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By R. A., D. L. Sponseller, Flinn

Using specially del'eloped titanium nitride crucibles and a pressurized syslem, it has been possible to determine the solzibilitv of liquid calcium in liquid iron and iron-base alloys. At 2925°F the solubility is 0.032 wt pet Ca in pure iron. The solubility is increased by aluminum, carbon, nickel, and silicon additions, and lowered by additions of gold. An inflection in the calcium-solubility curve occurs as carbon is added to iron. At approximately 0.87 Wt pet Ca the CaC, phase replaces liquid calcium, and the calcium concentration de- creases as more carbon is added to the iron. The maximum solubility, 0.36 wt pet Ca, was obtained in iron containing 10.5 wt pet Si. The data have important implications regarding the use of calcium in process metallurgy, as well as providing an interesting test of theories of metallic solutions. Reasonably good agreement is found with theories of Alcock and Richardson and of Wagner, and criteria are suggested which permit these theories to be applied more readily to systems of this type. AT the present time relatively little is known about the factors influencing solubility in liquid metals. Information of this type is important for such matters as the control of impurity levels in liquid metals, the use of magnesium in ductile-iron production, and the use of liquid-metal alloys as fuels and coolants in nuclear power plants. One important example of restricted solubility concerns the extent to which liquid calcium will dissolve in liquid iron. This is a matter of considerable interest in view of the strong potential of calcium for removing certain impurities in steel,. as well as the ability of calcium to desulfurize, inoculate, and produce spheroidal graphite in cast irons.' Since ferrous materials normally contain other elements in addition to iron, the interactions of third elements with the Fe-Ca system are of interest. In view of the foregoing, this investigation was conducted to determine the solubility of liquid calcium in liquid iron and the effects of various third elements upon the solubility. For reasons of theoretical and engineering importance, the elements investigated were aluminum, carbon, gold, nickel, and silicon. Numerous attempts were made in the early part of the present century to determine the solubility of calcium in both liquid iron and steel, employing a variety of open-melt and closed bomb-type systems.2-4 From the results of these tests Wever concluded that calcium is insoluble in liquid and solid iron.5 These investigations were unsatisfactory in that they failed to insure the presence of a liquid layer

Jan 1, 1964

By Carl F. Floe, John Chipman

THE system molten copper-oxygen-sulphur is of interest from both the practical and theoretical standpoints; practically, because oxygen and sulphur play an important role in the commercial production of copper, and theoretically because it offers a chance to study the reaction between an oxide gas, SO2, and a molten metal. Reactions of this type, such as that between CO or C02 and molten iron, are important in many metallurgical operations. Again, the determination of any gas-metal equilibrium is of theoretical interest and value insofar as it contributes to the general development of the laws for solution of gases in metals. This problem is being given an increasing amount of attention in modem metallurgy. This paper is the first of a series and presents the results of a determination of the solubility of sulphur dioxide in molten copper at temperatures from 1100° to 1500°C., and pressures from about 20 mm. of mercury to somewhat above atmospheric. REVIEW OF PREVIOUS WORK The solubility of gases in most liquids has been found to obey Henry's law, which states that for a fixed temperature the amount of gas dissolved is directly proportional to the pressure. However this law does not hold for liquid metals. Instead, it appears that for many gases, particularly the simple diatomic ones such as 02, N2 and H2, the amount dissolved in liquid metals is directly proportional to the square root of the pressure. This is known as Sieverts' law. It may be recognized as a special case of Henry's law, which applies when the solute gas is dissociated into atoms or when it reacts with the solvent metal to form solute molecules containing single atoms of the gaseous elements, as, for example: [2M -}-G2 = 2MGK =G) IYf X[I]] which, if the solubility is not too high and the concentration of metal therefore nearly constant, can be simplified to: [MG = Ki Pa,[2]] Following the same reasoning, it would be expected that the solubility of SO2 in copper would be proportional to the cube root of the pressure, the reaction being as follows: [6Cu + S02 = Cu2S + 2Cu20[3] K Cu2S X (Cu20)2(Cu)e(Psm)[4]] or, neglecting the change in metal concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume V of gas absorbed: [K1 =or Vdo,= K2/PBO [5] PsO]

Jan 1, 1941

By J. M. Callow

H. A. MEGRAW, New York, N.,Y.-One interesting thing that might be brought out in this connection is the cost of making sulphide gas. I had a communication the other day which suggested that, in view of the high cost of oil, sulphur and sodium sulphide, we might make use of a well-known chemical reaction to form this sulphide gas by the use of aluminum sulphide. It is difficult to see any advantage in this, however, since aluminum has been affected just as much as any other commodity by the rise in prices, due, to war conditions. RUDOLF GAHL, Miami, Ariz. (communication td the Secretary*) Mr. Callow refers to my paper, History of Flotation at Inspiration, which was presented at the Arizona meeting of the Institute. These notes of Mr. Callow's contain much valuable information on flotation practice, as is to be expected from an article written by an author of Mr. Callow's experience in this branch of metallurgy. Nevertheless, I cannot help contradicting a number of the statements made in the references to my paper. In passing, I will also say a word about the reference in Mr. Callow's paper to the article by Messrs. Laist and Wiggin entitled "Flotation Concentration at Anaconda, Mont." Mr. Callow calls attention to the fact that evidently Callow flotation machines are not very sensitive, inasmuch as one man per shift handles four 800-ton sections of Callow machines or 3,200 tons per day at the Inspiration plant. While-it has been the experience of the Inspiration company that the four sections of Callow machines in the Inspiration concentrator are easily handled by one American operator per shift, it is only fair to state that each man operating four sections is assisted by two Mexican helpers who constantly clean the bottoms of the machines. The tonnage per section, by the way, whether equipped with Callow,, Inspiration or Minerals Separation machines, is considerably in excess 4 800 tons.. Mr. Callow further says that local opinion at Inspiration is that, two 800-ton sections consisting of two 10-compartment and four 6-compartment Minerals Separation machines (these machines are of the Hebbard type) is the limit that one man can properly attend. I do not hesitate to say that I consider it perfectly feasible to have four such sections operated by one man, perhaps assisted by "one helper. The Minerals Separation machines of this type have undoubtedly an advantage as far as easiness of operation is concerned,

Jan 4, 1917

By E. F. Burch, R. W. Schoenberger

This paper deals with an investigation of the use of steam filtration for filter cake dewatering and shows that it may be applied on a practical scale. The advent of larger quantities of minus 1/4 in. coal in the raw feed to the preparation plant and the necessity of recovering this material has made the problem of meeting product moisture specifications more difficult. For a number of years thermal dryers have been used advantageously as a means of reducing fine coal moisture content where the over-all economics would justify such an installation. However, these units are not without their drawbacks because of high capital and operating costs, safety hazards and possible degradation of the product, and thus an alternative method of moisture reduction is highly desirable. After the various mechanical variables associated with filtration have been optimized, an examination of theory shows that surface tension and liquid viscosity are the only two remaining variables which might be altered to reduce moisture content. A lowering of the surface tension within the limits of normal wetting agent dosage results in a rather insignificant decrease in cake moisture content. Not until the dosage is increased to a point well beyond this limit is there an appreciable decrease in moisture. At these high dosage levels, interfacial tension is a major factor contributing to the appreciable moisture reduction obtained. Since no suitable method has been developed to recover and recycle this wetting agent, this phenomena is not of practical significance. On the other hand, a reduction in liquid viscosity has a pronounced effect on cake moisture. While it is readily apparent that one method of reducing liquid viscosity is to heat the entire feed slurry, it is equally apparent that this would not be an economic approach except, perhaps, in certain isolated cases. It does, however, suggest that water circuits should be designed to conserve heat as much as possible and to make use of any waste heat that may be available. The use of hot air as a heat carrying medium for drying porous materials on a filter has been practiced for many years. However, this method is restricted to materials with a high air rate in the order of 100 cfm/ ft2 because of the low heat release per unit weight of air passing through the cake. The normal fine coal filter cake has an air porosity far too low to make this a practical approach. Various types of radiant heating devices have been investigated and can significantly lower moisture content at reasonable thermal efficiency. However,

Jan 1, 1964

By T. B. Massalski, H. W. King

An hcp phase may be induced by cold working the ß&apos; phase of the Ag-Zn system. This phase reverts to ß&apos; on subsequent aging. No phase change occurs on cold working the o phase, but ß&apos; is formed when the deformed alloy is subsequently aged at room temperature. It is concluded that for alloys near 50 at pct Zn the ordered bcc ß&apos; phase is the equilibrium structure at room temperature. WhEN the disordered bcc ß phase of the Ag-Zn system is cooled to temperatures below 258o to 274oC, it transforms to a complex hexagonal phase <o.1,2 The nature of the o ß=o transformation has been the subject of some discussion,2&apos;3 and the structure of o has been described in detail.&apos; The latter phase appears to be stable on aging at room temperature but decomposes following cold work. When alloys containing approximately 50 at. pct Zn are rapidly quenched from the 0 phase field, the ß ? o transformation may be suppressed; but the ß phase undergoes an ordering reaction (ß ? ß&apos;). The ß&apos; structure may also be obtained as a result of cold working and aging at room temperature.4 Kitchingman, Hall, and Buckley4 have suggested that the decomposition of (o following cold work proceeds in two stages, (o ? ß followed by ß ? ß&apos;, but did not confirm this by experiment. When the ordered &apos; phases in the systems Cu-Zn5 and Ag-Cd6 are cold worked, they become unstable and transform to a close-packed hexagonal phase (( ) indicating that when order is destroyed in a ß&apos; structure the close-packed hexagonal phase may in many cases be more stable. It thus became of interest to study more closely the effect of cold work and annealing on the stability of both the ß&apos; and o phases in a Ag-50 at. pct Zn alloy. Predetermined weights of spectroscopically-pure Ag and Zn, supplied by Johnson and Matthey, were melted and cast under 1/2 atm of He in transparent vycor tubing. The ingot was homogenized for 1 week at 630°C and quenched into iced brine. Since mechanical polishing was found to induce a phase change, sections were first polished at room temperature, sealed in tubes under 1/2 atm of He, reannealed for several days at 630o or 200°C and then quenched into iced brine. Sections of the alloy thus prepared were found to be homogeneous when examined under the microscope. The sample quenched from 630°C (ß -phase region) was pink in color, whereas the sample quenched from 200°C (o-phase region) was silver. The latter sample showed the characteristic hexagonal anisotropy when examined under polarized light. Filings of the alloy were examined at room temperature, after various heat treatments, using an RCA-Siemens Crystalloflex IV diffractometer with filtered CuKa radiation. The X-ray reflections from flat powder specimens quenched from 630o and 200°C and sieved through 230 mesh were recorded graphically at a scanning speed of 1/2 deg per min. The resultant patterns are shown in Figs. 1(a) and 1(b) and may be identified as those of the 8&apos; and <02 structures respectively. The lattice parameter of the ß&apos; phase was determined as 3.1566Å.* This value compares very well withthatto be expected for a 50 at. pct Zn alloy from the data of Owen and Edmunds? and indicates that no loss of Zn occurred during casting. In order to study the effect of cold work upon the ß&apos; and o phases, filings made at room temperature and sieved through 230 mesh were mounted immediately in the diffractometer-i.e., without a strain-relief anneal. Changes in structure on subsequent aging were followed by scanning repeatedly over the regions of the low index reflections of the ß&apos; and o structures-i.e. , 28 from 35 to 44 deg. Immediately after filing the 8&apos; specimen, additional diffraction peaks were observed in the low-index region of the pattern, as shown in Fig. 1(c). These additional peaks do not coincide with those of the o structure, Fig. l(b), but may be indexed as the (10.0), (00.2), and (10.1) reflections of an hcp phase (<) with nearly ideal axial ratio. However, this hexagonal phase appears to be very unstable since within a very short time at room temperature it reverts back to the ordered ß&apos; phase, the reversion being complete within seven hours. The 5 ? ß&apos; reversion reaction is, therefore, very similar to those already reported in Cu-Zn5 and Ag-Cd6 7&apos;alloys. The action of filing caused the deformed surface of the originally pink ingot to become silver in color, indi-cating that the ( phase possesses similar reflecting properties to the o phase. Hence, the subsequent

Jan 1, 1962

By L. C. Brown, S. K. Behera

The diffusion rate in Ag-Sb couples is sensitive to con~pressive load with the width of Ag3Sb, the only phase present in the diffusion zone, increasing with stress up to 800 psi and remaining constant above this. Kirkendall marker experiments show silver to diffuse much faster than antimony in Ag3Sb and incipient porosity may therefore develop at the Ag/Ag3Sb interfnce restricting the transfer of atoms from the silver into the diflusion zone. Application of compressive stress reduces the tendency for porosity to develop and so increases the growth rate. In a recent paper Brown et al.1 observed a significant increase in the thickness of Cu2Te in Cu-Te diffusion couples on application of a compressive stress as low as 20 psi. Similar stress effects have also been observed in the Fe-A1,2 Al-u,3 arid cu-sb4,5 systems. It has been suggested that the increase in growth rates of intermetallic phases in these systems is due to a decrease in the amount of Kirkendall porosity with applied stress. In the present paper, results are presented of the effect of compressive stress on diffusion in Ag-Sb, together with a detailed examination of the Kirkendall effect. The Ag-Sb phase diagram6 shows that antimony has a moderate degree of solid solubility in silver, 5.7 at. pct at 350°C, but that there is essentially no solubility of silver in antimony. There are two intermediate phases— (hcp7) from 8.8 to 15.7 at. pct Sb and Ag3Sb (orthorhombic8) from 21.8 to 25.9 at. pct Sb. EXPERIMENTAL Diffusion couples were prepared from fine silver of 99.95 pct purity and from antimony of 99.7 pct purity. Both the silver and antimony were produced in the form of discs 1/2 in. in diam by approximately $ in. thick, with surfaces ground flat to 3/0 emery paper. Diffusion anneals were carried out in the apparatus previously described.1 A compressive load was applied to the diffusion couple through a lever arm system, with a reproducibility estimated to be ±10 psi. All runs were carried out in a protective hydrogen atmosphere. Following the diffusion anneal specimens were sectioned and polished and the width of the diffusion zone was measured metallographically. Composition profiles were measured using an electrostatically focused electron probe with a spot size of 10 , counting on Sb L radiation. Corrections for matrix absorptiori and fluorescent enhancement9 were not required. S. K. BEHERA, formerly Graducate Student, Department of Metallurgy, University of British Columbia, is now Postdoctoral Fellow, Whiteshell Nuclear Laboratories, Atomic Energy of Canada Ltd., Pinawa, Manitoba. L. C. BROWN, Junior Member AIME, is Associate Professor, Department of Metallurgy, University of British Columbia, Vancouver, B.C., Canada. Manuscript submitted June 14, 1968. IMD RESULTS Fig. 1 shows an electron probe traverse of a typical diffusion zone. In all couples examined only one intermediate phase was observed and the composition of this phase, 23 wt pct Sb, was in good agreement with the composition of Ag3Sb, 23 to 28 wt pct Sb. The presence of this phase was confirmed by X-ray diffraction of filings taken from the diffusion zone. The probe traverses showed no detectable solid solubility in either the silver or the antimony although the phase diagram indicates that some antimony, up to 6.5 wt pct pct Sb, should be in solid solution in the silver. However the width of this portion of the diffusion zone would be expected to be very small in view of the low diffusion coefficient in the silver, 4 x 10-l6 sq cm per sec at 350°C, 10 compared with that in the Ag,Sb, estimated as 3 x 10-8 sq cm per sec in the present work, and this region would therefore not be expected to be seen in the probe traverse. Application of stress resulted in a significant increase in the width of the diffusion zone, Fig. 2. At 350°C, the thickness of Ag3Sb increased from 250 at 0 psi to 400 p at the limiting stress of 800 psi, indicating an apparent 150 pct increase in the diffusion coefficient. Similar behavior was also observed at 400°C, indicating that the stress effect is not characteristic of just one temperature. The growth of Ag3Sb at 350°C and at various stresses is shown in Fig. 3. In every case the growth rate was parabolic indicating diffusion control. The kinetic curves all passed through the origin showing that delayed nucleation of Ag3Sb was not responsible for the stress effect and that it was a real growth effect. A series of tests were carried out in which diffusion was allowed to take place at a lower stress following an initial high stress diffusion anneal. Speci-

Jan 1, 1969

By J. J. Gilman, T. A. Read

FOLLOWING the deformation 01 zinc monocrys-tals, sharply bent basal planes are observed near several types of inhomogeneities. Three of these in-homogeneities have characteristics which are quite regular so that they can be studied and analyzed. These are compressive kink bands, "deformation bands," and the inhomogeneities near end restraints. The present paper describes experiments in which "deformation bands" were artificially produced, and bend plane phenomena are discussed in terms of dislocation theory. Also, two new bend plane phenomena are described. The importance of bend plane phenomena in the deformation of crystals is not widely recognized. Many phenomena may be explained in a manner similar to the discussion in this paper. Jillson1 has pointed out that the "punching effect" in zinc is a bend plane phenomenon and is not caused by prismatic slip.&apos; Bowles3 has suggested that they may be involved in diffusionless phase changes. Cahn4 has discussed the role of bend plane formation in the polygonization of zinc. Experimental Work Tensile Kink Bands: Because of the geometrical similarity between "deformation bands" and "kink bands" (compare Fig. 1 of this paper with Fig. 1 of the paper by Hess and Barrett"), the band shown in Fig. 1 of this paper will be called a "tensile kink band," and that shown by Hess and Barrett will be called a "compressive kink band." It is felt that the term "deformation band" should be reserved for banded structures in polycrystalline materials such as iron." Tensile kink bands seem to form spontaneously in aluminum crystals deformed by tensile loading.7-10 In zinc and cadmium crystals they do not form in good, carefully loaded specimens.&apos;." However, tensile kink bands can be produced artificially in zinc crystals. The present authors did this by scratching one of the flat surfaces of triangular crystals transversely with a sharp needle. Natural tensile kink bands caused by inhomogeneities sometimes appeared in deformed crystals which were identical in appearance with the artificially produced ones. Zinc monocrystals were grown by the Bridgman method in graphite molds. Chemically pure zinc (99.999+ pct Zn) was used and the molds were sealed inside evacuated pyrex tubes during growth. The crystal cross sections were equilateral triangles with a typical base of 0.210 in. The artificial kink band shown in Fig. 1 is typical of tensile kink bands in zinc. The band lies between two bend planes which run from upper right to lower left and is inclined oppositely to the slip bands which are sharply bent at the two bend planes. The general form of the artificial tensile kink bands was independent of the scratch depth (1 to 5 mils deep) and also independent of which side was scratched. These variables did cause variations, however. Deep scratches produced more localized kink bands than light scratches. Also, if the angle between the slip plane traces and a transverse scratch varied appreciably among the three sides, then localization of the resulting kink bands also varied. Furthermore, if the slip direction lay nearly parallel to the scratched side, the band was more developed near the scratched side than at the opposite edge. Scratches produced tensile kink bands for crystal orientations from xo = 15" to x, = 75". Fig. 2 shows a scratched crystal after deformation. One triangular side lies in the plane of the photograph. The right hand tensile kink band was produced by a transverse scratch on the upper right side. The next two kink bands were the result of scratches on the front surface. The kink band at the left was caused by a scratch on the lower back side. All four bands have the same general form. A longitudinal scratch was also made on the crystal shown in Fig. 2 to determine the effect of a scratch on the critical shear stress. The critical shear stress of the scratched region was 33.9 g per sq mm compared to 24.4 g per sq mm for the un-scratched region above it. Fig. 3 shows Laue patterns of the crystal shown in Fig. 2. Fig. 3a shows the pattern of the undeformed crystal. The orientation was x, = 21°, A, = 31". After deformation, Fig. 3b was made of the homogeneously deformed portion of the crystal. The spots are compact but split into two halves. This region was elongated 45 pct and its orientation was x = 14", X = 20"; the sine law predicts x = 14", A = 20.5". Fig. 3c was taken near the center of the middle tensile kink band of Fig. 2. The pattern shows a range of orientations and polygonization in this region. The spread in orientation was due to the fact that the basal planes were curved (see Fig. 1) rather than flat as in the ideal case. Some may also have been the result of elastic distortions and "local curvatures." The orientation range was x = 23" to 32", A = 30" to 42". It is apparent from Fig. 3 that the material inside and outside the kink band rotated in opposite directions with respect to the tension axis during deformation. The orientation calculated from the ideal configuration of Fig. 9,

Jan 1, 1954

By David A. Thomas, Eugene S. Meieran

MECHAMCAL, electrical, and other property measurements are often more easily made on wires than on sheets. In order to carry out transmission electron microscopy on the same material used for property determinations, we have developed a method for preparing thin foil specimens of wires. The technique was developed for 0.030 in. diam tungsten wires, and is a modification of the thinning techniques used by Wilsdorf, et al 1 A length of wire is first ground to about 0.010 in. thick by mounting the wire in low melting temperature wax, hand grinding a longitudinal flat, removing and reversing the wire in the mount, and then grinding a second parallel flat. The 0.030 in. wide and 0.010 in. thick strip is cut into 1/8 in. lengths to fit in the specimen holder of the electron microscope. Next the specimen is gripped in platinum-tipped tweezers (the anode) and placed 2 mm below a hol- low copper cathode with a 0.010 in. ID nozzle. Electrolyte, 10 pct NaOH, flows by gravity feed through the nozzle onto the specimen, as shown in Fig. l(a). Polishing is carried out until a shallow impression is made on one surface, and then the specimen is turned over and the opposite surface indented. The metal between the two impressions should be about half the specimen thickness, as is shown by the heavy line in the cross section in Fig. l(b). The entire specimen is then electropolishedin 2 pct NaOH until a hole appears at the location of the indentations. The apparatus is shown in Fig. 2, and is essentially the same as that used by Wilsdorf et al. at The Franklin Institute. Light is reflected by a mirror onto the bottom surface of the specimen! which is viewed by a stereoscopic microscope placed above it. Polishing is carried out until light is seen, indicating that a hole has formed, and then immediately stopped. The specimen is washed in water. alcohol, and ether, and is then ready for examination. The specimen should be reversed in its platinum clip during electropolishing to insure equal polishing on both sides of the impression. For tungsten, indenting at 120 v and 0.04 amp takes less than 1 min, and final polishing, at 10 v and 1 amp, less than 5 min. The portion of the specimen available for transmission microscopy surrounds the hole, as is seen by the dashed lines in Fig. l(b). Slight electroetch-ing accompanying electropolishing reveals the mi-crostructure, as seen in Fig. 3(a) by light microscopy. Low-magnification electron microscopy, as in Fig. 3(b), enables the same areas and grains to be viewed and identified when subsequently examined at high magnification. Fig. 4 is a typical structure of

Jan 1, 1963

By K. Tanaka, J. D. Mote, J. E. Dorn

It) an attempt to ulLcoce.lP the operative strain-rate-contl-olliy: dislocation nieclzanistns, specially oviented sizgle clystals of the intel-nzediate 1zexagonal phase containing Ag plus 33 at. pct A1 were tested in tension over a wide range of temperatures. Slip was observed to take place by the {0001} <1120> {l100} mechani fracture took place across the(i100) plane and winning occurred by the (i01Z) ?lechanisn. Basal slip exhibited a strong yield point over the -alzge from 77 to 450°K, the upper ,esolved shear st]-ess having the exceptionally high value of 10,500 psi over this entire ?-a?zge of tenzpei,atuves. The critical 9-esolved shear stress for prismatic slip decreased f7-om 48,000 psi at 4.3"K to 23,000 psi at 170°K (Region 1) follozcirg zt:lzich it decl>eased sloz&ly to 21,500 psi at 475°K (Res&apos;on II); from 475" to 575°K (Regioz III), the c7-itical esolced shear stress dec&apos;-eased precipitously to 2000 psi; and from 575" to 750°K (Region IV) it decreased less afi&apos;dly to a low value of about 500 psi. Pvistintic slip in Region I was pobably controlled by the tliel-nally activated riecharzisui of nucleation and g,-ozcth of kinks in dislocations lying in Peierls potential troughs. In Region II for prismatic slip the critical 1-esolved shear stress was slzocn to be deteemined by sh0l.t-range 01-dering, Overall the forgiorz fo basal slip, 7.c.lre1-e a Strong yield-point phenorlienu ia7as observed, the critical vesolved slzea?-stress was shoztn to be determined by n conibirzation 0-f Szizuki locking and short-range-order Izavderzizg, The precipitous decrease in the critical resolved shear stress with increase in ter,/pe7-atrir-e over Region HI was tentatively ascribed to a decrease in the degree of slort-)ange 07-del;iqq (0)- clusteing) and also the effect of fluctuations the degree of o?der, It is at pgreser2t zrtzce)taitz as to 1t1hethe1- these or other possi1)le effects are also ,esponsible. fo- the data obsel-ved 172 Region IV. 1NTEREST in inter metallic compounds stems not only from their role in dispersion hardening of polyphase alloy ystems but equally from their potentialities for high strength, hardness, and stability not only at atmospheric temperatures but especially at elevated temperatures. As summarized in a re- cent symposium of the Electrochemical Society on "Mechanical Properties of Inter metallic Compound", most of the experimental evidence regarding the mechanical behavior of intermetallic compounds centers about the effect of temperature on the hardness and ductility of polycrystalline specimens. The available data reveal that the plastic behavior of intermetallic compounds might be rationalized in terms of the usual dislocation mechanisms appropriate to a solid solutions providing the additional complexities arising from crystal structure, long-range ordering, short-range ordering, and defect lattices are taken into consideration. It is apparent, however, in terms of the history on a solid solutions, that a complete detailed mechanistic rationalization of dislocation processes may not be possible until the deformation processes are studied in single crystals of intermetallic compounds. The present paper contains a preliminary report on the plastic behavior of single crystals of the hexagonal Ag-A1 intermetallic phase over a wide range of temperatures. The results confirm the thesis that single crystal data provide a most effective method of identifying operative dislocation mechanisms in intermetallic compounds. EXPERIMENTAL TECHNIQUES Several factors prompted the selection of the hexagonal Ag-A1 intermetallic phase for this preliminar investigation on the plastic properties of single crystals of intermetallic compounds: 1) This phase has a wide solubility range5 which would permit future investigations on the effect of composition and axial ratios on slip mechanisms. 2) Although it undoubtedly exhibits short-range ordering (or clustering) this intermetallic phase is free from complexities arising from long-range ordering.6 3) Since the atomic radii of aluminum and silver are practically identical, the possible complications due to Cottrell locking are minimized. 4)Whereas the dislocations on the basal planes are expected to dissociate into Shockley partials and are thus susceptible to Suzuki locking, those on the prismatic planes probably remain complete. 5) The axial ratio, being 1.61, is almost ideal, suggesting that short-range ordering may be almost spherically symmetrical. The present investigation was conducted exclusively with the hexagonal Ag-A1 alloy containing 33 at. pct Al. Preliminary investigations revealed that this alloy undergoes basal slip by the (0001)

Jan 1, 1962

By H. C. Chao, L. H. Van Vlack

Small MnS inclusions with known crystallographic orientations were placed inside powder compacts of low-carbon steel. After the metal was axially campressed with negligible end friction, the deformstions for the metal and the inclusions were compared. The MnS inclusions deformed more when the [100] direction was aligned with the compression axis than when the [111] direction was parallel to this axis. The deformations of the inclusions in the two principal radial directions were equal for each of the above orientations. Inclusions with [110] compression alignments did not deform with radial symmetry. The relative deformation of the inclusion and metal was closely dependent upon the relatiue hardness of the two phases. The relative deformation of the two phases was not sensitive to the rate of deformation. RECENT studies by the authors1.&apos; suggested that the plastic deformation of MnS in steel would probably be highly sensitive to the orientation of the inclusions and to the temperature of the metal. This paper reports an investigation of these factors upon MnS behavior within steel. Manganese sulfide (MnS) possesses an NaCl-type structure and typically has extensive (l10) {110} slip as a separate (noninclusion) crystal.&apos; A secondary slip system, ( l 10) { l l l}, has also been observed where the major slip system is restricted. In general, MnS inclusions must be rated as a highly deformable second phase.3 The amount of sulfide deformation varies, however, with several composition and processing factors. Some of these have been only partially assigned. For example, it is known that minor amounts (<0.01 pct) of silicon within free-machining steels will increase the amount of MnS deformation,4 but the mechanism of the added deformation can only be surmised at the present. Manganese sulfide and steel have sufficiently comparable deformation characteristics so that slip which is started in steel may be continued through the sulfide inclusions and back into the steel if the crystal orientations are favorable.5 A more detailed discussion of previous work on the plastic deformation of NaC1-type crystals and on the plastic deformation of inclusions within a metal is given in Chao&apos;s work.6 EXPERIMENTAL PROCEDURE The manganese sulfide which was used in this study was prepared by previously described methods.&apos; Single crystals of MnS, both as cleavage cubes and as spheres, were oriented within steel powder compacts so that the desired crystal directions were parallel to the direction of axial compression. A four-stage hydrostatic compaction procedure was used and involved the following steps. In the first stage part of the powder was placed in a metal die 1 in. in diameter with a thick (1 in. OD, 5/8 in. ID) rubber liner which had one end plugged. The steel powder was hand-rammed, making it as dense as possible before placing a carefully sized MnS crystal (either as a sphere or as a cube) near the center. The crystal was oriented with the chosen direction vertical; viz., [001], [011], or [111], with the aid of a X10 microscope. A pair of tungsten wire threads 0.020 in. in diameter was inserted along the side of this (&apos;core compact" to locate the desired plane after the compression tests. After the crystal was positioned in the center of the die, more powder was added and carefully rammed by hand. The die was then capped with a rubber plug of the same hardness and thickness as that of the liner. The whole assembly as shown in Fig. 1 was compacted by a ram load of 54,000 lb (about 70,000 psi). In the second stage a smaller, 3/4-in, rubber-lined die was used to give a stress of approximately 120,000 psi. The above process was repeated with the initial compact serving as a core for a larger compact. The final product after sintering was a cylinder 1 cm long and 1 cm in diameter, having a density of 7.54 g per cu cm. This was close to the theoretical density since the metal contained a non-metallic phase. There was no evidence of MnS deformation during the hydrostatic compaction or subsequent sintering. Elevated-temperature hardness data were obtained by procedures previously described.2 Compression tests for inclusion deformation utilized the cylinders which were described above. The critical problem in these tests was the lubri-

Jan 1, 1965

By P. H. Lindon, J. C. Billington

Fe-O melts containing 0.045 pct 0 were deoxidized with Mn-Si-A1 alloys. Product compositions were reluted to the melt and alloy compositions and were found to be most sensitive to the aluminum content of the alloy. Low residual oxygen contents could be obtained when aluminum oxide was present in the Products because of the reduction of silica and manganese oxide activities. Flotation of the Products from a quiescent melt was followed both by analysis of the oxygen content and metallographic measurement of inclusion concentration. MnO-SiO2-A12O3 products were found to float most rapidly when their composition was such that their viscosity may be expected to be low. Changes in the particle size distribution indicates that particle coalescence occurred and differences in the degree of coalescence are thought to be responsible for the different flotation rates observed between products 0f differing composition. Measured flotation rates were slower than those Predicted from a model based on Stoke&apos;s Law, although alumina flotation might be reasonably accounted for by this model. Interfacial effects between oxide particles and the melt are believed to be responsible for the discrepancy. It has been recognized that deoxidation products constitute a large proportion of the nonmetallic inclusions present in killed steel. The amount of oxide inclusions which originate as deoxidation products depends largely upon three factors. These may be summarized, according to P16ckinger1 as: 1) Amount of primary products remaining in the steel prior to cooling. 2) Residual dissolved oxygen content of the steel after deoxidation. 3) Amount of secondary products, formed during cooling and solidification, which remain entrapped in the solid steel. In a well-deoxidized steel containing residual aluminum and/or silicon, the equilibrium dissolved oxygen content is usually very low and so the maximum amount of oxide which may be produced as secondary deoxidation products is small in comparison with the amount of primary products. It may be seen, therefore, that the amount of indigenous nonmetallic inclusions may be minimized if a low dissolved oxygen content is achieved by deoxidation and if the primary deoxidation products are efficiently removed. Oxides which originate by reaction of the metal stream with the atmosphere during teeming are not considered in the present study. It is known that two or more deoxidizers may result in a lower equilibrium oxygen content when used in conjunction with one another than when any of the individual deoxidizers are used alone. Equilibrium studies by Hilty and crafts2 and by Bell3 have shown that manganese increases the effectiveness of silicon as a deoxidizer, and Walsh and Ramachandran4 relate this to a reduction in the activity of silica in the products as the manganese :silicon ratio in the steel increases. It was also shown by Herty&apos;s work on deoxidation of steel by silico manganese alloys,5 that there existed an optimum ratio of manganese to silicon which gave a minimum inclusion content. This ratio was in the range 4:l to 7:l and the (FeO-MnO-SiO2) products formed by such deoxidation practice were found to lie in a composition range having very low liquidus temperatures (1170 to 1250°C approx). The optimum manganese:silicon ratio was then explained by postulating that these fluid products were able to coalesce and that the larger particles formed floated out of the steel very quickly as predicted by Stoke&apos;s Law. The present work examines the effectiveness of various Mn-Si-A1 alloys as deoxidizers and their effects on the composition and removal of primary deoxidation products from a quiescent melt. EXPERIMENTAL TECHNIQUE Approximately 250 g of prepared Fe-O alloy, containing 0.045 to 0.055 pct O, were melted in an alumina crucible and deoxidized at 1550°C by plunging a thin steel cartridge containing the deoxidizer below the melt surface. A high frequency induction furnace supplying current at 8.5 kHz was used to heat a graphite susceptor, the interior of which had been machined to give a wall thickness of 0.85 in. to form a receptacle for the alumina crucible. The iron melt was essentially quiescent as the induced current was concentrated at the external surface of the graphite susceptor by the skin effect. A nonoxidizing atmosphere was maintained over the melt by passing a continuous stream of argon through the lid of the susceptor. The melt temperature was measured before deoxidation, and again at the end of an experiment by means

Jan 1, 1970

By L. Delisle

This work represents the first step of an attempt to test the applicability of the electron microscope to the study of subgrain structures in copper. Observations on annealed and deformed single crystals and polycrystalline samples of copper are described. IN the course of study of the structure of fine tungsten wires and tungsten rods with the electron microscope, well defined subgrain structures were observed. The size, size distribution, and orientation uniformity of the etch figures varied widely in different samples. Figs. 1 and 2, electron micrographs of a tungsten wire and of a tungsten rod, respectively, are illustrations of the difference in size and size distribution of the etch figures in different samples of the same metal. The observed differences, as pointed out in a previous paper,&apos; appeared to be related to the heat and mechanical treatments of the samples. They were also consistent with the results reported in the literature on the mosaic structure of metals.&apos; For that reason a program of research was initiated in an effort to obtain more systematic evidence of the possible relation of heat and mechanical treatments to the subgrain structure of metals as observed in the electron microscope. The purpose of this paper is to present observations made on the effect of cold work on the subgrain structure of copper. Procedure Starting Materials: Copper was the metal studied because it can be obtained in a high degree of purity, much information is available in the literature on its properties and its response to cold work and heat treatment, it shows no allotropic change, and it is sufficiently hard to be handled without great difficulty. Two groups of specimens were used: 1—single crystals cast from spectroscopically pure copper and 2—polycrystalline samples of oxygen-free high conductivity copper. Single crystals were studied because it was hoped that the elimination of a number of variables, such as grain boundaries, orientation differences, degree of purity, would simplify the problem and perhaps permit a better understanding of the phenomena that would be observed. The polycrystalline samples were designed to give a general picture of the changes considered. The single crystals were made of copper which analyzed spectroscopically to better than 99.999 pct Cu. They were cast in vacuum, by the Bridgman method, in crucibles made of graphite with a maximum ash content of 0.06 pct. The mold design is shown in Fig. 3. It permitted casting crystals of the size and shape required for the experiments, so that the danger of introducing cold work in the original samples by cutting or other machining would be eliminated. The polycrystalline samples were pieces, 3/4 in. long, cut from a rod of oxygen-free high conductivity copper, % in. in diameter. A flat surface, 1/4 in. wide, was milled along the rods, polished, and etched. The samples were then annealed in vacuum at 850°C for 1 hr. Polishing and Etching: Work previously done on tungsten,&apos; polished mechanically and etched chemically," had shown that: 1—the general appearance of the etch figures of a given sample was not altered by repeated polishings and etchings under similar conditions; 2—variations in the time of etching and the concentration of the etchant changed the definition of the etch figures, but did not alter their general size nor orientation distribution within the limits of observation. Further work confirmed the reproducibility of the subgrain structures observed in, 1—single crystals and polycrystalline samples of copper when polishing and etching were repeated under similar conditions, and 2—specimens of tungsten and polycrystalline copper when electrolytic polishing and etching were substituted for mechanical polishing and chemical etching, respectively. On the strength of these observations, it was felt that, if conditions of polishing and etching were kept constant, changes observed in the subgrain structure of a sample upon deformation and annealing would be attributable to such treatments. For that reason the conditions of polishing and etching were kept as constant as possible. The single crystals were polished electrolytically in a bath of orthophosphoric acid in water, in the ratio of 1000 g of acid of density 1.75 g per cc to 1000 cc of solution, under a potential drop of 1.6 to 1.8 V. Electrolytic polishing was selected to prevent the formation of distorted metal in polishing. The same samples were etched by immersion in a 10 pct aque-

Jan 1, 1954

By D. V. Edmonds, C. J. Beevers

Tensile tests were carried out on a! titanium containing 850, 1250, and 2700 ppm 0, and up to -500 ppm H. The tests were performed at -196", -78", 20°, 150°, and 300°C at a strain rate of -1.0 x 10??3 sec-1. Increasing oxygen content, increasing grain size, and decreasing test temperature resulted in enhanced embrittlement of the a titanium by the hydrogen additions. Metallographic observations showed that this can be correlated with the influence of these parameters on the introduction of cracks into the a! titanium by fracture of titanium hydride precipitates. CRAIGHEAD et al.1 reported that the hydrogen content normally found in commercial-purity a! titanium (60 to 100 ppm) was sufficient to cause a substantial lowering of the impact strength, and they attributed this embrittling effect of hydrogen to the precipitation of titanium hydride. Lenning et al.&apos; found that in commercial-purity a titanium there is an almost complete loss of impact strength at about 200 pprn H, which is approximately half the value needed to eliminate the impact strength of high-purity a titanium. They also showed that the presence of 3000 ppm hydrogen reduces the room-temperature tensile ductility of commercial-purity material to a value of the order of 10 pct; the corresponding hydrogen concentration for high-purity titanium is over 9000 ppm. It thus appears that the detrimental effect of hydrogen on the mechanical properties of commercial-purity titanium becomes evident at much lower hydrogen contents than for high-purity titanium. The main difference between the two types of a titanium might be expected to be the higher level of interstitial impurity in the commercial-purity grade. Jaffee et a1.3 studied the influence of temperature and strain rate on the hydrogen embrittlement of high-purity and commercial-purity ! titanium. In general, the behavior was the same for both materials; embrittlement was enhanced by decreasing temperature and increasing strain rate. Recent results from tests on commercial-purity a titanium containing 850 ppm O and varying amounts of hydrogen up to -500 ppm showed that the degree of embrittlement by hydrogen is intimately related to the fracture characteristics of titanium hydride precipitates.4 The present paper considers the interrelationship between the mechanical properties and micro-structural features of commercial-purity a! titanium containing 850, 1250, and 2700 ppm 0 and varying amounts of hydrogen up to -500 ppm. 1. EXPERIMENTAL PROCEDURE Three types of commercial-purity titanium supplied by IMI* were used in the investigation, and for the *Address: Witton, Birmingham 6, United Kingdom. purpose of this paper are designated Ti 115, Ti 130, and Ti 160. The principal impurity elements are given in Table I. The material was received in the form of 12.7 mm diam bars having a fully recrystallized structure. Tensile specimens with a round cross-section of 4.5 mm diam and a gage length of 15.2 mm were machined from the bars. In order to develop the same grain size (mean linear intercept of grain boundaries) in each of the three types the specimens were annealed under a dynamic vacuum of <10?5 mm Hg, Table 11. Specimen hydriding was carried out in a modified Sieverts apparatus;&apos; hydrogen was taken into solution at 450°C and after holding the specimens at this temperature for 24 hr they were furnace-cooled to room temperature at an average rate of -100 C deg per hr. By this method nominal hydrogen contents of 0, 50, 100, 250, and 500 ppm were introduced into specimens of Ti 115, Ti 130, and Ti 160 (100 ppm (wt) -0.5 at. pct). The actual hydrogen contents were calculated from the weight differences obtained by weighing the specimens before and after the hydriding treatment. Tensile tests were carried out at temperatures of -196", -78", 20°, 150°, and 300°C on a 10,000 kg In-stron machine at a nominal strain rate of -1.0 x 10-3 sec-1. Fractured specimens were sectioned in planes parallel to the tensile axis, mechanically polished to 0.25 µm grade of diamond paste, and then attack polished using a solution containing by volume 99 parts H2O, 1 part HF, and 1 part HNO3. Although the latter treatment unavoidably opened out cracks and voids visible after mechanical polishing, it did reveal the grain structure, titanium hydride morphology, and deformation twinning structure.

Jan 1, 1970

By Charles M. Packer, Oleg D. Sherby, Roy H. Johnson

Originally round tensile specimens of a eutectic Zn-A1 alloy develop elliptical cross sections during superplastic deformation. This observation, coupled with a detailed study of the microstructure and preferred orieniation, suggests that crystallographic slip and continuous grain boundary migration or re-crystallization are important processes during super-plastic deformation. In spite of the extensive activity in superplasticity1-15 and the numerous explanations proposed, no single model has had universal acceptance. It has been established, however, that the general requirements for superplastic extension of two-phase alloys include an extremely fine, stabilized grain size of the order of a few microns, a temperature about equal to or greater than one-half the melting point, a critical range of strain rate, and a similarity in the mechanical strength of the major phases. The proposed models can perhaps best be characterized in terms of the important phenomena associated with them. These phenomena include: phase instability,1 diffusional creep by volume diffusion3 or grain boundary diffusion4,5 slip and continuous grain boundary migration or recrystalliza-tion,= grain boundary Sliding,7-9,13,14 and dislocation glide.&apos;5 In this paper, experimental observations will be reported which support a model involving slip and continuous grain boundary migration or recrystalliza-tion. Specifically, a correlation will be made between this model and the development of elliptical cross sections as originally round specimens are superplas-tically deformed. For the most part, superplasticity studies have been conducted with eutectic or eutectoid alloys. Probably the most thoroughly studied material has been the monotectoid Zn-A1 alloy.1,2,6,12,13,15 No attention to the eutectic Zn-A1 alloy has previously been reported, and the results discussed in this paper represent part of a general study of the superplastic properties of this alloy. MATERIALS The alloys used in this investigation were prepared by melting appropriate quantities of 99.99+ pct A1 and 99.999 pct Zn in air, mixing, and pouring into a water- cooled stainless-steel mold. Wet-chemical analysis was conducted with each heat of alloy prepared, using the procedure of Fish and smith.16 The composition of the eutectic alloy was 95.1 wt pct Zn. Ingots about 2 in. thick were rolled to 0.4-in. plate at about 300°C with a reduction of 5 to 10 pct per pass. Specimens were machined from the plate with the tensile axis parallel to the rolling direction. The specimens were round, with 0.150-in.-diam, 1.25-in.-long gage length, and 0.25-in.-diam threaded grip sections. EXPERIMENTAL PROCEDURE Specimens were mounted inside a uniform-temperature quartz tube which was surrounded by a double elliptical radiant furnace with a 12-in.-long uniform-temperature hot zone and a low thermal capacity. The tube extended through the top and bottom of the furnace and permitted rapid quenching of the loaded specimens when quickly filled with cold water at the conclusion of the test. The quench precluded any effects on specimen microstructure from a normal, slow cool. Constant stress was applied to test specimens by suspending a load on a constant stress cam of the type described by Hopkin.17 The design of this cam permitted application of a constant stress for elongations up to 200 pct. For greater elongation, approximately constant stress conditions were maintained by systematically reducing the load manually. RESULTS As part of an investigation of the superplastic properties of the eutectic Zn-A1 alloy, evidence was obtained for the development of elliptically shaped cross sections as originally round specimens were extended. For example, after an elongation of about 100 pct, a round specimen with an initial diameter of 0.150 in. became elliptical with major and minor axis of 0.128 and 0.88 in., respectively. Photographs are presented to illustrate the ellipticity developed during superplastic deformation, Fig. 1. The specimen shown was deformed at a stress of 500 psi, at a temperature of 285°C, and a strain rate of 2.28 x 10-2 min-1. The strain-rate sensitivity exponent* was measured at *The strain-rate sensitivity exponent, m, is defined as d In o/d In c where o is the steady-state flow stress and E is the strain rate. this temperature and in the strain rate range 10"3 to 10-1 min-1 was found to be about 0.5. This value is typical of those observed with superplastic materials. The material studied exhibited negligible strain hardening during superplastic deformation, the creep rate remaining constant under constant stress and temper-

Jan 1, 1969

By R. L. Skaggs, D. T. Peterson

The effect of carbon in solid solution on the plastic behavior of thorium was studied by measuring the flow stress of Th-C alloys from 4.2" to 573°K and at several strain rates. Carbon was found to strengthen thorium primarily by increasing the thermally activated component of the flow stress. The strengthening due to carbon was directly proportional to the carbon content and decreased rapidly with increasing temperature up to 423" K. The flow stress also increased with increasing strain rate. The strengthening appears to be due to a strong short-range interaction between carbon atoms and dislocations. A yield point was observed in the Th-C alloys which increased with increasing carbon content. JTREVIOUS study of the mechanical properties of thorium has been confined largely to the measurement of the engineering properties. Work prior to 1956 has been summarized by Milko et al.1 who reported that additions of carbon to thorium sharply increased the room-temperature strength. In addition, the yield strength was observed to decrease rapidly over the temperature range from 25" to 500°C. In 1960, Klieven-eit2 measured the flow stress of thorium containing 400 ppm C. He found that over the temperature range from 78" to 470°K the flow stress was strongly dependent on temperature and rate of deformation. A drop in the load-elongation curve, or a yield point, was observed over most of the above temperature range. Above 470°K, the flow stress was nearly independent of temperature and strain rate. This strong temperature and strain rate dependence of flow stress is not generally observed in fcc metals. It is, in fact, more typical of the behavior reported for bcc metals. Bechtold,3 Wessel,4 and conrad5 have pointed out the striking difference between the commonly studied bcc metals and fcc metals in regard to the effect of temperature and strain rate on the flow stress. Zerwekh and scott6 studied the plastic deformation of thorium reported to contain 12 ppm C. They found that this material did not obey the Cottrell-Stokes law as expected for fcc metals. In addition, they found values of the activation volume smaller by an order of magnitude than expected for an fcc metal. They concluded that thorium was strengthened by a randomly dispersed solute. Thorium differs from many other fcc metals that have been studied extensively in that it shows a relatively high carbon solubility at room temperature. Mickleson and peterson7 report the solubility limit at room temperature to be 3500 ppm C. The lowest value reported is that of Smith and Honeycombe8 who report the limit to be 2000 ppm C at 350°C. The pres- ent investigation was a systematic study of the flow stress and yield point phenomenon of thorium over a broad range of carbon content, temperature, and strain rate. EXPERIMENTAL PROCEDURE The thorium used in this investigation was produced by the reduction of thorium tetrachloride with magnesium as described by Peterson et a1.&apos; Chemical analysis of the original ingot after arc melting and electron beam melting is shown in Table I. Alloys were prepared by arc melting this thorium with high-purity spectrographic graphite. Threaded specimens with a gage length 0.252 in. diam by 1.6 in. long were used for the constant stress or creep measurements. These specimens were machined from rod which had been cold-rolled and swaged to % in. diam. Tensile specimens were prepared by swaging annealed 3/8 -in.-diam rod to 0.102 *0.001 in. The as-swaged wire was cut to lengths of 2 in., annealed, and the center 1-in. gage length elec-tropolished to 0.100 ±0.001 in. The specimens were gripped for a length of 3 in. at each end by a serrated four-jaw collet which was tightened by a tapered compression nut. No slipping occurred in the grips and negligible deformation was observed outside the 1-in. gage length. Both the creep and tensile specimens were annealed at 730°C under a vacuum of 1 x X Torr. The resulting structures consisted of equiaxed recrystallized grains with a grain size of 3200 grains per sq mm for the tensile specimens and 2200 grains per sq mm for the creep specimens. After the specimens were prepared, samples were analyzed for nitrogen, oxygen, and hydrogen. The results of these analyses are given in Table 11.

Jan 1, 1969

By R. H. Gautschi, F. C. Langenberg

Rare-earth additions were made to laboratory heats of Type 310 stainless to observe their effect on as-cast ingot structure, nitrogen and sulfur contents, and nonmetallic inclusions. Lanthanum had a grain-refining effect in 30-lb ingots, but results with 200-lb ingots were inconsistent. Cerium, lanthanum, and misch metal lowered the sulfur content when the sulfur exceeded 0.015 pct and the rare-earth addition was greater than 0.1 pct. The rare-eardh content in the metal dropped very rapidly within the first few minutes after the addition. The size, shape, and distribution of nonmetallic inclusions was not changed in 30-lb ingots, but changes were noticed in larger ingots. RARE-earth* additions have been made to austenitic Cr-Ni and Cr-Mn steels to improve their hot workability. The high alloy content of these steels often results in a considerable resistance to deformation and inherent hot shortness at rolling temperatures, particularly in larger ingots. Rare earths in the metallic, oxide, or halide form are usually added to the steel in the ladle after deoxidation although they can be added in the furnace prior to tap or in the molds during teeming. The literature- indicates that the effects of rare-earth treatments on these stainless steels are not consistent, and sometimes even contradictory. Since no mechanism has been presented which satisfactorily accounts for the claimed improvements, the effects of rare earths are a qualitative matter. The work described in this paper was initiated to expand the knowledge of the effects of rare-earth additions on melting variables such as ingot structure, chemical analysis, and nonmetallic inclusions. REVIEW OF LITERATURE Ingot Structure—Rare-earth additions to stainless steels have been reported to cause a change in primary ingot structure in that there are fewer coarse columnar grains. However, the results are inconsistent. While one investigation1 has shown a large reduction in coarse columnar crystals, another2 has been unable to observe this effect, particularly when small ingots were poured. Post and coworkers3 observed ingot structures for a number of years and found that the columnar type of structure is not definitely a cause of any particular trouble in rolling or hammering, provided the alloy is ductile. Knapp and Bolkcom4 found rare-earth additions to be quite effective in preventing grain coarsening in Type 310 stainless steel. Chemical Analysis—Many effects of rare-earth treatment on chemical analysis have been claimed in the literature. Russell5 observed that some sulfur is removed by rare-earth metals, and that a high initial sulfur content improved the efficiency of sulfur removal. Lillieqvist and Mickelson6 report that rare-earth treatment causes sulfur removal in basic open-hearth furnaces, but not in basic lined induction furnaces. Knapp and Bolkcom found no sulfur removal in acid open-hearth and acid electric furnaces, probably because the acid slag can not retain sul-fides. snellmann7 showed that sulfur could be lowered apprecfably with rare-earth additions; however, a sulfur reversion occurred with time. Langenberg and chipman8 studied the reaction CeS(s) = Ce(in Fe) + S(in Fe), and found the solubilit product [%Ce] [%S] equal to (1.5 + 0.5) X 10-3&apos;at 1600°C. Results in 17 Cr-9 Ni stainless were about the same as those in iron. Beaver2 treated chromium-nickel steels with 0.3 pct misch metal and observed some reduction in the oxygen content. He also noted an inconsistent but beneficial effect of rare earths when tramp elements were present in amounts sufficient to cause difficulty in hot working. It is not known whether rare earths reduce the content of the tramp elements or change the form in which these elements appear in the final structure. No quantitative data are available concerning a possible effect of rare-earth treatment on hydrogen and nitrogen contents. However, Schwartzbart and sheehan9 stated that additions of rare earths had no effect on impact properties when the nitrogen content was low (0.006 pct), but served to counteract the adverse effects of high nitrogen content (0.030 pct) on these properties. Knapp and Bolkcom4 analyzed open-hearth heats in the treated and untreated conditions and found the nitrogen content (0.006 pct) to be unaffected. These two results lead to the speculation that rare-earth additions can reduce the nitrogen content to a certain level. Decker and coworkers10 have observed that small amounts of boron or zirconium, picked up from magnesia or zirconia crucibles, increased high-tem-

Jan 1, 1961

By R. B. Adamson

The fatigue behauior of irradiated copper single crystals is compared to that of unirradiated crystals. Proton or electron irradiation did not substantially change the fatigue-lzj.e, fatigue-hardening-, or slip-line characteristics, while neutron irradiation did appear to alter these parameters. Postfatigue transrrzission electron microscopy did not reveal any marked structural differazces between irradiated and unirradiated specimens. Possible dislocatio~a mechanisnzs to explain the observed behavior are discussed. A LTHOUGH considerable work has been done to ascertain the effects of radiation on the tensile properties of metals (e.g., Refs. 1 and 2), little work of a basic nature has been reported on the effect of radiation on fatigue properties. Since it is known that fatigue properties are sensitive to conditions at the surface of the metal, it was felt that charged particle irradiation, whose penetration into metals is very small, might influence the fatigue behavior. To investigate this surface effect, irradiations with 10 mev protons and 1.5 mev electrons were conducted. The range of 10 mev protons in copper is about 0.236 mm; which is very small compared with the thickness of the specimens used (1.53 mm). The range of 1.5 mev electrons is somewhat larger, on the order of 0.665 mm.4 On the other hand, irradiation with reactor neutrons produces damage throughout the entire specimen, so neutron irradiation can be used to study the effects of bulk damage. The damage introduced by proton and neutron irradiation is expected to con!ist of large interstitial dislocation loops,5 tiny (<25A) vacancy loops," and/or various vacancy-rich regions called depleted zones.&apos; In the case of electron irradiation at about -173°C the damage is expected to consist of isolated Frenkel pairs.&apos; The effect of radiation damage on the fatigue properties of some engineering materials has been reported,g,10 but the results are not clear-cut or consistent. SPECIMEN PREPARATION Zone-refined copper was used to grow single crystals by a modified Bridgeman technique in an inert helium atmosphere. Using a seeding method, single crystals were obtained as bars about 6 in. long with a cross section of 3 by $ in. Immediately upon removal from the split-mold graphite boat in which they were grown, the very soft bars were embedded in a room-temperature setting plastic. They could then be cut into specimen lengths without introducing any long-range damage. Generally, four or five specimens plus one seed were obtained from each bar. The plastic material was dissolved away in acetone and the orientation of each sample was checked by the standard Laue X-ray

Jan 1, 1968

By John L. Lamont, Walter Crafts

ADEQUATE hardenability has long been recognized as one of the first requirements for producing desired mechanical properties in a heat-treated steel. Since the introduction of the Jominy end-quench test1 and the development of correlative information to expand its use, industry has had an effective measure of hardenability. Prediction and control of the hardenability have been made possible by Grossmann&apos;s principle2 for calculating hardenability from chemical composition; and Field&apos;s conversion3 from depth of half-martensite hardening to Rockwell C hardness has made the relation more quantitative. These developments have facilitated the design of new steels and the control of standard grades to the extent that it has been possible to establish tentative hardenability bands for some of the more commonly used alloy steels.4 As the depth of hardening of the Jominy test specimen is usually measured by Rockwell C hardness, it was considered that it should be possible to predict the hardness by a more direct calculation. It has been found that this can be accomplished by the addition of Rockwell C units proportional to the carbon and alloy content, grain size, and position in the Jominy test specimen. The calculation has been found to be fairly accurate, and because of its additive character is relatively simple to use. In principle the method of calculation is somewhat similar to the expressions developed by Herty, McBride, and Hollenback,5 Burns, Moore, and Archer,6 and Burns and Riegel.7 The calculation is started from a base that includes the effects of carbon content and position in the Jominy test speimen. Rockwell C units are added to the base in proportion to the alloy content and grain size. This sum represents the Rockwell C hardness up to the level at which a disproportionate increase of hardness is caused by the formation of martensite, and above this level an increment for martensite hardening is added. The effects of alloys are directly proportional to the amounts present and are independent of each other, the carbon content, and the position in the specimen. Furthermore, the factors for determining the martensite increment are dependent only on carbon content and are independent of cooling rate and alloy content. It is this absence of interrelation between the different factors that makes it possible to calculate the hardness and makes the method of calculation consistent with the principle that the character of the hardening reaction is governed primarily by carbon and that alloys exert their effect chiefly through control of the critical cooling rate. The principle of the calculation, and the effects of alloys on the critical cooling rate,

Jan 1, 1945

By Walter Craft, John L. Lamont

Adequate hardenability has long been recognized as one of the first requirements for producing desired mechanical properties in a heat-treated steel. Since the introduction of the Jominy end-quench test&apos; and the development of correlative information to expand its use, industry has had an effective measure of hardenability. Prediction and control of the hardenability have been made possible by Grossmann&apos;s principle2 for calculating hardenability from chemical composition; and Field&apos;s conversiona from depth of half-martensite hardening to Rockwell C hardness has made the relation more quantitative. These developments have facilitated the design of new steels and the control of standard grades to the extent that it has been possible to establish tentative hardenability bands for some of the more commonly used alloy steels.4 As the depth of hardening of the Jominy test specimen is usually measured by Rockwell C hardness, it was considered that it should be possible to predict the hardness by a more direct calculation. It has been found that this can be accomplished by the addition of Rockwell C units proportional to the carbon and alloy content, grain size, and position in the Jominy test specimen. The calculation has been found to be fairly accurate, and because of its additive character is relatively simple to use. In principle the method of calculation is somewhat similar to the expressions developed by Herty, McBride, and Hollen-back,5 Burns, Moore, and Archer,= and Burns and Riege1.l The calculation is started from a base that includes the effects of carbon content and position in the Jominy test speimen. Rockwell C units are added to the base in proportion to the alloy content and grain size. This sum represents the Rockwell C hardness up to the level at which a disproportionate increase of hardness is caused by the formation of martensite, and above this level an increment for martensite hardening is added. The effects of alloys are directly proportional to the amounts present and are independent of each other, the carbon content, and the position in the specimen. Furthermore, the factors for determining the martensite increment are dependcnt only on carbon content and are independent of cooling rate and alloy content. It is this absence of interrelation between the different factors that makes it possible to calculate the hardness and makes the method of calculation consistent with the principle that the character of the hardening reaction is governed primarily by carbon and that alloys exert their effect chiefly through control of the critical cooling rate. The principle of the calculation, and the effects of alloys on the critical cooling rate,

Jan 1, 1947

By John L. Lamont, Walter Craft

Adequate hardenability has long been recognized as one of the first requirements for producing desired mechanical properties in a heat-treated steel. Since the introduction of the Jominy end-quench test&apos; and the development of correlative information to expand its use, industry has had an effective measure of hardenability. Prediction and control of the hardenability have been made possible by Grossmann&apos;s principle2 for calculating hardenability from chemical composition; and Field&apos;s conversiona from depth of half-martensite hardening to Rockwell C hardness has made the relation more quantitative. These developments have facilitated the design of new steels and the control of standard grades to the extent that it has been possible to establish tentative hardenability bands for some of the more commonly used alloy steels.4 As the depth of hardening of the Jominy test specimen is usually measured by Rockwell C hardness, it was considered that it should be possible to predict the hardness by a more direct calculation. It has been found that this can be accomplished by the addition of Rockwell C units proportional to the carbon and alloy content, grain size, and position in the Jominy test specimen. The calculation has been found to be fairly accurate, and because of its additive character is relatively simple to use. In principle the method of calculation is somewhat similar to the expressions developed by Herty, McBride, and Hollen-back,5 Burns, Moore, and Archer,= and Burns and Riege1.l The calculation is started from a base that includes the effects of carbon content and position in the Jominy test speimen. Rockwell C units are added to the base in proportion to the alloy content and grain size. This sum represents the Rockwell C hardness up to the level at which a disproportionate increase of hardness is caused by the formation of martensite, and above this level an increment for martensite hardening is added. The effects of alloys are directly proportional to the amounts present and are independent of each other, the carbon content, and the position in the specimen. Furthermore, the factors for determining the martensite increment are dependcnt only on carbon content and are independent of cooling rate and alloy content. It is this absence of interrelation between the different factors that makes it possible to calculate the hardness and makes the method of calculation consistent with the principle that the character of the hardening reaction is governed primarily by carbon and that alloys exert their effect chiefly through control of the critical cooling rate. The principle of the calculation, and the effects of alloys on the critical cooling rate,

Jan 1, 1947