying with Cu on the activation energy between 600" and 750°K. Each plotted point is the average of not less than five independent test values between 600° and 750°K and not less than three at other tempera-

Jan 1, 1962

By O. P. Arora, M. Metzger, G. R. Ramagopal

Single-phase aluminum containing 0.0001 to 0.06 pct Cu was studied in strong acid, mainly through observations of hydrogen evolution. The strong influence of copper was exerted almost entirely through the imposition after a certain delay time of an auto-catalytic localized-corrosiott reaction. Additions of cupric ion to the acid produced lower accelerations. The significance of the quantity and distribution of copper was discussed, and the implications for intergranular corrosion and neutral chloride pitting were indicated. AN investigation of intergranular corrosion in single-phase high purity aluminum exposed to hydrochloric acid indicated the copper content of the metal to have an influence on corrosion at lower levels than previously suspected.&apos; The work reported here was a closer examination of the action of copper but dealt with general corrosion to gain the advantage of having a continuous measure of corrosion through the volume of hydrogen evolved, the reduction of hydrogen ion to hydrogen gas being the principal or only cathode reaction in strong hydrochloric acid. Previous work on the hydrochloric acid corrosion of aluminum was sometimes insufficiently structure-conscious and the need for care in evaluating it arises from the low solubility of the iron impurity,&apos; and of some alloying elements, and the known or possible presence in many of the compositions studied of second phases leading to greatly increased corrosion rates.3 These increases are attributed to the presence of low hydrogen-overvoltage cathodes provided by the second phase.3&apos;4 For the present single-phase work, a few studies which used high-purity base material and small copper additions5-&apos; provide the essential information most unambiguously. The corrosion rate was shown to be increased markedly by the introduction into the acid of small quantities of the ions of copper (and of certain other metals) which cement on the aluminum and provide cathodes of low overvoltage.5 When there was sufficient copper in the aluminum, the same result was produced during the course of corrosion leading to a rate which increased with time as the reaction was stimulated by one of its products (autocatalytic reaction). In 2N (7pct) HC1, an accelerating rate was observed at 0.1 pct Cu but not at 0.01 pct.5,7 The present work dealt with corrosion rate and morphology and their correlation with the quantity and distribution of copper catalyst for copper contents from 0.0001 to 0.06 pct. PROCEDURE A lot of high-purity aluminum containing 0.0021 pct Cu, 0.001 pct Fe and 0.003 pct Si (Alloy A) was alloyed with copper to yield aluminum containing 0.014 pct Cu (B) and 0.06 pct Cu (C). Later it was found necessary to include the lower copper Alloy K which contained 0.0001 pct Cu, 0.0004 pct Fe and 0.0004 pct Si. The upper limit for any other element can be confidently estimated as 0.0005 pct. No element other than copper appears to be present in quantities sufficient to have an effect on general corrosion as great as the observed effect of the copper in A, B, and C. The only other heavy metal detected by spectrographic examination was silver (< 0.0001 pct). The acid was made up from a selected lot of 37 1/2 pct CP hydrochloric acid containing 0.1 ppm heavy metals (mainly Pb), 0.05 ppm Fe, and < 0.008 ppm As and from water distilled from 1 megohm-cm demineralized water and believed to have contained negligible quantities of heavy metals influencing corrosion. Acid strength was adjusted to within 0.05 pct HCl of the stated value by using precision specific gravity measurements. Test blanks 10 by 41 mm were sheared from 1.65-mm cold-rolled sheet. Edges were finished by filing. The blanks were annealed in air at 645°C for 24 hr in alundum boats and rapidly water quenched. The anneal is thought to have produced a substantially homogeneous solid solution—for iron, copper, or silicon, for example, the annealing temperature was 200°C or more above the solvus-and the quench is considered to have preserved the high-temperature structure except for the condensation of lattice vacancies into dislocation loops.&apos; The 0.06 pct Cu alloy did not appear unstable in respect to slow precipitation reactions at room temperature since two pairs of tests failed to show significant differences between specimens heat treated 3 1/2 years earlier and specimens heat treated 1 or 2 days before.

Jan 1, 1962

By B. A. Cheadle, C. E. Ells

The ovienlalion of hexagonal a-zirconium crystals in cold-drawn Zircaloy-2 tubes and in both as-extruded and heat-treated Zr-2.5 wt pcl ND tubes has been rrleasured using the inverse Pole - figure technique. Uniaxial tensile tests hare shown the Zil-caloy-2 lubes to hare highly anisotropic delovmation behavior whereas heat-treated Zr-2.5 wt pet Nb tubes are nearly isotropic. The differences in deformation behavior are esbloilred from the observed textures of the tubes and the deformation systems known to oberate in Zircnloy,-3. Tlze vcsults lead to an explanation of the high effective strain observed fov the Zircaloy-2 tubes as colrzpared to heat-treated Zr-2.5 wt pet Nb tubes in restrained end burst tests at 280° to 300°C. THE Zr-2.5 wt pct Nb alloy. when heat-treated by quenching from temperatures slightly below the (a + p)/P phase boundary and subsequently aged at 500°C, has tensile strengths about 50 pct greater than those of 20 pct cold-worked Zircaloy-2.1 There is. therefore, considerable economic incentive to replace Zircaloy-2 with the heat-treated alloy in some in-reactor applications. notably for pressure tubes, where strength is a prime consideration. However, when tubes of Zr-2.5 wt pct Nb fabricated by extrusion and drawing prior to heat treatment were subjected to restrained end-burst tests at 300 °C. the circumferential expansion at failure1 was only 10 pct that of cold-drawn Zircaloy-2 tubes in similar tests,2 Table I. This result was not predicted from uniaxial tensile tests in which the ductilities of the two materials were quite similar.&apos; The detailed requirement for ductility in pressure vessels has not yet been worked out. and comparison of the relative merits of cold-worked Zircaloy-2 and heat-treated Zr-2.5 wt pct Nb is further complicated by the irradiation-induced loss of ductility and hydrogen pickup each will undergo from reactor operation.1,2 Nevertheless. the lower circumferential expansion of the Zr-2.5 wt pct Nb tubes raised serious doubts on the advisability of their use as pressure vessels. For this reason, an investigation to determine the cause for different ductilities of the two types of tubes was initiated. From a study of uniaxial tensile properties and crystallographic orientation it has been found that the fracture ductilities observed in the burst tests can be related directly to the crystallographic ori-

Jan 1, 1965

By R. J. Quigg, G. S. Doble

Commercial stress -relieved TD Nickel bar was shown to retain room- and elevated-temperature tensile strength after exposure up to 2501°F. Cold swaging increased both room -temperature and 2000°F tensile strength. After annealing at 2500°F the strengthening due to swaging was retained at 2000°F hilt eliminated at room temperature. Annealing produced changes in hardness and X-ray half peak width indicating the presence of recovery processes as 1071° as 1000°F but no recrystallization of swaged material was noted at any temperature. In contrast to swaging, rolling induced a recrystal-lized structure after annealing. The tensile strength of this recrystallized structure was comparable to the cold-worked condition. High-temperature tensile properties of as -received bar were highly anisotropic with the transverse tensile strength being one fifth the longitudinal value. The aniso-/ropy is affected by working direction and may he partially reversed by changing the direction of metal flow. The divergence in tensile strength, beginning above 550°F or- approximate one third the absolute melting point, is strain-rate dependent. T D Nickel is a commercial dispersion-hardened alloy containing 2 vol pct thoria. The dispersion, consisting of spherical particles 0.030 to 0.050 in diameter with an interparticle spacing of less than 1 is reported to maintain stable properties up to 2400°F.1 This stability of second phase results in maintenance of elevated-temperature strength at higher temperatures and longer times than normal nickel-base superalloys.2 The purpose of this paper is to describe the effect of various mechanical working operations on the strength and microstructural stability of TD Nickel bar. MATERIAL AND PROCEDURES All material used in this study was commercial TD Nickel bar. This material is produced by a chemical process which results in a nickel powder containing a dispersion of thoria particles. The powder is then pressed, sintered, extruded, and subsequently worked to bar stock. Three starting materials from three separate lots were used: as-extruded bar. 1-in.-diam stress-relieved bar, and 1/2-in.-diam stress-relieved bar. Since TD Nickel bar stock is cold-worked without a recrystalliza-tion anneal, the accumulated deformation or degree of cold work in these materials increases as the bar diameter decreases. Some of the 1/2-in.-diam bar was swaged to 1/4 in. diameter at room temperature in order to produce an as-worked condition for comparison with the stress-relieved stock. Tensile testing was performed on an Instron Tensile Tester at a constant crosshead speed of 0.020 in. per min. The 0.2 pct offset yield strength was measured from the load-crosshead movement plot. Specimen gage dimensions were 0.080 in. in diameter by 0.40 in. in length, producing a strain rate of approximately 0.050 min-1. Specimens were tested in air and heated within a resistance-wound furnace controlled to ±5°F. A 15-min soak at temperature was employed before testing. Samples were heat-treated in air and specimens machined after exposure with sufficient material removed to eliminate any surface contamination. X-ray line breadth was determined from a diffractometer scan of a transverse face of a bar using copper K, radiation. Metallographic preparation utilized standard mechanical polishing with Carapella&apos;s etch. Specimens for electron microscopy were electropolished in a 1:7 sulfuric/methaol solution and chromium-shadowed collodion replicas prepared. RESULTS AND DISCUSSION I) Effect of Elevated-Temperature Exposure on the properties of TD Nickel. The effect of various elevated-temperature exposures on the room-temperature tensile strength of TD Nickel is shown in Table I. In the unexposed condition the tensile strength, reduction in area, and hardness all increase with increasing accumulated deformation while the elongation decreases. After exposure at 2500°F the strength of all three materials decreases to about 65,000 psi and the elongations increase slightly. The apparent increase in strength of the 1-in. bar after a 2000°F treatment is probably experimental scatter. These results indicate that the room-temperature strengthening due to additional deformation is annealed out upon elevated-temperature exposure. In contrast to the room-temperature data, the 2000°F tensile strengths increase in order of increasing deformation even after exposure. Although some loss of strength occurs after exposure, much of the effect of working is still maintained at 2000°F. The room-temperature hardness after various

Jan 1, 1965

By D. L. Wood

INTERNAL oxidation&apos; is a process in which oxy-gen, diffused into a suitable alloy, causes precipitation of solute oxide particles as the oxidation front moves inward. During an investigation of internal oxidation now in progress it was observed that the grain size is relatively small in thin strip specimens that have been internally oxidized in the as-rolled condition. This may be due to the restraint of grain growth by the precipitated oxide particles. It was observed also that the grain size in unoxi-dized portions of partially oxidized specimens was

Jan 1, 1958

By E. S. Bumps, M. Baeyert, W. F. Craig

SOME time ago during a study of impact properties of tempered martensite,1 it was postulated that the consistently good ductility of tempered martensite might be caused by its relatively small and peculiarly shaped ferrite grains. The fer-rite grains of tempered martensite have approximately the same size and shape as the martensite "needles." Thus they form an interlocking mass of needle-shaped grains quite different from equiaxed or lamellar ferrite grain structures. When the common mechanical test methods are applied to steel, variations are often observed in the ductility of specimens that have closely similar hardness and tensile strength values. The ductility so measured appears to be structure dependent. When steel from the same heat has been heat treated to produce different structures with the same hardness, the elongation and reduction of area values from the tensile test and the transition temperature determined by the notched-bar impact test vary according to whether pearlite, tempered martensite, or other structural constituents were produced by the heat treatment. It has been widely recognized that tempered martensite gives a consistently good performance, when tempered to the same hardness as many other structures with which it has been compared. In recent years the isothermal transformation of austenite to specific structural products and the quantitative evaluation of the character of these products with respect to their nature and response to deformation has received considerable attention. The objective of the present study was to pursue somewhat further the dependence of ductility upon structure; specifically, it was desired to ascertain whether ferrite grain structure, including both shape and size of the grains, can account for the consistently good performance of tempered martensite in the notched-bar impact test. It was thought that a simple experiment would indicate whether the ferrite grain structure plays any part in the good ductility exhibited by tempered martensite in contrast to other steel structures with different types of ferrite grains. By determining the impact transition temperature, it was proposed to compare spheroidites having similar carbide particle size and spacing but obtained in such a manner that their ferrite grain structures would be very different. Spheroidite obtained by tempering martensite, with its small, needle-shaped grains, was to be compared with spheroidite from pearlite. If the latter is produced by sub-critical annealing, the ferrite grains correspond to the pearlite colonies. Thus, if the pearlite was not too coarse, the ferrite grains of spheroidite from pearlite are equiaxed in contrast to the needle-shaped grains of spheroidite from martensite. It was thought that the ferrite grain structure of spheroidite from martensite might depend to some extent upon the grain size of the prior austenite. The austenite grain boundaries limit the maximum attainable size of the martensite needles and thus of the ferrite grains in the derived spheroidite. In order to evaluate any possible influence of prior austehite grain size, spheroidites were to be prepared from martensites that had been formed from fine-grain austenite and also from coarsened austenite. As the carbide particle size and distribution were to be essentially alike in the various spheroidites, the difference would be in the ferrite grain size and shape. Thus any marked difference in transition temperature could be attributable to the character of the ferrite grain structure. There are certain considerations in assuming that these spheroidites would be equivalent in all respects except ferrite grain structure, and an attempt was made to take them into account. One of the considerations was the choice of the carbon content of the steel. An approximately eutectoid steel was selected for two reasons. First, the pearlitic structure would contain no proeutectoid ferrite which might complicate the picture by producing a non-uniform ferrite grain structure in the resulting spheroidite. Then, too, the high-carbon content would inhibit ferrite grain growth during the sub-critical treatment. Another factor to be taken into account was the choice of an alloying element to assure a martensitic structure throughout on quenching the impact specimens. Nickel was chosen, because it is a common alloying element and resides in the ferrite both upon its formation from austenite and throughout tempering. The formation of alloy carbides, or even a large solubility of the alloying element in cementite, would have complicated the interpretation by changing the composition of the ferrite .during spheroid-ization. The possibility of temper brittleness was minimized insofar as possible by using a tempering temperature as high as consistent with the 1 pct of nickel in the steel, namely, 1150°F. While it certainly is not claimed that no difference other than ferrite grain structure could exist between the spheroidites, nevertheless, reasonable precaution has been exercised within the limits of steel metallurgy. It is believed that any large difference in transition temperatures would reflect the difference in ferrite grain structure and that relatively good ductility in the spheroidites from mar-

Jan 1, 1951

By B. Wilshire, P. W. Davis

It has been shown that grain-boundary migration during high-temperature creep can reduce or even prevent the formation of intercrystalline voids, giving a considerable increase in ductility.&apos; A similar observation has been made in a recent investigation of the creep properties of various grades of nickel and nickel alloys. The results can be illustrated by the observations made on: a) Pure vacuum-cast nickel (99.993 pct Ni) b) Impure vacuum-cast nickel (99.97 pct Ni) c) Pure nickel containing internal voids (produced by a process of intering). d) A substitutional solid solution alloy of pure nickel containing 1.16 pct Sn. All the materials were given a high-temperature anneal (>850°C) to produce a stable grain size of 7 to 10 grains per linear mm. The apparatus and techniques used to obtain the present results have been described elsewhere.&apos; In this series, grain growth was observed only in the highest-purity, vacuum-cast metal. Thus we may consider that in the other materials grain-boundary migration was prevented by either preexisting voids or solute atoms. The effect of migration on the creep ductility of the above materials can be seen from Fig. 1, which

Jan 1, 1962

By J. W. Rutter, K. T. Aust

Competitive growth of recrystallized grains into striated single crystals of zone-refined lead produced preferred orientations of the coincidence type after annealing at 175°C, but not at 300°C. This preferred orientation development was found to result from the higher mobility and lower energy of large -angle coincidence boundaries compared to large-angle noncoincidence boundaries. These mobility and energy difference provide a useful basis for explaining many cases of preferred orientation observed in annealed metals. DURING a study1 of the mobility of grain boundaries in zone refined lead, it was observed that the temperature dependence of the grain boundary migration rate is smaller for large-angle, coincidence-type grain boundaries than for large-angle noncoincidence ("random") boundaries. This observation is illustrated schematically in Fig. 1, which shows log rate of grain boundary migration vs reciprocal absolute temperature for two large-angle boundaries. The upper curve refers to a coincidence-type boundary of the sort discussed by Kronberg and Wilson.2 While the mobilities of these two boundaries are similar at 300°C, the coincidence-type boundary has a greater mobility, by a factor of about: four, at 175°C than does the noncoincidence boundary illustrated in the lower curve. The observation described above suggested a simple experiment for testing the role of grain boundary mobility in the development of preferred orientation in annealed, high-purity lead. On the basis of this observation, it would be expected that if a large number of grains of different orientations are growing competitively, and if relative grain boundary mobility is a controlling factor, then the specimen procluced by boundary migration will contain crystals having random orientations if annealing is done at 300°C, while preferred orientations of

Jan 1, 1962

By M. N. Pathasarathi, P. A. Beck, T. J. Koppenaal

EARLIER work1 indicated that in rolled and annealed copper the volume fraction of the cube-texture component may increase on continued isothermal annealing. Merlini found2 that in rolled copper the well-known increase in the amount of cube-oriented material with increasing annealing temperature3 is concurrent with grain growth, which takes place after recrystallization is complete. It was found that both in copper2 and in aluminum4 the texture resulting from primary recrystallization, even if this is followed by some grain growth, may in general comprise, in addition to the cube-texture component, four symmetrical texture components of the general type (123)[412], i.e., components not very far from the ideal orientations of the rolling texture. The volume fraction of the cube-texture component increases on further annealing at the expense of these four components.&apos; The present work was undertaken to study quantitatively the increase in the volume fraction of the cube-texture component in the course of normal grain growth, under varying conditions. Since the grain-gr3wth behavior of A1-Mn alloys has been already investigated in some detaiL5 an A1 + 0.8 pct Mn alloy was chosen for this work, in which the extent of normal grain growth can be effectively controlled by the inhibiting effect of a dispersed second phase. EXPERIMENTAL PROCEDURE High-purity aluminum of the following composition was used: A1 99.997 pct, Cu 0.0004 pct, Fe 0.0005 pct, and Si 0.001 pct. A high-purity A1-Mn master alloy was prepared by dehydrating manganese chloride at 500°C and reacting it with molten high-purity aluminum at 750°C in a graphite crucible.5 The Mn metal reduced from the salt by the molten aluminum goes into solution in the latter. The master alloy? containing 13 pct Mn, was solidified under conditions suitable for minimizing segregation. An ingot of the final alloy, to be used in the experiments, was per pared by melting high-purity aluminum and the necessary amount of master alloy in a graphite crucible, and by pouring the molten alloy into a graphite mold preheated to 700°C through a box containing graphite baffles designed to intercept most of the aluminum oxide films floating in the melt. The melt was then solidified by placing the mold on a water-cooled copper plate and by keeping the top of the mold hot, in order to minimize piping. The 6 1/2 in. long, 11/4-in.diam ingot consisted largely of a single crystal. Chemical analysis showed that there was little segregation from the bottom (0.83 pct Mn) to the top (0.81 pct Mn). Spectrographic analysis of the ingot showed that the impurity content remained essentially the same as that of the aluminum used. The ingot was processed so as to obtain a uniformly small grain size. without banding. The ini-tial steps of rolling in the form of a flat bar and of annealing, down through a thickness of 0.4 in., are shown in Table I. At this point the bar was cut into four sections, each approximately 3 in. long, which were processed separately as shown in Table If. The table also gives the penultimate grain sizes obtained in each section by annealing prior to the final rolling of 90 pct RA. During the final rolling the strips were reversed end to end between passes. Annealing treatments were given in a salt pot furnace, with the temperature controlled to 1°C. All annealing of section "6s" was carried out above the solvus point to avoid the formation of second-phase precipitate. The penultimate annealing was sufficiently short to give a relatively fine grain size in spite of the high temperature. Section "6L" was processed in a similar manner, except that the penultimate annealing was much longer, so as to allow considerable grain growth. Section "4" was given the two final

Jan 1, 1961

By W. A. Backofen, F. de Kazinczy

FRACTURING under conditions of particular interest is identified with the junction of curves relating tensile yield and fracture stresses to test temperature; the intersection point gives the lowest stress, for brittle fracture (at the ductility transition temperature). An expression for is found in Cottrell&apos;s brittle-fracture analysis, Eq. [15],1 while measurements of this stress and temperature have been reported for a low-carbon steel heat treated to differ-

Jan 1, 1962

By W. F. Domis, F. von Gemmingen, F. Garofalo

The effect of rain size on the creep behavior of an austenitic iron-base alloy has been studied at 1300° F under conditions of constant stress. The average grain diameter varied between 9 and 190 p (ASTM 10.7-2). The subgrain size and apparent activation energy for creep were not found to depend in any systematic manner on gain size. Grain hozmdary serrations were observed in all specimens tested. The variation of the secondary-creep rate, 2,, with the pain diameter, 1, is given by: es = K(213m + 1 )/l.]; 1, is the grain diameter zohere is reaches a minimum. Results in the literature shoujthat 1,increases as the temperature increases. At low creep temperatures is is therefore proportional to 12, at intermediate temperatures <, exhibits a minimum, and at high creep temperatures is is proportional to 1/1. The dependence ofis on the stress, u, is given by: t, = A" (sinh acrln, a and n show little variation with 1. The dependence of A" on 1 is given by: A" = KA[(21k + 13)/1]. For 1 » >>lmn = 4, and at constant values 01- isat lozu stress levels, the steady-state stress is given by the Hall-Petch relation. The variation of c, with grain size is believed to he associated particularly with grain boundary generation of dislocations which becomes more important with increasing temperatures. SEEMINGLY inconsistent experimental findings have led to a certain amount of confusion concerning the effect of grain size on creep behavior. The confusion is attributed to a lack of test results obtained over sufficiently wide ranges in grain size, stress, and temperature. Experimental results presented in this paper and results available in the literature1-5 show a consistent behavior and lead to a unified concept for the dependence of secondary-or steady-state creep rate on grain size. In accordance with this concept, which is substantiated experimentally, secondary-creep rate should increase with increasing grain diameter at low creep temperatures, leading to greater creep strengths for fine-grained materials. At intermediate temperatures the secondary-creep rate should decrease to a minimum and then increase as the grain size is increased. At high creep temperatures the secondary-creep rate should decrease with increasing grain size, leading to greater creep strengths for coarse-grained materials. Whether a temperature is high or low for creep in a metal or alloy depends primarily on its melting temperature. MATERIAL AND TEST PROCEDURES The material tested was an austenitic iron-base alloy of the following composition (wt pct): C, 0.005; N, 0.017; Mn, 1.26; Ni, 14.21; and Cr, 17.18. Two 15 -lb ingots were forged and hot-rolled to 5/8-in.-diam bars which were then cold-rolled and cold-swaged to a diameter of 0.49 in. These were sectioned into 3-in.-long blanks and heat-treated at various temperatures to obtain different grain sizes. The procedures employed and the results obtained are summarized in Table I. The secondary treatment at 1400° F followed the primary treatment without intermediate cooling to room temperature. This final treatment was employed to minimize various effects arising from heating to different temperatures during the primary treatment, particularly differences in intragranular dislocation structure, segregation of interstitial atoms at grain boundaries, and density of grain boundary ledges. The intragranular dislocation structure was examined by electron transmission metallography after each of the treatments described in Table I. Isolated dislocations and a few tangles were observed but no evidence of subgrains was found after any of the treatments. No grain-size effect was evident on the density and distribution of dislocations. Stabilization of grain boundary structure is particularly important because, as will be discussed later, grain boundaries influence high-temperature creep behavior. Magnetic-permeability measurements after each treatment and

Jan 1, 1964