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By J. C. Bierlein, R. A. Dodd

Endurance strengths at 10' cycles, fatigue-hardening rates, and endurance strength/0.2 pct proof stress ratios have been determined jbr a range of Cu(Ni), Cu(Si), and S.R.0. Cu(Au) solid solutions. Some douht is cast on simple cross slip models of fatigue hardening in view of opposite composition dependencies of hardening displayed by Cu(Si) and Cu(Au). The temperature dependencies of hardening also are the opposite of predictions made on the basis of a cross slip model. A correlation apparently exists between the fatigue strength/0.2 Pc~ proof s1.re.s~ ratios and rates of fatigue hardening. An increase in PS/PS due to alloying or temperature change is accompanied by a decrease in hardening rate, and vice versa. In recent years there has been much interest in the determination of the dislocation structure of fatigued metals and alloys. The accumulated evidence, e.g., Refs. 1 to 5, suggests that the structure may be dependent on the stacking fault energy, 7, of the fatigued metal in the same way that fatigue hardening rates have also been shown to apparently depend on u .6' 7 The above research followed the various earlier theories relating crack nucleation to ease of cross slip, e.g., Refs. 8 to 131 so "ggesting that y may indeed be the parameter of principal significance in all facets of the fatigue process. However, comparatively little attention has been paid to correlating engineering fatigue data with observations of the above type. Certainly, it would be useful if potential engineering fatigue performance could be assessed from a knowledge of easily determined alloy properties, and the present research originated from this standpoint. TO investigate the widest Possible range of 7 would require the use of two solvent bases, e.g., aluminum and copper, but a reasonable coverage can be provided by copper-based solutions alone. Therefore, it was decided to work with Cu(Ni) and Cu(Si) solid solutions, the approximate stackillg fault energies of which are given in Table I. The y range extends from low, Cu(7.5 at- Pet Si), to moderately high in Cu(2-5 at. ~ct ~i) and two of the Cu(Ni) alloys. The values listed in Table I should be regarded as qualitative only, being derived as follows. Dillamore and smallman14 quote a value of 85 i 30 erg.cm-2 for the stacking fault energy of pure copper, based on an earlier value due to Howie and swannl5 corrected by Brown's formula.'' Since the ratios (alloy)h(pure copper) have been reported17,18 for Cu(Ni) alloys containing up to 30 pct Ni, approximate ) values for these alloys can be computed, and a rough estimate of 7 for Cu(50 at. pct Ni) obtained by extrapolation. The relatively low y value obtained in this way for Cu(50 at. pct Ni) coincides with the observation of Nakajima19 that the stacking fault probability is a maximum at this composition. Likewise, the y values for the three ~u(~i) alloys are estimates based on values given by Swann and Nuttingo corrected on the basis Of Brown's estimate that the true 7 values are probably 2.3 times greater than those originally computed. In addition to the above alloys it was decided to investigate short-range ordered (s.R.O.) CU(AU) alloys containing up to 25 at. pct Au. This last alloy has been shown to have a well-defined planar arrangement of dislocations when deformed,21,22 probably due to cross slip being restricted by the S.R.O. Engineering fatigue data was to be represented by the determination of endurance strengths, and these were to be correlated with fatigue hardening and mechanical property data. EXPERIMENTAL I, order to study the desired properties and property changes, the following alloys were prepared: Cu(2.5 at. pct Si), Cu(5.0 at. pct Si), Cu(7.5 at. pct Si), Cu(5.0 at. pct Ni), Cu(25.0 at. pct Nil, Cu(50.0 at. pct Ni), Cu(5.0 at. pct AU), Cu(15.0 at. pct AU), Cu(25.0 at. pct AU). The copper and gold were zone-refined, while the silicon was semiconductor grade. The nickel was of 99.95 p,t. purity.* All alloys were induction-melted in a *Kindly supplied by the International Nickel co. helium atmosphere, appropriate precautions being taken to avoid segregation in the Cu-Au series. Rod stock was obtained by rolling and swag,ng. A few Bridgman single crystals were grown for fatigue-hardening studies, but most material was machined into polycrystalline fatigue speciments of the design shown in Fig. 1, and into polycrystalline tensile and fatigue-hardening specimens of simple cylindrical design. All specimens except Cu(Au) were annealed; the latter were quenched from above T, to produce short-range order. A few of the quenched alloys were examined for long-range order by step-scanning over

Jan 1, 1969

By F. H. Froes, D. H. Warrington

Electron microscope evidence which indicates that TaC may precipitate at random sites in the matrix is presented. Initially the particles are almost spherical and coherent with the matrix. However, as they grow in conditions in which there are insufficient vacancies to relieve lattice strain, the particles rapidly lose coherency in two directions and continue to grow as plates with approximately the full lattice mismatch strain present perpendicular to the plane of the plate. The necessary relief of strain comes from dislocations loops which do not become visible until the later stages of aging. The rapid decrease of apparent strain to low values of appoximately 1 pct at small particle sizes arises not from a complete incoherency but from applying a model wrong for the particle shape and strain distribution. PREVIOUS work has shown that MC-type carbides may precipitate intragranularly in austenitic stainless steel on dislocations,1&apos;2 in association with stacking faults,3&apos;4 and randomly through the matrix,5-7 In investigations of the matrix precipitate by thin-foil electron microscopy, considerable lattice strain has been found to occur around the precipitating phase.7&apos;8 Attempts have been made to evaluate the amount of lattice strain by using the methods developed by Ashby and brown.9,10 Values of the linear strain, much less than the 17 pct theoretical mismatch (for TaC), have been reported; it has been suggested that this is due to either a loss of coherency1&apos; or vacancy absorption which occurs during either the initial nucleation or growth of the precipitate." This report is an extension of earlier work7 that dealt with the precipitation of TaC from an 18Cr/12Ni/ 2Ta/O.lC alloy after it had been quenched from 1300°C and aged between 600" and 840°C. In particular, the shape of the precipitate particles and the amount of strain in the matrix, due to the precipitate, have been studied. The work described here is part of a wider investigation of factors that affect carbide precipitation in austenitic stainless steel," details of which are to appear elsewhere. RESULTS The present investigation can be conveniently split into two aspects of the strain-fields surrounding the matrix particles: 1) information derived from the strain-field which indicates the shape and habit plane of the precipitate particles and 2) the magnitude and sign of the strain-field. The Shape and Habit Plane of the TaC Precipitate. In the early stages of aging twin lobes (normally black F. H. FROES, formerly at the University of Sheffield, Sheffield, England, is Staff Scientist, Colt Industries, Crucible Materials Research Center, Pittsburgh, Pa. D. H. WARRINGTON is Lecturer, Department of Metallurgy, University of Sheffield. Manuscript submitted November 1, 1968. IMD on white background, i.e., for the deviation parameter, S > 0) that indicate the strained region of the matrix define the position of the particles by bright field transmission electron microscopy. The actual particles were not detected until they were approximately 120Å diam; below this size they were too small to be imaged in the electron microscope. This meant that particle growth that had occurred before this stage had to be inferred from the matrix strain-field contrast. In all cases when diffraction effects were observed from the precipitate particles, a cube-cube orientation relationship (i.e., (llO)ppt Il<llO>matrix and {1ll }ppt {III} matrix) existed between the precipitate and the matrix. From the matrix precipitate particles lying along edge-on {111} planes (e.g., at A, Fig. I), the precipitates are seen to be plate-like with their diameter being roughly 18 times their thickness after 5000 hr at 650°C. However, the exact shape of the particles cannot be determined because of the masking effect of the strain-field contrast. If a dark-field micrograph, using a precipitate reflection, is studied, Fig. 2, a number of the projected images of the TaC particles [on the (110) foil surface] apear to have straight edges parallel to projected f111) planes. Thus, it appears that in the later stages of aging the TaC particles are plate-like with some tendency for the edges of the plate to be bounded by the matrix close-packed {ill} planes (though the general shape of the particles in the plane of the plate is circular and thus the "diameter" of the particles has a real physical significance). It should be noted that the bands of fine discrete particles observed in Figs. 1 and 2 are not the matrix precipitate discussed in this paper but are precipitates associated with extrinsic stacking faults3j4 occurring on (111) matrix planes. **£** ****** \ *x 23 Fig. 1—18/12/2~a/0.1~ alloy. Solution treated at 1300°C for 1 hr, water quenched, and aged 5000 hr at 650°C. The (112) directions shown are the traces of the e&e-on (111) planes. Foil normal [110]; operating reflection (331); bright field micrograph.

Jan 1, 1970

By Ross C. Anderson, William I. Weisman

THE manufacture of anhydrous sodium sulphate or salt cake from natural deposits in the United States has been in general somewhat of a marginal undertaking. Competition from foreign sources and from large quantities of byproduct sodium sulphate produced domestically in the manufacture of hydrochloric acid and other chemicals has existed and continues. For example, most of the sodium sulphate produced is a byproduct or co-product in the manufacture of hydrochloric acid through the reaction of sodium chloride with sulphuric acid. In recent years, many manufacturers of rayon have installed equipment to recover sodium sulphate from waste spin bath liquors; today this is an important source. Before World War II large quantities of sodium sulphate were imported from Germany. In 1949 imported material from Europe again appeared on the domestic market. Natural sodium sulphate from Canada in substantial quantities also enters the United States markets. Despite this kind of competition, numerous attempts have been made to exploit various natural deposits of sodium sulphate in this country, but only a very few of these have survived economically over a period of years. One of these few operations is the plant of the Ozark-Mahoning Co. located 13 miles south of Monahans in West Texas. Several factors contributing to the successful life of this plant may be summarized as follows: 1—Geographical location. Monahans is reasonably close, freightwise, to the Kraft paper mills in Texas, Arkansas, and Louisiana; the Kraft paper industry is the greatest consumer of sodium sulphate in the United States. 2—Availability of natural gas as low cost fuel. Proximity of the natural gas fields of West Texas has been a tremendous asset, as the availability of low-cost natural gas is to all industry throughout the Southwest. 3—The nature of the deposit. The occurrence of sodium sulphate brines in southeastern New Mexico and West Texas has been very well described by Lang,&apos; who writes that the brines are found in the Castile formation of the Delaware basin. Here weathering has altered the anhydrite so that a relatively porous gypsiferous zone overlies a dense impervious mass of anhydrite. This porous zone provides traps where percolating ground waters that have picked up soluble salts may lodge. These traps or pockets are the natural brine reservoirs exploited at Monahans. Although several hundred wells have been drilled, currently some 25 wells serve to supply brine to the plant. All are within 1 1/2 miles of the plant and are conveniently tied together by an electric power system serving electric motors driving the pumps. Having the raw material in the form of a brine which can be pumped from shallow wells makes possible much simpler and more efficient handling than if it were in form of solids. By contrast, other deposits of sodium sulphate, such as those in Arizona, Nevada, and North Dakota, are in the form of the solid minerals, thenardite and mirabilite, which present somewhat more of a mining and mineral dressing problem.&apos; The largest producer of sodium sulphate from natural sources in the United States is at Searles Lake, Cal., and there a brine also is utilized. 4—Water. Substantial quantities are needed for cooling towers and for operation of gas engines. An area underlain with brine is not a promising source of fresh water, but fortunately, after a long search, an adequate supply was found nearly two miles from the plant. It may be appropriate to discuss briefly the grades of sodium sulphate offered on the market. Salt cake is the name usually applied to the grade of sodium sulphate used by the Kraft paper industry. It may be a low analysis byproduct, 95 to 97 pct sodium sulphate, with as much as l 1/2 to 2 pct residual acid, or it may be a natural product. Usually salt cake is considered a low grade product, but a great deal of a higher grade of material is marketed under this name. The specifications for glassmakers&apos; salt cake are somewhat higher than those of the paper industry, usually requiring 98 pct sodium sulphate. Technical anhydrous sodium sulphate is a high grade material and usually exceeds 99 pct sodium sulphate. It finds the biggest market in the textile industry and is used as a builder in some synthetic detergents. Glauber&apos;s salt, Na2SO4. 10H20, is usually of high purity. Preferred for some uses, it normally has been recrystallized from an anhydrous salt. A unique manufacturing process has been developed at Monahans. This process results in the production of an exceptionally high grade of salt cake, and qualifies for nearly all uses, including many which specify the technical anhydrous grade. All of the finished product, which is very white, passes a 10-mesh U. S. Standard screen, and is retained on a 200-mesh U. S. Standard screen. It is over 99 pct Na2SO4 with main impurities being sodium chloride and magnesium sulphate. Iron content is less than 0.01 pct. As mentioned, the raw material at Monahans is a brine drawn from wells. Attention was first attracted to this location because a so-called alkali

Jan 1, 1954

By George Simkovich

It was hypothesized that solid-state point defects should alter the flotation properties of solids. Tests conducted on pure AgCl and AgCl doped with CdC12 show that atomic point defects exhibit an important role in the floatability of AgC1. Tests conducted on PbS doped with Ag2s or Bi2S3, also show that the defect structures resulting from these dope additions, i.e., a combination of electronic and atomic point defects, contribute significantly to the flotation of PbS. IT has been established that flotation occurs only when a finite contact angle exists between a solid and a gaseous bubble.&apos; This angle, measured through the liquid phase, is expressed by the equation where the are inter facial free energies and the subscripts S, G, and L represent solid, gas, and liquid phases, respectively. As is seen in Eq. [I] three interface free energies, sG, sl, and GL, enter into the contact angle equation. Therefore, any variation in these energies which sufficiently varies the contact angle will, in turn, vary flotation processes. Changes made in any of the phases concerned, i.e., gas, liquid, or solid phase, are reflected through the changes occurring in two of the surface energy terms. Thus, a change in the liquid composition would be noted in sL and GL, and it is this phase, the liquid, which is most frequently altered in flotation studies., Changes in the solid phase must be reflected through the changes occurring in the sG and sL terms. In particular, it is hypothesized that changes in the surface concentrations of point defects in the solid-phase will alter the sG and sL terms which, in turn, will be reflected by flotation results. As an illustration of this hypothesis one may consider the defect structure and the flotation of AgC1. The bulk defect structure of AgCl is essentially one involving equal number of cation vacancies and interstitial cations.3 Upon adding CdC1, to AgC1, a greater number of silver ion vacancies are created in the bulk of the crystal.4 On the surface of the crystal the smaller binding forces and the free space accomodations may also allow for the creation of "surface interstitial anions", which will be designated as ad-anions. Thus, the point defect structure of the surface of AgCl doped with CdCl, will consist of cation vacancies and/or adanions. If the molecular forces responsible for the surface energies, ?SG and ?sL, are significantly altered by the presence of these surface point defects, then differences in flotation results will be noted as the concentration of these defects is varied. The defects present in AgCl are predominantly atomic in nature. In the case of PbS both electronic and atomic defects are present.5 This compound conducts electrically by either electrons or electron holes depending upon whether excess lead or excess sulfur is present. Upon disolving BiS3 in stoichio-metric PbS, one increases the concentration of cation vacancies and the number of electron carriers in the bulk of the crystal.5" At the surface, the possibility of ad-anions must also be considered. Conversely, upon dissolving AgS in stoichiometric PbS one increases the concentration of interstitial cations and the number of electronhole carriers in the bulk of the crystal.5,6&apos; At the surface the interstitial cations will be designated as ad-cations. Thus, the point defect structure of the surface of a PbS crystal doped with Bi2S3 will consist of a number of cation vacancies and/or ad-anions and an excess of electrons. Conversely the point defects on the surface of a PbS crystal doped with Ag2S will consist of a number of ad-cations and an excess of electron holes. Again, as in the case of AgC1, should the molecular forces responsible for the magnitude of the interface free energies, ?sG and ?sL, be significantly altered by the presence of these surface defects then significant differences in flotation results will be noted as the concentration of these defects is varied. EXPERIMENTAL To test this hypothesis flotation tests were conducted on pure and doped AgCl and on PbS doped with either Bi2S3 or Ag2S. Preparation of the AgCl samples was performed as follows: AgCl and weighed amounts of CdC1, were melted in a porcelain crucible. The melt was then forced through a capillary tube and the particles emitted solidified in air as they fell about 1.5 meters. Spherical particles, -0.50 + 0.25 mm, were separated from the remaining solidified material

Jan 1, 1963

By S. Storchheim

MORE and more attention is being paid to the bonding of metals in their solid states. For a better understanding of this technique for joining metals and how it is affected by changes in temperature, pressure, and time at temperature and pressure, a detailed report concerning nickel to aluminum bonding has been published.&apos; In order to broaden the knowledge accrued, some additional work concerning solid state joining of aluminum to copper and aluminum to zirconium was performed. The investigation of the Al-Cu system was considerably more extensive than the investigation of the Al-Zr system. For the A1-Cu system, not only were tensile sudies made but intermetallic penetration rate investigations also were carried out. The effect of temperature on intermetallic penetration rate for the A1-Cu system was determined at 11 tsi pressure, held 2 min. Procedure Apparatus: The hot pressing technique was the means of solid state reaction used and required the equipment depicted in Fig. 1. The following procedure was involved: The two metals to be reacted were placed in an aquadag-lubricated 18-4-1 tool steel die, 16 in. high by 1.440 in. ID, between punches of 1.366 in. diam made of the same material. A thermocouple well was located in the die body 3½ in. down from the top of the die, while another well was located centrally in the bottom punch 8½ in. from the bottom of the die. This die assembly was located in three cylindrical ceramic heating furnaces placed in tandem. Each furnace was controlled individually by a Variac power transformer. In turn, the die and furnaces were placed in a water-cooled stainless steel pot which could be evacuated. A cover, which contained a centrally located Wilson seal with an 18-4-1 1 in. diam ram running through it, was bolted on the pot. After sealing, the pot was evacuated by a roughing pump to 200 microns pressure, after which a diffusion pump was used to bring the pressure down to 5 to 15 u. At this pressure, the furnaces were turned on. As soon as they started to heat, out-gassing of the entire unit raised the pressure to 30 to 400 p. By the time the specimens were at temperature ready to be pressed, approximately 4/2 hr, the vacuum pumps had re-established the 5 to 15 u pressure. Once the desired temperature was reached, the required pressure was applied for a predetermined length of time to the 1 in. ram, through to the top punch, and to the specimen. When the time for keeping the specimen under pressure had elapsed, the pressure was released, the energizing coil current turned off, and the assembly allowed to cool. After cooling, the die was removed from the pot and the specimen was ejected. Specimen Preparation: Two different types of specimens were made for this investigation. One was for subsequent tensile testing, while the other was for determination of intermetallic alloy zone penetration into the parent metals. Tensile Bars—Commercially rolled copper pieces in. thick or zirconium sheet pieces 1/32 in. thick and 1.366 in. diam were placed between commercial 2-S aluminum rod 1 in. thick and 1.366 in. diam. This sandwich in turn was slipped into a 2-S aluminum sleeve 1.438 in. OD and 1.370 in. ID. This sleeve lined the couple up and prevented the aquadag lubricant from getting in between either the A1-Cu or Al-Zr interfaces. Immediately prior to the specimen assembly, the copper or zirconium was abraded on the flat surfaces with 320 grit silicon carbide paper, producing clean smooth surfaces. The aluminum was chemically cleaned just before assembly by: l—degrease in acetone, 2—distilled water rinse, 3—immersion for 3 min in 5 pct NaOH at 70" to 80°C, 4—distilled water rinse, 5—immersion for 2 min in 50 pct HNO3 solution at room temperature, 6—distilled water rinse, and 7—drying in a blast of gas. After the A1-Cu sandwiches were hot pressed and ejected, the specimens were machined such that the aluminum sleeve was removed, and the remaining aluminum was then threaded; the bar so produced was tested later for tensile strength. In all the instances where Al-Cu couples were tested, the specimens broke during the test at the Cu-A1 interface and never within the aluminum or copper. The ultimate tensile strength values at times showed considerable scatter for a set of given reaction conditions. Because of this, as many as three to five specimens were made for a particular set of conditions. The trend of the average tensile strengths obtained was not as conclusive as was the trend of the maximum tensile strengths, the latter values being obtained under optimum reaction conditions. Therefore, the values of ultimate tensile strength given herein are maximums.

Jan 1, 1956

By V. Leroy, A. G. Guy

Serious disagreements are often found between experimentally determined intrinsic diffusion coefficients and those calculated employing the usual form of the vacancy theory. In the new theory it is proposed that the total intrinsic flux, Ji, of component i, is the sum of a part, f, due to the usual random exclzanges of component i with the vacancies, and a second part, Ji, due to exchanges with the uacancies composing the net vacancy flux. The present treatment, while less powerful than that of Manning, has the advantage of easy uisualization and of facilitating the application of the vacancy-flux effect to complex systems. IT is becoming increasingly evident that there are serious deficiencies in the version of the vacancy theory of diffusion that has been widely used for the past 20 years. One type of evidence is the frequent lack of agreement between intrinsic diffusion coefficients and tracer diffusion coefficients, even taking account of the thermodynamic factor. A second kind of evidence is the observation of a Kirkendall shift larger than theoretically possible, that is, larger than can be accounted for without assigning a negative value to one of the two intrinsic diffusion coefficient.&apos;- The thermodynamic factor could conceivably make both coefficients negative, but not just one. It is clear that a cause of these anomalies, apart from any inadequacy of the usual vacancy theory, might lie in an oversimplified treatment of the data. Adequate experimental techniques, including the use of moderate pressure during the diffusion anneal, are now available to insure that porosity, lateral expansion, and so forth, can be kept negligibly small in most cases. The effect of differences in atomic volume can be of major importance, and it is essential that one of the available methods4 be used to account for this factor. In the present treatment this is accomplished by the consistent use of moles per cubic centimeter as the unit of concentration. Of the various possible inadequacies of the vacancy theory, attention will be given here only to effects of the net vacancy flux. annin&apos; has previously considered this question, beginning with an analysis of atomic jumping of tracer atoms. When he added the effect of a concentration gradient, new terms arose that could be associated with the flow of vacancies. The present treatment uses quite a different approach. The usual vacancy flux, J,, is introduced explicitly, and a simple analysis predicts major changes in the intrinsic diffusion coefficients from this cause. The usual assumptions are made that only a vacancy mechanism is operative, that the formation of voids can be neglected, and that changes in the partial molal volumes, vl and v2, are negligible. The significant diffusion coefficients for the present topic are Dl and D,, the intrinsic coefficients, which enter in the equations, where the flux Ji, moles per sq cm per sec, is that crossing the Kirkendall interface. The concentration, ci, is in units of moles per cu cm, and the concentration gradient, aci/ax, is evaluated at the Kirkendall interface. It will be recalled&apos; that the calculation of Dl and D2 involves the measurement of areas on the diffusion curve with respect to the positions of the Kirkendall and Matano interfaces. In the case of the anomalies mentioned earlier, the Kirkendall shift is too large to be accounted for by the diiferetzce in fluxes (J2 -J1), given by Eqs. [I] and [2]. The logical inference is that the flux of the solvent atoms, J1, is actually in the same direction as the flux of the solute atoms, Jz. In terms of Eq. [I] this requires that Dl have a negative value. However, it would be somewhat misleading to state that the solvent atoms are diffusing up their own concentration gradient. The explanation that will be advanced here pictures competing processes producing the net flux of solvent atoms: 1) diffusion of the solvent atoms down their own gradient by random exchanges with vacancies; and 2) diffusion of solvent atoms in the opposite direction by exchanges with the net vacancy flux. ACTION OF THE NET VACANCY FLUX Theories of vacancy diffusion can be formulated with varying degrees of refinement, and the present theory has purposely been kept as simple as appeared adequate to explain the phenomenon in question. In particular the following aspects have been neglected: 1) the gradient of vacancy concentration in comparison to the gradient of the atomic species; 2) departure of vacancy concentration from the local equilibrium value; 3) variation of the jump frequency, LO, with the specific surroundings of the atom-vacancy pair being considered; 4) correlation effects. These and other refinements can be considered once the essential mechanism has been established. The essential idea of the present analysis is to calculate the total intrinsic flux, Ji, of component i as the sum, JlJ?±j{ [3] where J; is attributable to the usual random atomic jumping, and J{ is a contribution arising from the net vacancy flux, J,. The latter quantity, of course,

Jan 1, 1967

By D. H. Desy, L. C. Fincher

The magnesium-rich end of the Mg-Ti phase diagram was investigated. The liquidus, solidus, and solvus boundaries to 1 pct Ti were established. All alloys were prepared by saturating molten magnesium with titanium in a consumable titanium crucible under inert gas maintained at 230 psig. The liquidus of the Mg- Ti system was determined by analysis of dip samples taken from 700° to 1300°C under equilibrium conditions in a pressurized inert atmosphere furnace and by analysis of small ingots rapidly poured and quenched from 1400° to 1500°C. The solubility of titanium in magnesium ranged from 0.018 wt pet Ti at 700°C (0.012 wt pet at 650°C by extrapolation) to 1.035 wt pet Ti at 1500°C. The solidus for compositions ranging from 0.03 to 1.00 wt pet Ti was determined to be 650° ± 1°C by thermal analysis. The titanium solid solubility values ranged from 0.08 wt pet at 350°C to 0.19 wt pet by extrapolation to 650°C. The freezing reaction is peritectic. No intermetallic compounds were found in the system; the phase in equilibrium with molten magnesium saturated with titanium was found to be titanium with magnesium in solid solution. Solid titanium will dissolve at least 1.32 wt pct Mg. PREVIOUS investigations of the Mg-Ti system have shown considerable disagreement on the solubility of titanium in liquid magnesium. Furthermore, the solid solubility of titanium in magnesium has not been well established. Liquidus curves for previous work and for the present investigation are shown in Fig. 1. Aust and Pidgeon1 used a dip-sampling method on molten magnesium held in equilibrium with solid titanium under a protective atmosphere to determine the solubility and found that it ranged from 0.0025 wt pet Ti at 651°C to 0.015 wt pet Ti at 850°C. Eisenreich2 introduced titanium into molten magnesium by means of TiCL4 adsorbed on BaCl2. Ingots were then cast at various temperatures. Making the assumption that only the titanium dissolved in magnesium at the time of casting was soluble in H2SO4, Eisenreich determined the solubility of titanium in molten magnesium to range from 0.003 wt pet at 655°C to 0.115 wt pet at 800°C. Eisenreich also determined the solid solubility of titanium in magnesium to be 0.015 wt pet at room temperature and 0.045 wt pet at 500°C. Since the solid solubility just below the freezing temperature for the bulk of the alloy was much larger than the liquid solubility just above the freezing temperature, Eisenreich concluded that the freezing reaction was peritectic. Obinata et al.3 equilibrated molten magnesium with titanium in hermetically sealed titanium containers which were then furnace-cooled. The titanium content of the magnesium was then determined and found to range from 0.170 wt pet at 700°C to 0.85 wt pet at 1200°C. No intermetallic compound was found in the system. The Armour Research Foundation4 determined two points on the solvus by electrical resistivity methods: 0.00057 wt pet at 200°C and 0.0008 wt pet at 300°C. At higher temperatures, data were meaningless with no trends observable. The authors of this report believed that the lack of significant data at the higher temperatures was due to variations in specimen geometry, although there was no positive evidence to verify this supposition. The present investigation was undertaken to clarify the uncertainty in both the liquidus and solvus of the magnesium-rich end of the Mg-Ti system. EQUIPMENT AND MATERIALS The equipment used in this investigation, with some modifications, was essentially that used by Crosby and Fowler5 in their determination of part of the Mg-Zr phase diagram. The equipment, as modified for this work, is shown in Fig. 2. It consists of a sealed furnace chamber which can be pressurized with inert gas so that melts can be made above the boiling point of magnesium at atmospheric pressure. Melts are made by induction heating in a titanium crucible which, after diffusion of sufficient magnesium into the walls of the crucible to saturate the titanium at the sampling temperature, comprises the solid phase in equilibrium with the molten magnesium. Dip samples may be taken with the sampling tube, or the entire furnace may be tilted so that ingots may be poured into a mold in the side chamber. The principal difference from the earlier apparatus is in the thermocouple, which in the present equipment is enclosed in a protection tube and immersed directly in the melt. The tips of both the thermocouple protection tube and the sampling tube, which dip into the melt, are made of high-purity titanium. The 4 1/2-in.-long titanium tip of the sampling tube is threaded into a steel tube, O in Fig. 2, which extends through the top of the furnace. To determine whether the temperature at the tip of

Jan 1, 1969

By P. K. Koh

With identical annealing heal treatment the development of major annealed texture component seems to depend primarily upon the degree of cold reduction. Cube texture was evident on annealing- 1/2-, 1,/4- , and 1/8-mil tapes at 760°C, but it dissap-)eared on 927°C annealing of 1/8-mil tape cold reduced 96.9 pct. Some cube texturee remained as tile strongest 927 °C annealed texture component in 1/4- and 1/2-mil tapes cold reduced 93.8 and 87.5 pet, respectively. The switching coefficient increases and the squareness ratio of the hysteresis loop decreases proportionally with increasing cube pole concentration. PREVIOUS studies 1,2 on the 1/8-mil ultra-thin molybdenum permalloy tape established cold rolled and annealed textures and their magnetic performance for switch-core and coincident-current memory applications, The major cold-rolled texture was found to be of {110}<335> which is quite similar to the cold-rolled texture of silver and 70-30 cartridge brass. The major annealed texture components were found to be of {120)-- <001> and {113)<785>. Although the direction for easy magnetization for this type of alloy by the single-crystal technique is not avaliable, knowledge from related studies indicated [Ill] as the easy magnetization direction, similar to that of nickel.&apos; Therefore, a cube orientation, if present in the tape core, would be most detrimental to its magnetic performance.3 In its cold-rolled state the tape had < 111 > directions in the rolling plane 14.5 deg from the rolling direction.&apos; But the coercive force of the tape in such condition will be excessive due to large amounts of internal stresses, and therefore makes its use impossible for memory applications due to long switching time. In lower nickel alloys, suchas 50-50 nickel-iron and 65 pct Ni-Fe sheets, previous investigators4"7 found the presence of cube texture on annealing at 900° to 1000°C. Although no cube texture was found in annealed 1/8-mil tape,"&apos; its presence in some annealed 1,/4-mil tape cores was firmly established a year ago as verified by significant differences in magnetic properties. The present investigation is devoted to the orientation study and related magnetic measurements on three thicknesses of the ultra-thin tape, namely, 1/8 mil, 1/4 mil, and 1/2 mil, cold rolled directly from annealed 4-mil stock in the cold-rolled state as well as after they were annealed at 760°C (1400° F) and 927°C (1700°F). The results obtained might serve to elucidate the development of annealed texture as well as to establish clearly the importance of preferred orientation on the magnetic performance of such memory tape core despite its well-known low magnetic anisotropy exchange energy. EXPERIMENTAL PROCEDURE Samples were taken from one production heat (0.010 wt pct C, 0.004 P. 0.016 S, 0.80 Mn. 0.29 Si. 79.69 Ni. 4.42 Mo. 0.054 Co, 0.002 Ti, 0.12 Al, 0.04 Mg, 14.56 Fe). Annealed 4-mil sheets were cold re-

Jan 1, 1962

By F. E. Rizzo, L. R. Bidwell, D. F. Frank

THE poor high-temperature oxidation resistance of the refractory metals becomes an important problem as higher operating temperatures are sought. A meaningful analysis of their oxidation behavior requires a knowledge of the phases that can appear during oxidation as well as their relative stability. Although several extensive investigations have been carried out to obtain this information for the W-0 system,1-10 serious inconsistencies still remain. First, the standard free energies of formation (AG°) determined in recent studies which used the solid electrolyte galvanic cell technique6,7,9 differ significantly from those obtained primarily from gas equilibration measurements.1,3,4,10 The disagreement is especially large for the highest oxides. These data have been used to predict the decomposition temperatures of WO2. 72 and WO2.90.1 A considerable extrapolation is required, resulting in a large uncertainty in the decomposition temperatures. Second, Bousquet and perachon3 have presented convincing evidence, ob- tained by gas equilibration measurements, in support of the long-contested existence of W30. Phillips and chang,ll on the other hand, were not able to observe this phase under similar experimental conditions. The purposes of this work, which is part of a continuing investigation of the W-Mo system, were to resolve the discrepancies between the AGO measured by gas equilibration and solid electrolyte galvanic cell techniques, to extend the latter measurements to lower temperatures, to redetermine the WO2.72 and WO2.90 decomposition temperatures, and to apply the more sensitive electromotive-force method to the question of the existence of W3O. I) EXPERIMENTAL PROCEDURE The measurement of ?G° of reaction by the use of calcia-stabilized zirconia solid electrolyte galvanic cells has been described previously.12 The method is based on the measurement of the difference in chemical potential of oxygen between an electrode containing the two oxides of interest and a reference electrode of known oxygen activity. Two different types of cell holders were used in this study. The first type of apparatus has been described earlier." It consisted of two solid electrodes separated by a disc of electrolyte. Both electrodes were exposed to the same stream of purified helium. With this design a gaseous transport of oxygen between the two electrodes is possible. The second type of apparatus, which has also been described earlier,14 effectively separated the two electrode atmospheres. It utilized a closed-end impervious, calcia-stabilized zirconia tube that was open to the atmosphere. The tube served as an electrolyte for the cell and provided a means for separating the anode compartment, which was held under a static vacuum, from an air reference cathode. The cells and reactions of interest are described in Table I. High-purity tungsten metal was obtained from the Fansteel Metallurgical Corp. and the Allied Chemical Corp. Table II contains an analysis of each material. WO3 was prepared by oxidizing the metal in air at approximately 600°C in high-purity recrystallized alumina boats and by the dehydration of reagent-grade tungstic acid in alundum boats. The two methods of preparing WO3 resulted in slightly different purities.

Jan 1, 1968

By H. F. Silliman, Daniel R. Hull, John R. Freeman

IN the normal operation of a brass-rolling mill, sheet and strip has, for the most part, been finished in comparatively thin gauges, involving a substantial amount of coldwork and a considerable number of anneals. This condition has been disturbed by the prep0nderance of cartridge brass, which is not rolled to thin gauges, and particularly by brass for artillery cartridge cases, on which the mill may finish its work at a thickness between 0.400 and 0.900 in. Obviously, the amount of rolling and the number of anneals to which such a product can be subjected are small compared with strip that is carried to a thickness of a few hundredths of an inch. As a result, critical examination into the internal condition of metal has been made on an extensive scale at a stage of manufacture that would not, in normal times, have been chosen for complete inspection. Under these conditions, a type of defect has been recognized that is not seen at thinner gauges. It might be more accurate to call it the appearance of a defect, since it refers to an apparently laminated, discontinuous structure, which, in fact, does not exist as such, and disappears after suitable treatment. For this reason it has been called a phantom lamination, which the authors consider an appropriate term. It is the purpose of this paper to describe the phenomenon and the conditions of its occurrence and, at least tentatively, to discuss its nature and cause. Great numbers of phantoms may be found in 2: 1 brass, either hot-rolled or cold-rolled. They are also found in 70-30 brass, sometimes when hot-rolled and generally when cold-rolled. It is not believed that phantoms are confined to these alloys but this paper is limited to them for the purpose of description. HOT-ROLLED 2:I BRASS For illustration, therefore, a typical cake of hot-rolled 2: 1 brass has been chosen. This was rolled to a slab 7/8 in. thick, from a casting 5 in. thick by 24 in. wide by 18 in. high, which was believed to have been sound. After hot-rolling and cooling, the slab was sheared and a portion of such a shear cut is shown in Fig. 1. It would be difficult to convince anyone viewing this specimen that the metal was not unsound. The impression would be confirmed by the appearance of a tensile break, as shown in Fig. 2. This is an ordinary tensile-test piece from metal just described. Although there was nothing in its tensile strength or elongation that suggested unsoundness, it appeared run through with pipes and laminations. To question the reality of such a condition would imply questioning the obvious. But, considering the history of the metal, it w0uld be difficult to believe that it could be so bad as it appeared. It seemed reasonable, though, that if the defects were what they appeared to be, they could be traced back from the sheared or broken face.

Jan 1, 1945

By John T. Norton, Matthew J. Donachie

Residual lattice strai?zs were produced in 2024 aluminum and ingot iron by uniaxial tensile deformation. These strains were rneasured on the original surface and ulith depth below the surface. The strains conformed approximately to those from a macroscopic stress distribution but they were not truly macroscopic in nature. The exact mechanism which apparently causes the coherently difi9,acting region of each grain to behave as if macroscopically stressed was not determined. MACROSCOPIC stresses in metals produce strains in the lattice which result in X-ray line broadening and line displacements. The latter effect can be utilized in a technique for determining stresses in metals as first shown by Lester and born.&apos; Subsequent advances in technique have enabled the X-ray method of stress measurement to be satisfactorily applied to many problems involving residual stresses of a macroscopic nature, such as those due to welding, grinding, shot-peening, and so forth. In the case of stresses such as those described above, the correlation of X-ray- and mechanically determined data has been generally good. However, plastically extended polycrystalline metals have sometimes been reported2 to show line displacements upon release of the applied tensile load, yet the nature or origin of the residual lattice strains, rls, producing these displacements has never been clear. As will be pointed out, this lack of clarity regarding the macroscopic or microscopic nature and origin of these stresses casts doubt on the validity of results achieved by the commonly accepted techniques of X-ray stress measurement. This anomalous behavior requires clarification to remove the doubts concerning X-ray stress measurement. The present paper is the result of an investigation of the interesting behavior of such plastically extended polycrystalline metal bodies. The studies were originated to carry out the following tasks: 1) Observe whether a residual lattice strain is produced as a result of plastic extension and show whether any residual lattice strains produced can be related to the usual concept of a macrostress. 2) Examine the origin of any residual lattice strains observed. 3) Consider the implications or consequences of the existence of such residual lattice strains on the problem of X-ray stress measurement. THEORY 1) Lattice Strains. The theoretical developments necessary for the treatment of lattice strains and their relation to stresses follow from the classical theory of elasticity and have been adequately covered by arrett. For an isotropic solid under homogeneous deformation, it can be shown that, for uniaxial stresses where Dl is the macrostress acting in the longitudinal direction; E$L is the lattice strain in the plane defined by the surface normal and the longitudinal direction at an angle, , from the surface normal; ET is the similar strain in the transverse plane; E is Young&apos;s modulus; and v is Poisson&apos;s ratio. Eq. [2] is independent of angle + and Eq. [I] is a linear function of sin2, see Fig. 1, and can be solved analytically for DL if E and u are known and EL is measured. Thus, a uniaxial macrostress will be indicated by a linear E,L vs sinZ plot and a

Jan 1, 1962

By William D. Klopp, Joseph R. Stephens

ThE phenomenon of high ductility associated with a phase transformation, termed super plasticity, has been reported for a number of alloy systems. Abnormally high ductility has been observed during tensile testing of cast eutectic alloys of Pb-Sn and Mg-cu.1 Brasses of Cu-37 at. pct Zn and Cu-40 at. pct Zn elongate up to 180 pct when tested near their transformation temperature.&apos; Enhanced ductility was also observed in Cu-47 at. pct Zn tested near the order-disorder transformation temperature. The most remarkable super-plastic effect reported to date is for the eutectoid alloy A1-60 at. pct Zn, where elongations up to 1000 pct have been reported.3 underwood4 has recently summarized the conditions that normally accompany the superplastic effect which are: 1) a phase transformation or allotropic change or order-disorder transformation; 2) an externally applied stress; 3) presence of an interface between two phases; and 4) a metastable structural condition. In addition, higher ductility is observed when the specimen is tested at slow deformation rates rather than under impact. The purpose of this note is to present evidence of the superplastic effect in a Cr-30 at. pct Co alloy. In addition, low-temperature bend ductility data are given for the alloy in the quenched, metastable, single-phased condition and in the slow-cooled, two-phased, near-equilibrium condition. Sixty-gram alloy ingots were prepared by noncon-sumable arc melting of iodide chromium and electron-beam-melted cobalt. These were cast into rectangular ingots and fabricated to 0.035-in. sheet by rolling at 2300°F. Attempts to roll at slightly lower temperatures invariably resulted in severe cracking, apparently due to presence of the brittle a phase below the transformation temperature of 2230°F. Tensile specimens with a 0.25 by 1.0 in. reduced section were cut from the sheet by electrical discharge machining. The specimens were heated at 2400°F for 1/2 hr to obtain a recrystallized, bcc, single-phased structure. Temperature of the specimens was subsequently raised or lowered to the desired test temperature and held for 10 min prior to testing at a crosshead speed of 0.01 in. per min. Fig. 1 shows the chromium-rich side of the Cr-Co phase diagram.6 The alloy composition investigated is near the point of maximum solubility of cobalt in chromium, and the alloy is two-phased when in equilibrium at temperatures below 2230°F. The results of tensile tests conducted at temperatures indicated by X&apos;s in Fig. 1 are summarized in Figs. 2, 3, and 4. Tensile elongations shown in Fig. 2 increase from 11 pct at 1900°F to a maximum of 160 pct at 2250°F. The elongation then decreases to 44 pct as the test temperature is further increased to 2600°F. The proximity of the temperature of highest elongation and the solvus temperature suggests that a superplastic effect is present in Cr + 30 at. pct Co similar to that observed for other alloys that show anomalous ductility. The variation of upper yield stress with temperature is shown in Fig. 3. A small peak in yield stress occurs at 2250"F, coincident with the maximum in

Jan 1, 1967

By Oscar Weiss

An aerial magnetometer survey was carried out by the author&apos;s geophysical organization over the Vrede-fort dome, where Witwatersrand beds are wrapped around a granite plug 25 to 30 miles in diameter. The well-known magnetic shales of the Lower Witwatersrand system (to be referred to as LWW) give strong negative anomalies over the out-cropping portion of the dome. This is unusual as these same shales cause positive anomalies over large areas near Johannesburg and along a strike of 130 miles between the East Rand and Klerksdorp. It is suggested that the negative polarization is caused by heat and stresses connected with the doming. This negative polarization of sedimentary beds, which usually cause positive anomalies, is a good example of how "magnetic lows" can be caused by "structural highs." Significant magnetic anomalies should be tested by gravity and seismic methods irrespective of the sign of the anomalies. South of the line X — Y (see Fig 2 and 5) the gravity anomalies are smaller over the LWW beds and magnetic anomalies suddenly become weaker and even change signs by becoming positive. This peculiar phe- nomenon is explained by faulting which truncated the nearly vertical LWW shales at depth. In this manner the mass of the LWW beds has been reduced together with the weakening of the negative magnetic anomalies by positive poles which occupy the truncated end. Furthermore, by uplifting the beds between f1 and f2 (Fig 2) positive polarization becomes predominant, thus causing positive magnetic anomalies. General The Vredefort dome is one of the internationally known geological structures, which, among others, has attracted the attention of numerous American geologists. It was for this latter reason that our aerial magnetic results over this structure were selected by us for publication in the United States of America. A full description of the exposed geology has been published by Nell and readers are referred to this paper, which is subject to only slight modifications inasmuch as the subdivision of the Witwatersrand system (to be referred to as WW system) is concerned. The Vredefort dome is about 60 miles southwest of Johannesburg. The WW system, after being exposed in the vicinity of Johannesburg, plunges with southerly dips beneath the Vent-ersdorp and Transvaal systems. Along a section southwest from Johannesburg, as shown diagrammatically in Fig 4, we see no outcrops of the WW system until the Vredefort dome, where the Upper and Lower WW system are wrapped around an almost circular arc of a granite mass. Here the whole WW system is overturned around the perimeter of a huge granite plug 25 to 30 miles in diameter. Less than half of the circumference of this dome is exposed; the rest is covered by Karroo dolerites and sediments. The determination of the exact shape of the concealed part of the dome has been a matter of considerable interest and obviously geophysical methods were eminently suited for obtaining this information. A good start was made with a gravimeter survey carried out by the Geological Survey of the Union of South Africa.2 Our own

Jan 1, 1950

By E. Marburg

Most ingots complete solidification vertically rather than transversely. This conclusion is based on complete solidification patterns of big-end-up and big-end-down ingots developed from dumped and split ingots. New mechanisms for segregation in ingots are proposed. Internal soundness in ingots is found to depend upon adequate width of vertical core. A LTHOUGH it has long been recognized that the A internal soundness of ingots is principally been recognizedthatthedependent on the process of solidification, knowledge of this process is still only fragmentary. The mechanisms causing the several types of segregation in ingots, which mechanisms are necessarily related to the solidification process, are not well understood. In absence of a better conception of the solidification process, it seems hardly surprising that mold design varies widely. Guiding principles for mold design are needed. At stake in the improvement of ingot quality are not only improved properties of steel but also appreciably higher yields of sound steel, which would considerably decrease manufacturing costs. In the present study, following a general description of the several types of segregation in ingots, Fig. 1, complete solidification patterns of a big-endup and a big-end-down ingot, including the zones of accelerated solidification, have been reconstructed. In both ingots, a core of vertical solidification extends from the base cone to the hot-top junction. Based on the finding that ingots complete solidification vertically rather than transversely, as has been previously assumed, new mechanisms for segregation in ingots are proposed. Internal soundness in ingots is found to depend upon the width of the vertical core, which in turn depends principally upon the width to height (w/h) ratio of the ingot. Solidification patterns of ingots are of three general types: 1—those in which vertical solidification does not reach the top, 2—those in which vertical solidification just reaches the top of the ingot, and 3—those in which vertical solidification reaches the top some time before transverse solidification would reach the middle of the ingot, so that a vertical core of definite width at the top of the ingot is developed. Axial defects vary characteristically with the solidification pattern. Examples of ingots of each type are presented. Dumped ingot data reported by Nelson&apos; have been used in developing families of curves of transverse and vertical solidification, and in deriving the effect of the w/h ratio upon the solidification pattern. Photographs of many ingots split at Homestead and at Duquesne Works, United States Steel CO., as well as those published by the British Iron and Steel Institute,&apos; have been studied and analyzed. In the interest of brevity, only typical ingots of each type or classification from the above sources have been reproduced. Segregation in Ingots Segregation in ingots falls into three principal classifications: 1—lamellar segregation, as revealed in sulphur prints (Figs. 2 and 3); 2—zone segregation, or broad variations in composition; and 3— interdendritic, or microsegregation. The last class, of minor importance, is not considered here. When liquid metal cools, according to the theory of differential or selective solidification,2 metal of relatively high purity selectively solidifies first. Liquid segregates (principally carbon, phosphorus,

Jan 1, 1954

By R. C. Amero

FULLERS earth is a general name applied to claylike minerals that have high natural ad-sorptive powers. They are usually distinguished from ordinary clays by a higher content of combined moisture and a lower apparent density. The definition is based on the ancient use of the material for fulling, or cleansing woolen cloth of oil and grease; a more modern definition should mention the ability to decolorize oil and should differentiate between fullers earth, which is naturally active, and certain bentonites which only develop decolorizing power after being leached with strong mineral acids. The distinction between fullers earth and activable bentonite is not a sharp one, since all types of intermediate clays can be found that are more or less naturally active, yet more or less responsive to acid treatment. The differences seem to depend somewhat on the amount of leaching that has been effected by natural ground waters. Physical Properties The principal mineral constituent of activable bentonite is montmorillonite, a hydrous aluminum silicate to which the following formula is generally assigned: Al,Si,O,, (OH), • 12H,O Fullers earth, as well as bentonite, is usually composed of some variety of montmorillonite, but in the United States the largest tonnage of fullers earth is mined from deposits of attapulgite. Attapul- gite is a clay mineral composed of monoclinic crystals of colloidal size, having a fibrous shape similar to that of asbestos. A sectional model of the attapulgite "molecule" is shown in Fig. 1. A single unit is about 18.0 A wide and 12.9 A high. The length of the molecule is variable, but this same molecular pattern is repeated to form needlework crystals, rather than flakes, as is characteristic of the montmorillonite crystals. Attapulgite has been assigned the following formula,&apos; although actually, the magnesia has been largely replaced by alumina: (0%) . (OH), • Mg, . Si, • Olp . 4H20. The fibrous nature of the mineral is clearly shown in the electron micrograph, Fig. 2. Although the deposits contain 5 to 30 pct quartz and carbonate minerals, impurities in the commercial products are held at a low level, principally by selective mining on the basis of oil decolorizing efficiency. The particle size distribution of this fullers earth has been estimated from settling rates, using sodium citrate as a dispersing agent.&apos; Since Stokes&apos; law only applies to spherical particles, the equivalent particle diameter calculated below is probably more nearly an index of diameter rather than length of the needlelike crystals: Eqnivalent Arbitrary Particle Distribution, Size Diameter Pci Classil3catian 0.05 mm 0.80 0.80 pct sand 0.05-0.02 mm 10.96 0.02-0.01 mm 9.65 42.10 pct silt 0.01-0.005 mm 11.40 0.005-0.002 mm 10.09 2-0.5 micron 10.61 0.5-0.2 micron 29.09 56.58 pct clay 0.2-0.05 micron 14.86 0.05 micron 1.96 The differential thermal analysis shown in Fig. 3 is unique and supports the theory that this is a distinct mineral species.&apos; ~ Other general properties of the mineral as shown in Table I.

Jan 1, 1952

By R. L. Stephenson

The effect of fabrication variables on the creep-rupture properties of TZM (Mo-0.5 pct Ti-0.08 pct Zr-0.03 pct C), Cb-TZM [columbium-modified TZM (7140-1.5 pct Nb-0.5 pct Ti-0.8 pct Zr-0.05 pct C)], and TZC (Mo-1.2 pct Ti-0.25 pct Zr-0.15 pct C) has been studied at 982º. 1093º, 1204º, and 1315°C for rupture times up to 1000 hr. The creep tests were performed in vacuum creep furnaces, employing cold-trapped oil-diffusion pumps, operating at pressures 2 X 10-7 tory. After-test chemical analyses showed no significant changes in interstitial content. The creep-rupture properties of TZM, fabricated according to current mill practice, were determined in the stress-relieved and in the re crystallized conditions to provide control data. Specimens of TZM, Cb-TZM, and TZC fabricated according to each of two experimental fabrication schedules were then tested. The schedules differed in terms of in-process annealing temperatures and warm -working temperatures. The data make several conclusions evident. Fabrication variables do indeed have a profound effect on the long-time creep-rupture properties of molybdenum alloys. Strengths of these alloys compare very favorably with those of other refractory metal alloys in the temperature range studied. FOR several years we have been engaged in the evaluation of the creep-rupture properties of promising refractory metal alloys. We consider the determination of these properties to 1000 hr at several temperatures necessary for a valid comparison. Such an evaluation indicated that the creep strengths of Mo-0.5 pct Ti and TZM (Mo-0.5 pct Ti-0.08 pct Zr-0.03 pct C) compare favorably with those of other refractory metal alloys. Tensile and recrystallization data of other investigators1,2 show an effect of fabrication variables. More specifically, those fabrication schedules which produce high strength through work hardening exhibit the least thermal stability. A similar conclusion was reported by perkins3 for Cb-TZM. This would lead one to expect that, in terms of creep, those materials showing higher strength at short times and low temperatures would exhibit lower strength at long times and high temperatures. If these expectations were fact, a substantial improvement could be made in these alloys by optimizing their fabrication schedule in terms of their anticipated service temperature. We therefore undertook a study of the effect of fabrication variables on the long-time creep properties of TZM, Cb-TZM (Mo-1.5 pct Cb-0.5 pct Ti-0.08 pct Zr-0.05pct C) and TZC (Mo-1.2 pct Ti-0.25 pct Zr-0.15 pct C). MATERIALS All materials used were supplied by the Climax Molybdenum Co. of Mich. Our original intention was to test the same heat of each alloy in different conditions. Fabrication difficulties prevented this; however, heats with nearly identical analysis were selected. The compositions of the materials used are listed in Table I. All materials were supplied in the

Jan 1, 1970

By C. E. Westley, R. R. Beebe

Recent works by Plaksh et al.,1,2 Glembotsky,3 and others have renewed interest in the effects of oxidation on the surface activity of the sulfides. Since considerable supporting data are available on galena-potassium ethyl xanthate, this system is being studied at South Dakota School of Mines and Technology by contact angle measurement, using the technique of McGlashan and McLeod.4 The contact-angle method is well adapted to investigation of the influence of small amounts of oxygen on the establishment of a stable contact angle on galena in potassium ethyl xanthate solution. Samples of massive galena containing less than 0.001 pct Cu, 0.001 pct Ag, and 0.01 pct Zn are mounted in castable plastic and ground and polished manually in a glove box containing the desired proportions of oxygen and purified nitrogen. Oxygen and nitrogen contents of the test atmosphere are determined with an Orsatt analyzer. In this way a reproducible surface is created in contact with whatever oxygen concentration is desired. Water and all reagents are prepared and stored in the test atmosphere. An absorbent is used to control carbon dioxide that might be present. Final polishing is done with levigated alumina on a glass plate. The prepared sample is placed in the test solution and transferred to the contact angle apparatus in a sealed box, and the test is conducted while both sample and solution are maintained under a slight positive pressure of the test atmosphere. Table I gives the results of contact angle measurements made at various 02-Nz concentrations.5 Each value of contact angle is the average of at least six individual measurements made with different bubbles at different locations on the sample surface. A period of 20 to 25 min has been found by preliminary tests to be sufficient to permit develop- ment of maximum angle, and all measurements are made after at least this much time has elapsed. Exposure of prepared samples to pure water under the test atmosphere before exposure to the xanthate results in a small but measureable and consistent reduction in contact angle. This is particularly true in the oxygen-deficient atmospheres; for example, at 2.2 pct O2 such water contact reduces the average angle about 8" from that obtained by immediate testing in xanthate. The general trend of increasing contact angle with increasing oxygen concentration corresponds to the results of Plaksin et a12 The absence of diminish-ment of contact angle at very high oxygen concentration has been attributed to the high concentration of xanthate per unit of galena surface: At oxygen concentrations below 1 pct (the limit of accuracy of the Orsatt analyzer), no contact angle is obtained. Furthermore, no contact angle is obtained at any oxygen concentration in the absence of xanthate. This result seems to be in disagreement with those cited by Plaksin.1 Further work on the interaction of galena and potassium ethyl xanthate or a similar collector as influenced by oxygen is contemplated. The true nature of the interrelation is as yet unknown. For example, it is not known whether the governing oxygen reaction is with the mineral, with the reagent, or with both.

Jan 1, 1961

By J. H. Smith, H. W. Paxton

ALTHOUGH many structural and kinetic investigations have been made for alloys of iron and nickel, only meager data exist from thermodynamic investigations. The purpose of this note is to estimate the free energy of the Fe-Ni solid solutions from thermodynamic data available for ternary alloys containing iron and nickel. The lack of a description of the thermodynamic behavior for the Fe-Ni system has required the structural and kinetic analyses of the system to assume some form of solution behavior, usually regular, e.g., the mar-tensite transformation analysis of Kaufman and Cohen, 1 consistent with the limited thermodynamic data. Indications that this system could exhibit ideal solution departures might have been suggested by the large deviations from additivity rules observed in the density and lattice-parameter measurements of Jette and Foote2 who interpreted this in terms of possible solute-solvent interactions. Later Turkdogan et al. 3 and more recently Ward and wright 4 found a minimum in the graphite solubility in liquid Fe-Ni solutions near the concentration of FeNi3 with deviations from linearity persisting at all concentrations. This was interpreted by Ward and wright4 to indicate negative heats of solution and was suggestive of short-range ordering. The infinitely dilute activity coefficient of carbon (?oC) was also observed by smith5 to pass through a maximum near the FeNi3 concentration in Fe-Ni solid solutions. Recent investigations of the liquid solutions over the entire concentration range by Zellars et a1.&apos; and Speiser et a1.," using vapor-pressure determinations, revealed both negative departures from Raoult&apos;s law and a nonregular solution behavior. The solid alloys have been studied by Oriani 8 and Kubaschew-ski and von Goldbeck6 employing gaseous H2/H2O equilibria with Fe and FeO. Both investigations were in substantial agreement, indicating very small departures from ideality. However, Oriani observed the formation of Fe3O4 (instead of FeO) at XFe= 0.441 which severed the equilibrium and precluded experimental investigation of the nickel-rich alloys. Heat-capacity and heat-content measurements have been evaluated by Montgomery10 and found generally unsatisfactory for gleaning thermodynamic information. This is due to the unknown final states of the alloys caused by the interference of the martensite transformation on cooling iron-rich concentrations and superlattice formation, magnetic transformation, and the varied heat treatments used by investigators of nickel-rich concentrations. As an alternative to the experimental difficulties, indirect estimates of the solid-solution behavior have been made by Fleischer and Elliott11 and Smith et a1.12 From their measurements of the solubility of Fe-Ni alloys in liquid lead, Fleischer and Elliott calculated the nickel activity (aNi) (and integrated for aFe) by assuming: 1) liquid lead has no solubility in solid Fe-Ni alloys, 2) Henry&apos;s law is obeyed throughout the liquid lead-rich phase (0— 12 at. pct Nil, and 3) Henry&apos;s law constant is independent of relative iron and nickel concentrations. The estimate of Smith et a1.12 was obtained

Jan 1, 1964

By Donald Jaffe, Michael B. Bever

The solidification of Al-Zn alloys (2 to 70 pct Zn was investigated at different rates of solidification. The resulting structures were studied; the amounts of nonequilibrium eutectic were measured and compared with the amounts calculated on the assumption of no diffusion in the solid. The compositions of the cored primary constituent were investigated by quantitative autoradiography after activation of the zinc by neutron irradiation. These compositions were also determined from microhardness values. IN a recent investigation of the soltdification of aluminum-rich AI-Cu alloys,&apos; the amounts of non-equilibrium eutectic were measured and compared with the amounts calculated on the assumption of no diffusion in the solid. The compositions of the cored primary constituent were investigated by quantitative autoradiography. The work reported here extends the investigation of nonequilibrium solidification to the Al-Zn system in the range from 2 to 70 pct Zn. In addition to autoradiography, microhard-ness values were used to determine compositions on a micro scale. Solidification Experiments The alloys contained approximately 2. 6, 12, 20, 30, 50, and 70 wt pct Zn and the balance aluminum. According to published diagrams the eutectic reaction occurs at 382°C between the eutectic liquid (95 pct Zn), a (82.8 pet Zn), and $ 498.9 pct Zn). Solid-state reactions at lower temperatures (due to the miscibility gap between 350" and 275"C, the eutectoid at 275&apos;C, and the precipitation from supcrsaturated a) did not affect this investigation. Even if they occurred to any appreciable extent, they did not alter the evidence pertaining to the solidification structures. The alloys had to be of high purity to avoid radioact~ve contamination during activation. The aluminum analyzed 0.015 pct Si, 0.009 pct Fe, less than 0.004 pct Cu, and less than 0.006 pct Mg with traces of sodium and titanium; the zinc was reported to be at least 99.99 pct pure with traces of iron and magnesium. The alloys were prepared under argon in an induction-heated, bottom-pouring furnace, and poured into a coated steel mold, which could be preheated to temperatures up to 700°C in order to control the rate of solidification. The pouring temperatures ranged from about 40" above the liquidus for 2 pct Zn alloys to about 130°C above the liquidus for 70 pct Zn alloys. As soon as the melt entered the mold, the readings of a thermocouple placed % in. above the bottom of the mold were recorded by a recording potentiometer. Cooling at the rate induced by the initial temperature of the mold was continued to a temperature 100°C below the liquidus; the mold with its contents was then quenched in icy brine. Quenching from a fixed interval below the liquidus was used to provide a standardized procedure, since the solidus and liquidus temperatures and the interval between them vary greatly over the composition range investigated. The temperatures from which the samples were quenched were below the equilibrium solidus, but under nonequilibrium conditions some liquid was still present. This residual liquid solidified during the quench. The samples measured 314 in. diam and 11, in. height. Drillings for chemical analysis were taken

Jan 1, 1957

By N. A. D. Parlee, E. M. Sacris

OVER 55 years ago, Sieverts and Hagenacker1 and Donnan and shaw2 made determinations of the solubility of oxygen in liquid silver, over a rather short range of temperatures (973° to 1125°C), using quartz bulbs, mainly at 1 atm. From the results of their investigations, Mizikar, Grace, and parlee3 plotted % O vs 1/T and obtained the following straight-line equation for solubility at 1 atm: log % O = 723.7/T - 1.0949 Recent work on the kinetics of the Ag-O2 system394 indicated there might have been some error due to reaction with the direct heated silica bulbs. Thus it became important to redetermine the solubility with the silver contained in a better refractory such as alumina, and by induction heating where the walls of the container were not so strongly heated. It was also desirable to extend the temperature range. A modified Sieverts apparatus of fairly standard type was used except that a special type of reaction tube was employed, Fig. 1. Dried argon with a guaranteed purity of 99.9 pet, and dried medical-grade oxygen with a guaranteed purity of 99.6 pet containing a little nitrogen, were the gases used. The measuring system consisted essentially of a manometer and a water-jacketed 100-cc gas buret with an open-end vertical tube parallel to the buret. This tube has the same diameter as the buret in order to give the same capillary effect on the mercury. A screw leveling device was used with the buret leveling bulb to help provide accurate pressure readings. A 2-mm ID capillary line connected the buret to the reaction chamber, helping to reduce the dead volume, which was determined with argon. The heating medium was a 2.5-kw output induction furnace. The induction coil was made of a 3/16-in. copper tubing with eight turns and an inside diameter of 4 cm. The reaction bulb was made of a quartz tube 18 cm long and 3 cm in inside diameter, Fig. 1. Inside the quartz tube were two alumina crucibles (Mor-ganite Triangle RR, XN10 and XN5) one inside the other. Below these two was an alumina disk. The disk prevented the corners of the outer crucible from expanding against the quartz tube. The solid sample (99.994 + pet Ag), which had been previously cleaned by air oxidation and repeated removal of scum, was placed inside the inner crucible. An alumina disk with a hole at the center covered the two crucibles. In order to decrease the dead volume, an evacuated quartz "filler" tube was placed on top of the crucible cover. The part of the reaction tube above the spherical joint was made up of Pyrex glass with a flat glass top. It was here that a prism was placed to facilitate the use of an optical pyrometer, previously calibrated at the freezing point of silver. This type of reaction bulb and furnace assembly was specially designed for this work, and used in preference to the relatively new water-

Jan 1, 1965