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By A. E. Powers, J. F. Libsch

THE simultaneous influence of time and temperature upon the tempering process in steel is well known. Hollomon and Jaffe¹ have expressed the effect of time and temperature upon the progress of tempering by a single parameter, T (c + log t); where T is the absolute temperature; t, the tempering time; and c, a constant characteristic of the steel and treatment. It was found that when hardness data for plain carbon and low alloy steels were plotted vs. this parameter, a master tempering curve was obtained which satisfied all the data for a given steel and a given hardening treatment. Roberts, Grobe, and Moersch² successfully applied the tempering parameter to various tool steels, including high speed steel for tempering times ranging from 6 min to 100 hr. The influence of tempering time and temperature upon the physical properties of high speed steel has also been extensively investigated.'" Recently, the use of induction heating for very rapid tempering treatments has received attention. The authors% have shown that tempering treatments of only a few seconds duration may be successfully applied to plain carbon and low alloy steel. However, the influence of such short tempering treatments in high speed steel has not been explored. Since high speed steel is a highly alloyed steel exhibiting physical reactions during tempering that are often relatively slow and large in magnitude, it is an interesting steel for the study of tempering reactions. It was the purpose of the present investigation, therefore, to study the early progress of reactions leading to secondary hardness in high speed steel, type 6-5-4-2, and to determine if induction-tempering treatments of a few seconds duration are able to produce results equal to those of more conventional long-time tempering cycles. Experimental Details The chemical compositions for two different heats of W-Mo high speed steel used in this study are given in Table I. Table II summarizes the heat treatment given various groups of specimens cut 21/2 in. long and centerless ground to ¼ in. diam. Hardening treatments consisted of preheating to 1600°F (870°C) for V2 hr and then oil quenching from 2250°F (1230°C). Heat I was subjected to the high temperature in a salt bath for 3 min, while specimens of heat II were austenitized in a carbon-block muffle furnace for 10 min. Specimens of series E were immediately refrigerated to — 318°F (— 195°C) in liquid nitrogen following the hardening treatment to transform the major portion of the retained aus-tenite. Specimens of series F and G were subzero cooled to — 100°F (-75°C) in a dry ice-alcohol mixture. Induction tempering was performed with a Lepel high frequency converter operating at a frequency of approximately 300,000 cycles per sec. Heating cycles were controlled and recorded for each specimen using a chromel-alumel thermocouple, percussion welded to the surface of the specimen, and a modified high speed instrument with a timer previously used and described.' Temperature oscillation of the specimens, while being held at the tempering temperature, was ± 15°F (8°C). Tempering Treatments: After hardening, specimens were tempered between 900" and 1500°F (480" and 815°C) to study the progress of retained austenite decomposition and secondary hardening. The specimens tempered in salt for 1 hr (series C, G, and I) were considered to represent conventional treatment and are used for comparison with rapid tempering treatments. Several induction-tempering cycles were employed: 1—flash tempering, i.e., induction heating to the tempering temperature and immediately cooling (series A, E, and F); 2—induction heating for 60 sec at temperature (series B); and 3—double-induction tempering by two successive heating and cooling cycles (series D). All specimens tempered by induction were heated at an initial rate of 450°F (250°C) per sec except those of series E, which were heated at an initial rate of 1300 °F

Jan 1, 1952

By J. H. Wernick, S. Geller

A number of new AB, compounds, in which A is a rare earth or yttrium atom and B is Al, Mn, Fe, Co, or Ni, having the cubic MgCu, structure (Laves phase) are reported. In most of the compounds, the interatomic distances are normal; the lanthanide contraction is observed. However, in the compounds CeB2, B = Fe, Co, Ni, Ce appears to have a valence substantially greater than three; in CeAl2, Ce appears to be trivalent. These results are interpreted as vesulting from an energetically more favorable situation for the 4f electron of Ce to be lost to the 3d band of Fe, Co, nnd Ni. Evidence for the existence of homogeneitj! ranges in these compounds is presented. THE purpose of this paper is to report on the crys-tallographic investigations of a large number of new compounds, Table I, with the MgCuz structure (cubic Laves phase). It is a part of a continuing study of the magnetic properties and structures of binary systems involving the rare earths. In a previous paper' some of the magnetic properties of such systems were reported briefly. We have also reported2 a number of compounds of the CusCa type. The compounds were prepared by induction melting in Argon atmosphere of mixtures of stoichiomet-ric amounts of the constituent elements.* For most of the compounds fused alumina or silica crucibles were used as the containing vessel; graphite crucibles were used to prepare CeA12, NdAl2 and TbA12. X-ray powder photographs were taken with CrKa radiation and the use of Straumanis-type Norelco cameras of 114.6 mm diam. The compounds AB2 belong to space group Fd3m-Ol with 8A in a): (000; 01/2 '/2;3) + 000-; b % XA and 16B in dl: (000; oVa %; 3) + 5/87; % %; 7e % Vs\£>. Because the intensities of the reflections on the powder photographs of the different compounds are similar, relative intensities were computed only for DyMnz for CrKa radiation, Table 11. In the calculation of intensities, the Thomas and umeda3 atomic scattering factors, corrected for dispersion,4 were used. The agreement between observed and calculated intensities leaves little doubt that DyMnz has the MgCuz structure. Crystallographic data for the ABz compounds are given in Table JII. Twelve of these compounds have been reported by other authors. A comparison of the published results with our work is given in Table W.* ers of elements of lower purity, to peritectic reactions in some cases, and to the presence of homogeneity ranges in these alloys, so that melting losses would still result in single phase alloys. The possibility of existence of homogeneity ranges in these compounds was investigated systematically only for GdMnz. At room temperature, the solid solution range is between

Jan 1, 1961

By S. E. Haszko

SEVERAL new XGa2 intermetallic compounds, Table 1, where X is a rare earth, having the AlB, structure were prepared as part of a continuing study of the magnetic and structural properties of rare-earth alloys.' In this note, the crystallographic results of these compounds are presented. Chart, Eq. 121 for the data in Fig. 1 can be adequately represented by The corresponding standard free-energy change is AF; = -4.576 T log K = -20,900 + 10.20T [5I At low nitrogen concentrations the ratio of mole fraction to weight percentage is a constant so that the mole fraction X of nitrogen is given by X = 0.0392 [%NJ. At low values of X, the activity and the concearation approach each other, hence K, = 0.0392 K,, where K, is expressed in terms of the mole fraction of nitrogen. Hence Eqs. [4]. and [5] become

Jan 1, 1962

By R. E. Cech, J. H. Hollomon

KURDJUMOV and Maksimova reported experiments with manganese steels and high carbon steels' and with an Fe-Ni-Mn alloy' in which mar-tensite was formed isothermally over a range of temperatures. They found in some cases that mar-tensite formation could be suppressed by rapid quenching to liquid nitrogen temperature. From their microstructural observations of martensite formed isothermally, they concluded that the rate controlling step is nucleation rather than growth. Kulin and Cohen,3 in an attempt to reproduce these experiments, found that with a steel having the same composition as that reported by Kurd-jumov and Maksimova, the transformation to martensite was essentially complete above the temperature range of Kurdjumov and Maksimova's isotherms. The possible reasons for this disagreement were not considered. Recent papers by Das Gupta and Lement4 and Kulin and Speich5 report the formation of isothermal martensite in a high chromium steel and in an Fe-Cr-Ni alloy, but neither paper can be considered a verification of the original Kurdjumov and Maksimova results. Further, in neither case were the authors able to suppress the formation of martensite entirely. Because of the important bearing the Kurdjumov and Maksimova results have to an understanding of the mechanism of martensite reactions it was felt that an experimental investigation directly concerned with checking the validity of their results was in order. This paper describes the results obtained on the isothermal transformation over the temperature range from —79" to —196°C of an alloy of iron, nickel, and manganese. Experimental Apparatus A 15 lb heat of an alloy containing 73.3 pct Fe, 23.0 pct Ni, and 3.7 pct Mn was melted by induction and cast under argon. The ingot was forged to 1-in. bar and a portion rolled to 1/16x1 1/2-in. strip. This strip was pack-homogenized 300 hr at 1100" in a helium-filled sealed iron tube. The composition after homogenization was 73.2 pct Fe, 22.94 pct Ni, 3.73 pct Mn, 0.05 pct C, and 0.015 pct N. The strips were cut to 1/2-in. width for dilatometer and metal-lographic specimens. Only the center portion of the 11/2-in. strip was used in the present investigation. The dilatometer employed was similar in design to one described by Flinn, Cook, and Fellows." A concentric fused auartz rod and tube assembly with hooks for holding the specimen was mounted so as to transmit the specimen dilation to a 1/10,000 in., 1/10 in. travel dial gage. The dilatometer proper was mounted by means of extension arms to a counterweighted sliding member on a vertical standard. This method of mounting permitted rapid transfer of the dilatometer from the austenitizing furnace to the quenching bath and low temperature chamber. A small electrical vibrator on the dilatometer kept frictional effects of the quartz members at a minimum. The austenitizing unit was a vertical, molybdenum-wound, hydrogen atmosphere furnace maintained at a constant temperature ±3°C by means of constant power input. A 12-in. stainless steel jacketed copper liner having 1/2-in wall thickness acted to equalize the temperature in the hot zone of the furnace. This liner, closed at the bottom end and open at the top to permit entrance of the dilatometer and specimen, was kept filled with dry nitrogen gas. A chromel-alumel thermocouple was placed inside the tube to determine the temperature. The 4-in. dilatometer specimens in the chamber varied less than 1/2° across the specimen length except for a 1 1/20 drop at the end nearest the open end of the furnace. The low temperature isothermal holding bath was a double Dewar arrangement similar to one described by Turnbull7. The outer bath was filled with a refrigerant at a temperature lower than the desired holding temperature. The inner bath was filled with Freon "11" or "12" or a mixture of both, depending upon the holding temperature. This inner bath which tended to be cooled by the outer bath was kept at a constant temperature by introducing a small amount of heat with a manually controlled electric heater. Stirring was accomplished by bubbling dry air through the bath. A Leeds and North-rup type K potentiometer was used to measure the inner bath temperature as indicated by a five element copper-constantan thermopile. The bath temperature was maintained within ±0.2°C of the desired temperature by occasionally adjusting the heater current so as to keep the Leeds and Northrup galvanometer at zero deflection with a constant setting of the potentiometer. Isothermal tests were usually continued for 300 to 400 min and another reading made at approximately 1000 min if the bath, unattended overnight, had not deviated in temperature more than 5°C. Transformation curves are drawn dashed (Fig. 1) through the time region where temperature was not controlled precisely. Experimental Procedure Dilatometer specimens of 1/2x1/16-in. strip were cut to 41/2-in. length and holes were drilled for the quartz hooks with proper spacing to give a 4-in. measured length. A thermocouple consisting of 0.012-in. diameter chrome1 and alumel wires was spot welded to the specimen and threaded between the dilatometer rods to binding posts near the dial

Jan 1, 1954

By R. F. Mehl, R. F. Bunshah

A fast amplifier technique has been developed for the measurement of the rate of propagation of martensite in an Fe-29.5 pct Ni alloy. The time of formation of one plate of martensite is 3x10 sec and the rate of propagation is 3300 ft per sec approximately. IT has been known for some time that the plate-like structural unit of martensite forms from austenite with great rapidity. Wiester1 and Hane-mann, Hofmann, and Wiester took motion-pictures of the transformation as it occurs in a 1.65 pct C steel; they demonstrated that a single plate formed fully in the time interval between successive frames, viz., 1/20 sec, thus setting an upper limit. Forster and Scheil,3 using an Fe-Ni alloy with 29 pct Ni, recorded the sonic characteristics of the process electrically, upon an oscillograph, setting the upper time limit at 0.002 sec. Forster and Scheil,~ measuring the change in electrical resistance in the same alloy upon a cardiograph, set a limit of 0.02 sec. Forster and Scheil5 later, employing the same alloy, improved their technique, reporting an upper limit of 7.10 sec. In studying signals of such short duration, it is an important question whether the frequency response of the electrical system used is high enough compared to frequency of the pulse measured, or, put differently, whether the system is able to reproduce without distortion the signal arising, in this case, from the formation of a single martensite plate. Forster and Scheil (referring only to their last paper) obtained signals of a frequency of 30 kilocycles (hereinafter kc); this was about the frequency response of the equipment used; thus, if the signal had a frequency higher than 30 kc, it would still appear as a signal of frequency 30 kc. All of these results thus provided upper limits only. Recent developments in electronics have made available equipment with very high frequency response, very high sweep-speeds, high gain, etc. The electrical characteristics of such equipment, used in the present study, are given in Table I. Such equipment offers obvious attraction in the study of the rate of propagation of a martensite structural unit—and perhaps of other structural alterations proceeding at a very high rate. This paper reports an attempt to develop a technique employing such equipment to measure the time of propagation of a martensite structural unit and the variation of this with temperature, with the mode of formation—athermal and isothermal—in both polycrystalline and single-crystal samples; and from such measurements to obtain the rate of propagation. As will be seen, the results obtained are useful theoretically. Materials All data presented here are for an Fe-Ni alloy of the following analysis: 29.5 pct Ni, 0.027 pct C, 0.135 pct Mn, 0.094 pct Si, balance Fe. There were several reasons for choosing this alloy: 1—it is substantially the one used by previous investigators; 2—it exhibits both the athermala and the isothermal' mode of formation of martensite, both studied in detail by Machlin and Cohen; 3—the subzero temperatures of transformation in this alloy are experimentally very convenient; 4—it exhibits the "burst phenomenon";" 5—the change in electrical resistance upon the formation of martensite, a decrease, is great, approximately 50 pct.' The polycrystalline specimens were in the form of wires of 0.025 in. diameter; the single crystals were 1x1/4x1/4 in. Experimental Methods Electrical Apparatus: Fig. 1 is a schematic drawing of the electrical circuit used. The principle used in these measurements is the same as that used by Forster and Scheil." A small direct current, about 1 to 2 amp, is passed through the sample. When a martensite plate forms, the resistance of the sample changes and a high frequency signal is generated. This signal is picked up by the probes attached to the sample, fed into the bank of amplifiers and thence to the vertical deflection plates of a cathode-ray oscilloscope. The signal itself triggers the oscilloscope trace which flashes across the tube face and is photographed by means of a 35 mm movie camera at the end of a light-tight hood. The camera has no shutter. As soon as the signal flashes

Jan 1, 1954

By P. G. Shewmon, F. N. Rhines

THE determination of the self-diffusion coefficient of magnesium has been made possible recently by discovery1-1 of a radioactive isotope, Mg28 having a half-life of 21.3 hr,1 and subject to manufacture in useful quantity. In the present research this material was condensed from the vapor phase upon a surface of high purity magnesium. The progress of diffusion of the tracer atoms into polycrystalline magnesium was followed by machining layers and measuring the change in the intensity of radiation as a function of the distance of each layer from the surface. The self-diffusion coefficient was found to be 2.1 X 10-8 sq cm per sec at 627°C, 3.6 X 10-9 sq cm per sec at 551°C, and 4.4 X 10-10sq cm per sec at 468°C; the activation energy is about 32,000 cal per mol. Experimental Procedure Since there was no other published measurement of a diffusion velocity in any magnesium-base material, is was necessary to employ a number of new experimental techniques. The short half-life of Mg28 made it necessary to complete the entire experimental procedure within three or four days. This meant that the work had to be done where a cyclotron was readily accessible and that all operations, prior to the diffusion heat treatment, had to be so designed as to minimize their time requirements. Unusual problems were imposed also by the chemical reactivity of magnesium, its high vapor pressure, and the fact that no satisfactory method for elec-trodepositing magnesium on magnesium is presently available. Finally, the machining and handling of the easily air-borne radioactive-magnesium chips involved certain health hazards, resulting in the need for further experimental restrictions. Preparation of Mg28 The Mg28 was produced in the Carnegie Institute of Technology syncrocyclotron by the neutron spallation of chlorine.5 his involved bombarding a 2 gram crystal of high purity NaCl with a beam of 350 mev protons for a period of 2 hr, after which the crystal was dissolved in warm water and the Mg28 was concentrated and purified by chemical means (see Appendix). About 50 microcuries of Mg28 thus were obtained in the form of magnesium oxinate (8 hydroxyquin-olatc?), which was ignited in air to produce MgO. This in turn was reduced to magnesium metal vapor, by the method of Russell, Taylor, and Cooper," in the vacuum apparatus shown schematically in Fig. 1. Here the essential part is a tantalum ribbon, slightly dished to receive the MgO. The ribbon, pre- viously outgassed at high temperature, is heated to about 1700°C by passing an electric current through it, whereupon tantalum oxide is formed, magnesium vapor is released almost instantaneously, and condensed partly upon the diffusion sample. Diffusion-Sample Preparation: Hot-extruded magnesium rod, 21/32 in. round was used in making the diffusion specimens. The magnesium analyzed as follows: 0.004 pct Al, 0.027 pct Fe, 0.040 pct Mn, 0.0004 pct Cu, 0.0002 pct Ni, and less than 0.01 pct Ca, 0.0004 pct Pb, 0.0011 pct Si, 0.001 pct Sn, and 0.001 pct Zn. A brief study of the crystal texture of this material revealed a sharp fiber texture with the (001) plane roughly parallel to the extrusion axis. Cylindrical samples 1/2 in. long by 5/8 in. were machined from this rod, the end faces dressed on 3/0 emery, and lightly etched with 20 pct HC1 in water. These samples then were annealed for at least twice the intended time of diffusion, at the intended diffusion temperature, in order to stabilize the grain structure at about 1 mm average diameter. The annealing treatments were conducted in argon in the same apparatus and in the same manner as the subsequent diffusion treatments, which will be described presently. Thus, a strain-free plane surface was produced, but there remained a layer of MgO which had largely to be removed before the layer of Mg28 was deposited. Most of this layer was taken off by two light passes over 3/0 emery paper. The balance of the oxide and a thin layer of metal were then removed by etching 5 to 10 min in 4 pct nital (4 pct HNO3 and 96 pct ethyl alcohol) made with absolute alcohol. There followed immediately three quick rinses in: 1-49 1/2 pct methanol, 49 1/2 pct acetone, and 1 pct formic acid, 2-50 pct methanol and 50 pct acetone, and 3-pure benzene. This procedure is essentially that of Sturkey.7 The resulting surface, which was of almost elec-tropolished brightness, remained plane and was free of cold work. It could be kept clean by storing under benzene, or in a desiccator; short exposure

Jan 1, 1955

By H. S. Cannon, F. N. Rhines

The application of a static load to a copper powder compact during sintering at an elevated temperature accelerates the rate of sintering in such a way that a given load induces the same proportional increase in rate for all times of sintering. It is shown that sintering under a load is like creep under a fixed load in that the stress required to accomplish a given degree of densification is proportional to the logarithm of the sintering time. VIRTUALLY all of the theories of sintering that have been put forward within recent years have contained the assumption that the chief driving force of the process is the surface tension resident in the exposed surfaces and internal pores of the compact, or powder mass. An externally applied load might be expected to provide a somewhat equivalent driving force for sintering. It is known that the application of a compressive load, during sintering, hastens densification, but it is by no means clear whether sintering under the influence of surface tension alone and sintering under an applied load are fundamentally similar processes. The present study was undertaken in an effort to obtain an answer to this question and with the hope that the answer may contribute to an understanding of the mechanism of sintering. It has been found that there is a close relationship between sintering and creep processes. Copper powder compacts were sintered in hydrogen at 1000 °C under dead loads of 0 to 165 psi and the progress of sintering was observed by means of density measurements. Using a commercial reduced oxide copper powder, see Table I, cylindrical compacts Yz in. x x in. high were made at a pressure of 12,500 psi. For sintering, these were placed in a cylindrical graphite container into which they fitted snugly. A compressive axial load was applied to the compact through a graphite rod of similar diameter, which rested upon the upper end face of the compact; iron weights, in suitable amount, were placed upon the graphite rod to provide the load. This assembly was encased in a vertical silica tube within a resistance-type furnace capable of maintaining a substantially constant temperature within the working zone. After various predetermined times at temperature, the samples were removed from the furnace and their density was measured by conventional means. The heating-up and cooling-down times have been included in the computed sintering time, using the assumption that the sintering rate doubles for each increase of 10 °C in temperature. The experimental results are presented in Table 11. Upon metallographic examination of the specimens, it was found that there was no apparent change in the shape of the pores as a result of loading, i.e, no flattening, Fig. 1. Substantial contraction away from the container walls was observed in all samples sintered with loads of 10.5 psi and less.

Jan 1, 1952

By H. S. Cannon, F. N. Rhines

IT. H. Hausner( Sylvunia Electric Products Inc., Bay-side, N. Y.)—The results reported by the authors are interesting because they contribute some information on the principles of sintering and also because of a certain practical value for the manufacture of powder . metallurgical parts in production. Pressed powder compacts are frequently sintered in a boat in several layers so that the lower layers are actually sintered under the weight of the upper layers and, therefore, are frequently deformed. The authors gave information on this deformation process by determining the effect of the load on the density. The experimental setup of the authors, however, has a disadvantage—that the sintering occurred in a cylindrical container so that the deformation was stopped in the direction of the diameter. The authors should have rather called this a study of hot-pressing than of sintering. I want to call the attention of the authors and others interested in sintering under load to the experimental work described by Dawihl and Rix.' These authors sintered cylindrical compacts under a lengthwise ten-sional load of 0 to 25 g and found that the shrinkage in length and diameter changes considerably with the load, but that the volume shrinkage is affected very little by the load. H. S. Cannon (authors' reply)—We wish to thank Dr. Hausner for calling attention to the experimental work of Dawihl and Rix. The fact that they found volume shrinkage little affected by varying tensional loads during sintering seems to support the contention that the forces due to loading are equivalent to and additive to the forces which cause densification. This contention is the basis of our comparison of sintering and creep.

Jan 1, 1952

By R. W. Heckel, H. W. Paxton

The growth of grain boundary films and Widmanstiitten plates of proeutectoid cementite in hypereutectoid steels ulas considered quantitatively in three plain carbon steels and one "pure" iron-carbon alloy. Growth was found to take place at a slower rate than would be predicted on the basis of a model invoking rate control by long range diffusion of carbon. The films in the pure alloy grew faster than those in the plain carbon steels. A possible explanation is suggested. In 1904, Nernsst' and Brunner2 postulated that ionic crystals growing in supersaturated aqueous solutions grew at rates determined by diffusion through the solution to the growing crystal interface. The gradient down which the diffusion took place was assumed to be fixed by the supersaturated bulk solution concentration, the concentration dt the crystal surface and some arbitrary distance. The flux of material to the crystal was described as Flux where D is the diffusion coefficient, A the crystal surface area, Ci the bulk solution concentration, Co the saturated solution concentration, and 6 the thickness of the diffusion zone. It is obvious that the expression is an adaptation of F+ick's3 first law of diffusion (steady state). This was the initial formulation of what will be defined here as "diffusion controlled growth," i.e., growth limited by the long range diffusion of a component either to or from the advancing interface assuming both phases at the interface to be in equilibrium. This idea of equilibrium interface concentration implies an infinite reaction rate at the interface. Volmer, Zener,' and 11schner6 have derived expressions for the diffusion controlled growth of spherical precipitates in metallic systems. These analyses agree that the growth in a given direction should be parabolic with time. Brown and Hawkes7 observed that graphite, formed both from the decomposition of cementite and from the decomposition of eutectoid austenite in cast irons, grew according to a parabolic relationship and, therefore, concluded that the laws of diffusion controlled growth, as defined above, were obeyed. They, among others, failed to consider, however, that parabolic growth is a necessary, but not sufficient, condition for diffusion controlled growth. Mehl and Dube"' have pointed out that equilibrium may not be realized because the concentration at the interface cannot change instantaneously from that of the bulk to the saturation value. Furthermore, they propose that an equilibrium solute concentration in the parent phase adjacent to the precipitate would remove the thermodynamic activity gradient across the interface and, thus, stop the growth process. Frisch" has also emphasized the importance of interface concentrations that vary throughout the growth of a new phase. The variation in activity across an interface, as discussed by Onol' and Cahn and Hilliard,12 is of fundamental importance to this question. Ham13 considered the data of Turnbull14 on the growth of barium sulfate in aqueous solutions. He concluded that the data could be analyzed in terms of a radiation-type boundary condition. Flux across interface = K (c, - C,) [21 where C, is the concentration in the solution at the interface, Co the saturated solution concentration, and K the proportionality constant. The edgewise growth of Widmanstlitten plates, frequently referred to as the rate of lengthening, was first considered by Zener.'' Basing a mathematical analysis on steady-state (constant velocity) growth he concluded that where G is the growth rate, D the solute diffusivity, Ci the concentration in the bulk, Co the equilibrium interface concentration, C, the concentration in the precipitate, a a constant, Y the radius of curvature of the edge of the plate, and rC the critical radius, i.e., the radius which would increase the activity of solute at the interface at equilibrium under the influence of capillarity to that of the bulk. Zener1'

Jan 1, 1961

By Elmars Ence, Harold Margolin

The Ti-Fe and Ti-Fe-0 systems were re-examined because of the controversy regarding the existence of Ti2Fe, and to consider all available data points to the existence of Ti,Fe. The Ti-Fe-0 system contains two ternary compounds: E, corresponding to Ti2Fe; and y. SEVERAL authors have investigated the constitution of titanium-rich alloys of the Ti-Fe system. The most extensive study of titanium-rich portions of the Ti-Fe system was by Van Thyne, Kessler, and Hansen,' who investigated this system up to 50 pet Fe and used the highest purity materials available for their alloy preparation (iodide titanium was used for alloys up to 20 pet Fe). According to Van Thyne et al., phase relationships in the region of investigation are governed by phases a,ß, and TiFe. No evidence of an intermetallic compound Ti,Fe was found. although earlier. works by Laves and Wallbaum,' and Duwez and Taylor' reported its existence. Rostoker's study on the occurrence of TilX phases" confirmed the findings of Van Thyne et al. Rostoker proposed that the compound Ti Fe found by Duwez does not exist but is actually a ternary compound, Ti1Fe3O, originated by inadvertent oxygen contamination. The partial isothermal section of the ternary Ti-Fe-0 system as reported by Rostoker' seems to confirm this explanation. In the course of phase diagram work conducted at New York University, however, certain irregularities were observed to be associated with ternary systems of the type Ti-Fe-X. The ternary phase 6, observed in the systems Ti-Fe-Mo' and Ti-Fe-V." was found to be structurally identical to the com-pound Ti2Fe as reported by Duwez and Taylor, and to Rostoker's compound Ti1,Fe2O. Since the amount of oxygen possibly present in the Ti-Fe-Mo and Ti-Fe-V systems could not account for the observed amounts of the compound, it appears that the d phase in these systems is not Ti,Fe,O. On the other hand, considering the amounts of the 6 phase, particularly in the Ti-Fe-Mo system, the location of the phase was uncertain. It was felt that the introduction of the Ti2Fe phase would alleviate some of the inconsistencies of the two systems. Because of the uncertainties relating to the phase Ti2Fe, or Ti1Fe2O, it appeared worthwhile to re-examine the Ti-Fe and Ti-Fe-O systems in the vicinity of these compounds with highly sensitive metallographic techniques and with X-ray methods. Experimental Procedure Alloy Preparation—For the study of the binary system four alloys were prepared, containing 26.9 (30 wt pct), 34.0 (37.5 wt pet), 41.2 (45 wt pet), and 56.3 (60 wt pet) atomic pet Fe, and for the ternary Ti-Fe-O system 18 alloys were prepared in the composition range of 1.6 to 16.9 atomic pet 0 and 24.3 to 55.7 atomic pet Fe. The materials used for the Ti-Fe alloys were iodide titanium (99.98 pet Ti, 0.002 pet 0) and Ferro-vac-E iron (99.95 pet Fe, 0.0052 to 0.0072 pet 0). For the Ti-Fe-O study the materials used were sponge titanium containing less than 0.06 pet 0, Ferrovnc-E iron, and Baker's analyzed TiO2. The nominal weight and atomic percentages of the ternary alloys prepared are shown in Table I. Melting—Charges of 10 to 15 g were melted in a nonconsumable arc furnace in argon atmosphere according to the technique described elsewhere.'" Since there was practically no weight loss through the various stages of melting and oxygen losses have not been observed previously, it appeared justifiable to use nominal composition for interpretation of data. Iodide titanium control buttons, of the same mass as the Ti-Fe charges, and melted under the same conditions, were used to check hardness pickup during melting. A hardness increase of 2 to 3 Vhn was found. Heat Treatment—The specimens were annealed in quartz capsules under argon. To avoid contact between the specimen and capsule material all specimens were wrapped in titanium sheet. The annealing times are given in Table 11. The attain-

Jan 1, 1957

By R. Scot Clark

The reactively sputtered silicon dioxide capacitor -was developed for use in the monolithic integrated circuit, thereby requiring the capacitor to be fabricated on an oxidized silicon slice. The silicon dioxide film is formed by reactively sputtering silicon in a 50 pct Ar-50 pct 0, atmosphere and the physical properties are indistinguishable from silica. A practical upper limit of capacitance per unit area of 0.25 pf per sq mil is reached with the capacitors fabricated from the Si0, film. Methods shown to enhance this value are double stacking the thin-film capacitors and addition of aluminum to the silicon cathode during sputtering to form an aluminosilicate dielectric. A major contribution to the field of diffused integrated circuits would be the addition of auxiliary passive devices for replacement of diffused passive devices which are currently being fabricated for many integrated circuits. This accomplishment would increase the flexibility of the diffusion process in order to concentrate more on transistor parameters rather than on fabricating diffused resistors and capacitors. To pursue this technique, a thin-film SiOz capacitor was developed which has _ proven applicable to many integrated circuits. Although the SiOl capacitor has an application, the major deterrent from extending the integrated circuit into many useful areas such as low-frequency linear application is the low dielectric constant of SiO, and the low usable capacitance in an integrated circuit. This paper will cover the sputtering techniques used for forming the SiO, film, the physical and electrical properties of sputtered SiO,, and yield information concerning the application of these capacitors to integrated circuits. REACTIVE SPUTTERING Reactive sputtering is simply the sputtering of a metal or semiconductor in glow discharge in the presence of a reactive gas. The material to be sputtered is seen in Fig. 1 as the cathode of the system and is bombarded with positively charged ions of the ambient gas. In this investigation, the ambient gas is composed of 50 pct Ar and 50 pct O2 at a pressure of approximately 2.5 X l0-' Torr. The ions are accelerated toward the cathode in the cathode dark space by the electric field and upon striking the cathode effect a momentum energy transfer to the surface atoms. The transferred energy is sufficient to dislodge a surface atom or atoms and these particles diffuse through the glow discharge to the collector or anode. Several mechanisms of oxidation in the reaction chamber can be considered during reactive sputtering. 1) The surface of the cathode is oxidized and the oxide is subsequently sputtered. 2) Oxidation and sputtering occur simultaneously. 3) Sputtering of the cathode material is followed

Jan 1, 1965

By A. S. Grove, C. T. Sah, E. H. Snow, B. E. Deal

A summary of- several recent investigations in to the properties of the metal-oxide-silicon system is presented. A major portion of these studies makes use of the MOS capacitance-z)oltage method of' analysis. The particular areas of investigation which are reported include: 1) a general survey of the electvical properties of thermally oxidized silicon surjbccs; 2) a study of ion migration through silicon dioxide films ; 3) measurements of electron and hole mobilities in surface inversion layers; 4) a study of impurity redistribution due to thermal o.ridatiotz; and 5) measurements of the rates of oxidation oj-heavily doper7. silicon. THE importance of the metal-oxide-semiconductor (MOS) system in the semiconductor industry is well-known. In addition to its importance in the "planar" device technology,' the MOS structure is now also used in the fabrication of active solid-state devices. Consequently, extensive efforts have been made recently to obtain a better understanding of the characteristics of this system. A summary of some studies of the MOS system conducted in our laboratories during the past year is presented. For the most part these studies used silicon as the semiconductor, along with silicon dioxide and aluminum as the other two components of the system. Since the MOS capacitance-voltage method of analysis was used extensively in these studies, we will first briefly describe its nature and consider some of the possible causes of deviation of experimental observations from the simple theory. We will then outline the various related areas of investigation carried out in our laboratories and will briefly indicate some of the results. It should be noted that the purpose of this paper is merely to provide a brief summary of MOS studies. More detailed discussions of the various areas of investigation are given in the references cited. PRINCIPLES OF THE MOS C-V METHOD OF ANALYSIS' A sketch of the MOS structure is shown in the upper portion of Fig. 1. In this case the insulating film is Si02 and the semiconductor p-type silicon. If a large negative bias is applied to the metal field plate, holes are attracted to the silicon surface. The silicon then behaves much like a metal and the capacitance measured is that of the oxide layer alone, Co. If a small positive bias is applied to the aluminum, holes are repelled and a region depleted of majority carriers is formed at the silicon surface. This depletion I-egion adds to the width of the dielectric and the measured capacitance begins to drop. With increasing positive bias, the width of the electrical depletion region increases. At some large positive bias an inzevsion regiotr is formed at the surface and additional charges induced in the silicon appear in the form of electrons in this narrow inversion region. Thus the depletion-region width approaches a maximum value and, consequently, the capacitance reaches a minimum value and then either levels off or rises again depending on the measurement frequency and the rate of equilibration of the minority carriers in the inversion layer.3 Band diagrams, along with the corresponding charge distributions, are shown in Fig. 1 for the above bias conditions. If minority carriers cannot accumulate at the surface to form an inversion region, the depletion-region width continues to increase with increased positive bias and the capacitance drops toward zero as in a reverse biased p-n junction. The effect of a work-function difference $hs between the metal and the silicon, and of surface charges per unit area Qss located at the oxide-silicon interface, is simply to attract charges in the silicon much like the applied bias. It can be shown that this results in a parallel shift of the capacitance-voltage characteristic along the voltage axis by an amount corresponding to AV = -$bIs + Qss/Co. Theoretical curves have been calculated4 giving the capacitance of the MOS structure C normalized to the oxide capacitance Co vs the quantity VG here VG is the voltage applied to the metal field plate. In Fig. 2 such calculations are shown as points for a particular oxide thickness and bulk impurity concentration for a p-type semiconductor. (For an n-type semiconductor the curves would be mirror images of these.) All three cases, i.e., low frequency. high frequency, and depletion, are indicated. Also shown in the figure are recorder tracings of the characteristics of actual devices. These characteristics have been shifted along the voltage axis to compensate the effect of surface charges and work-function difference. It is evident that agreement between experiment and theory is good. The nature of this shift along the voltage axis is

Jan 1, 1965

By B. L. Averbach

Recovery and primary recrystalliza-tion in cold worked metals are usually considered as two competing processes. Some of the effects which usually accompany recovery are: alleviation of stress corrosion tendencies, changes in thermal emf,1 damping capacity,2 electrical resistivity,2 and magnetic properties,3 and only minor changes in hardness or the related strength properties. During primary recrystalliza-tion new unstrained grains are formed at the expense of the strained matrix. These new grains eventually become visible metallographically, and nucle-ation and growth kinetics have been indicated for this process.4,5 Frequent attempts have been made to study the cold-working phenomenon by observations on the line broadening by X ray diffraction patterns. Relatively few measurements of line intensities have been made, although Brind-ley and his collaborators, 6,7,8 by means of film techniques, compared the intensities of cold worked Cu, Ni, and Rh patterns with those from chemically precipitated powders. These precipitated powders were presumed to be strain free, and it was found that the intensities for the cold-worked materials progressively decreased as the Bragg angle increased except for the first line, where there was an increase due to reduction in extinction. This was interpreted as a randomness in atomic position induced by cold work. Such randomness is similar to that caused by thermal agitation and has been described as "frozen heat" displacement of 0.08-0.10 A from the mean atomic position. In a recent study9 on the effect of cold work in metals on their powder pattern intensities, the changes in integrated intensity for heavily cold worked alpha brass were observed as a function of the annealing temperature. These measurements were made with a manually operated Geiger-counter spectrometer using CuKa radiation monochromated with a rock salt crystal. Intensity measurements were made with a scaling meter over small intervals of angle, and the equipment was so arranged that the diffracted and incident beams made equal angles with the specimen. Intensities could be compared directly by simply interchanging specimens, and comparisons from day to day were made with a standard whose line intensities did not change on aging. It was shown that a cold worked alpha brass standard was stable for at least a year. Table 1 indicates the results of the integrated intensity measurements on a 70 Cu-30 Zn brass. In the sample preparation, a brass plate was first cold rolled 50 pct and then filed, screened to —325 mesh, compacted into briquettes at a pressure of 60,000 psi and finally annealed for one hour at various temperatures up to 400°C. The briquetting pressure did not seem to influence the integrated intensities, and most of the cold work was introduced by the filing. Although this method of cold work is not quantitative, it was used to obtain random orientation (and thus uniform diffraction lines) in order to make accurate measurements of integrated intensity. Back reflection patterns were taken in each case to check the uniformity of the lines, and from the observed line broadening it was apparent that this type of plastic deformation was quite severe. Care was taken to traverse the entire background of the pattern and to assign to each peak the total intensity above this background. The bases of the diffraction lines were quite broad and spread out over several degrees, even for the narrow peaks. The theoretical intensities were calculated to include a temperature correction, a dispersion correction, and a Lorenz- polarization factor corrected for the crystal monochromated beam. In Table 1 it was necessary to match the calculated and observed values at only one point, and the rest of the experimental values were converted directly to this arbitrary scale. The integrated intensities in Table 1 are listed in arbitrary units, and the accuracy was sufficient to reproduce any of the measured line intensities to within + 1.5 units. It is evident that the percentage error on the strongest line (111) was quite low. The calculated values and the observed intensities for the cold worked material matched reasonably well. As the annealing temperature was raised, however, the intensity of the strongest reflections, particularly the (lll), decreased measurably. Since the background intensities of all of these patterns were identical, such behavior could be interpreted as a primary

Jan 1, 1950

By J. Washburn, R. Drouard, E. R. Parker

Temperature dependence of the rate of recovery in zinc single crystals after a simple shear deformation at low temperature was investigated. Some tentative suggestions regarding the annealed and strain-hardened states of a crystal are discussed. RECOVERY may be defined as the gradual return of the mechanical and physical properties of strain-hardened metal to those characteristic of the annealed material; an increase in temperature increases the rate of recovery. The annealing process in strain-hardened polycrystalline metals is complicated by the inhomogeneity of strain which always exists in aggregates. Polygonization in bent regions of the crystals and growth of new almost strain-free grains starting at points of severe local distortion1-:' make it almost impossible to isolate and study the recovery process. Homogeneously strained single crystals, however, do not polygonize or re-crystallize and hence they can be used advantageously to study recovery. In such crystals strain hardening is completely removed by recovery alone. Since recovery is a process whereby certain lattice disturbances introduced by plastic flow are gradually reduced, a knowledge of the rate and temperature dependence of this process for various conditions of prestrain might be helpful in formulating a model of the strain-hardened state. For simplicity it seemed desirable to limit the type of prestrain to the simplest obtainable, i.e., simple shear strain. In the experiments to be described, recovery was studied by observing changes in the stress-strain curve of prestrained zinc single crystals held for various times at temperatures above that employed for straining. Single crystals were grown from the melt by a modified Bridgeman technique from Horse Head Special zinc 99.99 pct pure, and from spectrographically pure zinc 99.999 pct pure. They were grown as 1 in. diameter spheres and acid-machined' to the final specimen contour. The test section was a cylinder about 1/8 in. high and 3/4 in. in diameter. The conical sections adjacent to the test section were cemented into the grips so the load could be transmitted to the crystal as uniformly as possible. The specimens were oriented so that in testing the maximum shear stress was applied along one of the slip directions, [2110], in the (0001) plane. Details of the production and testing of such specimens have been presented.' Each test was carried out according to the following schedule: 1—The crystal was strained at — 50°C until it reached a maximum shear stress, ,,,. The strain rate was approximately 5 pct per min in all cases. 2—After straining, the crystal was unloaded before the temperature was changed. Unloading required about 3 min. 3—The temperature of the specimen was then increased from — 50°C to the temperature, T, of recovery. This change in temperature was completed in a time of less than 2 min. The specimen remained at temperature, T, for a time, t, which differed for the various specimens. 4—Thereafter the temperature was again reduced to — 50 °C in approximately 3 min. 5—While at —50°C, the stress-strain curve after recovery was obtained. 6—The specimen was then unloaded and annealed for 1 hr at 375 °C in a helium atmosphere to bring about complete recovery. Cooling to room temperature after anneal required 90 min. 7—The same crystal could be re-used for another test because the plastic properties after annealing closely duplicated those of the original crystal. The specimen was immersed during the test in a bath of methyl alcohol which, through a system of tubes, could be pumped through either of two heat exchangers to regulate the temperature; this was accomplished by circulating the liquid through coils immersed in a bath of acetone and dry ice for cooling or in a bath of warm water for heating. Test temperatures were thus maintained constant within ±1°C. The — 50°C temperature was low enough so that no measurable recovery occurred during unloading and reloading. The stress-strain curve continued after recovery along a path below, but approximately parallel to, the path of a curve obtained in an uninterrupted test. Fig. 1 shows some of the results from a specimen of 99.999 pct Zn. The amount of downward displacement of the curve due to recovery was a

Jan 1, 1954

By E. C. W. Perryman

The recovery of X-ray line broadening, hardness, and electrical resistivity from cold worked AI-Mg alloys has been investigated. The results, together with those from density measurements, suggest that magnesium atoms freeze in the excess vacancies formed by cold working, and that this affects the climb of dislocations during the recovery process. PREVIOUS work1, " has shown that while 1 pct Mg increases the activation energy for recrystalliza-tion, it decreases the activation energy for the recovery of mechanical properties and decreases the subgrain size both after cold working and annealing. A similar result has been reported by Varley2 for an A1-2 pct Mg alloy. With plastic deformation at high temperatures, McLean and Farmer' and Rachinger have found that magnesium appears to retard the motion of dislocations and, furthermore, they find little or no effect of magnesium on the size of subgrains formed during high temperature deformation. In view of the apparent contradictions as to the effect of magnesium on subgrain size, the recovery process in Al-Mg alloys has been investigated more thoroughly by studying the annealing out of X-ray line broadening, hardness, and electrical resistivity from alloys cold worked at room temperature. Material Used—The chemical analyses of the alloys are given in Table I. Fabrication—The material used was cold rolled 20 pct at room temperature, the grain size prior to the last cold rolling operation being similar to that used in previous work; i.e., 230. The experimental procedure for annealing, determination of X-rav half-veak breadth. hardness measurement, electEica1 resistivity, and density and metallographic examination was exactly the same as previously described." Variation of X-Ray Half-Peak Breadth with Annealing Time—Isothermal annealing curves at 100°, 200°, and 250°C were obtained for material cold worked 20 pct. The half-peak breadth of the (333) Ka, line directly after cold working is shown as a function of magnesium content in Fig. 1. Only with the 2.87 pct Mg alloy was overlapping of the a, and n.. reflections observed to any appreciable extent. To separate these, Rachinger's method' was used. Typical isothermal annealing curves are shown in Figs. 2 and 3 for 100" and 200°C, respectively. These curves are similar to those obtained previously for super-purity aluminum except that the

Jan 1, 1957

By Louis Raymond, John E. Dorn

The object of this investigation was to analyze the recovery that arises when the stress on a specimen undertaking creep is reduced. For this purpose annealed specimens of high-purity aluminum were precrept under a stress of 1000 bsi to a strain of 0.08 following which the stress was reduced for various periods of time to 10, 250, 500, or 700 psi. When the original stress was reapplied the subsequent creep curve lay above that for the unre-covered state and below that for the original annealed state. Analyses on the kinetics of this recovery as a function of the temperature gave a stress-sensitive activation energy that decreased as the reduced stress was increased from a value of 64,000 cal per mole at 10 psi to 37,000 cal per mole at 750 psi. Recovery was also detected and measured during creep under the reduced stress. Following a short initial period, the creep rate under the reduced stress increased monotonically until it reached the secondary-creep rate for the reduced stress. The temperature dependence of this phenomenon was also shown to be correlatable in terms of the previously deduced activation energy for recovery. The activation energies for creep of most pure metals at high temperatures have been shown to agree well with those for self-diffusion.'j2 Since the true secondary stage of creep is usually due to the steady-state balance between the rate of strain hardening and the rate of recovery, it is generally thought that the activation energy for recovery of the creep-induced substructure equals that for creep itself. A shoft time ago, however, Ludemann, Shepard, and Dorn~ found that the activation energy for recovery of the creep-induced substructure in high-purity aluminum under zero stress was almost twice that for self-diffusion, namely about 65,000 cal per mole; obviously recovery under reduced stresses differs in some significant way from the recovery that accompanies the secondary stage of creep. The major purpose of this investigation is to study the effect of stress on the re- covery of the creep-induced substructure in order to provide a better understanding of the recovery mechanism itself. EXPERIMENTAL TECHNIQUE High purity aluminum, containing 0.004 pct Cu, 0.002 pct Fe, and 0.001 pct Si, used in this investigation, was in the form of 0.100-in.-thick sheet which has been cold-rolled to the H-18 temper. Creep specimens were milled from the sheet with their tensile axes in the rolling direction. All specimens were then heated at 686°K for 1 hr followed by air cooling in order to produce an annealed structure which exhibited a uniform equiaxed grain size of about 4 grains per mm. Tests were run in creep machines fitted with Andrade-Chalmers type of lever arms so contoured as to maintain the stress constant to within 0.05 pct of the reported values. Constant temperatures to *O.l°K were obtained by complete immersion of each specimen in a temperature-controlled and agitated bath of molten KN02-KNOs mixture. Where changes in temperature were involved, the change was effected in less than 2 min by manually replacing one bath by another controlled at the second temperature. Displacements over the gage section were sensed by linear differential transformers, the output of which was autographically recorded. The calculated strain measurements were sensitive to 5x EXPERIMENTAL PROCEDURE The following analyses are based on extensions of the previously announced effect of the temperature on the creep strain,2 namely for a = constant, where e = the total true tensile creep strain for a given applied true tensile stress, t = the duration of the test, R = the gas constant, T = the absolute temperature, Q, = the activation energy per mole for creep which is independent of the stress, / = a function of 8, = and of the stress, and a = the stress. The validity of this correlation for high-purity aluminum is demonstrated in Fig. 1 for temperatures in the near vicinity of 600°K; the activation energy for creep, Q,, which is approximately that for self-diffusion, is insensitive to the applied stress

Jan 1, 1964

By H. L. Couch, J. D. Lubahn

In decarburized mild steel, the strain hardening arising from 1/2 pct strain can he partly recovered by subsequent heating, even though re crystallization or grain growth does not occur. This recovery varies from 5 pct in an hour at room temperature to 70 pct at 800°C. The variation with temperature was qualitatively similar to that reported for copper, but occurred at lower temperatures. Except for the initial portion (Bazdschinger effect), the stress-strain curve following recovery can be superimposed on the original curve by shifting it to the left. In other words, the tensile behavior is essentially the same after straining and heating as if there had been less strain and no heating. The importance of this observation in understanding simultaneous deformation and recouery is explained. AN earlier investigation1 on copper showed that strengthening due to strain hardening was augmented by heating at moderate temperatures, but was diminished by heating at higher temperatures, Fig. 1. Auxiliary experiments1 indicated that recovery and strain aging are independent processes, which may proceed simultaneously, and whose effects are additive as indicated in Fig. 1. In order to study recovery by itself, similar tests were made on decarburized mild steel, where strain-aging effects are known2 to be absent. MATERIAL, TESTING PROCEDURE The specimens were made from rimmed, hot-rolled SAE 1020 steel 0.040 in. thick, by stamping out rectangular blanks and end holes, Fig. 2, and pack milling the reduced section. These were wet-hydrogen treated2 for 16 hr at 720°C to remove carbon and nitrogen completely and then heated 1 hr at 850°C in vacuum to stabilize the grain size. Auxiliary ex- periments showed that heating up to 800°C will not cause grain growth. They were prestrained 5 to 7.5 mils per in. using the special grips shown in Fig. 2. Such small strains are less than the "critical" strain for recrystallization and, therefore, will not cause recrystallization, even at high temperature. The recovery treatment after prestraining and before the retesting consisted of heating for 1 hr in wet hydrogen at the desired temperature. In one test, Huggenberger gages were used to define more accurately the loading and unloading curves. Fig. 3 illustrates the creep during the early stages of unloading, the hysteresis due to cold stretching, and removal of hysteresis by heating.3 RESULTS The load-deflection curves had ratner widely differing shapes for different specimens, both before and after the recovery treatment. Some specimens showed perfectly smooth curves, Fig. 4, while others exhibited an inflection more or less suggestive of a yield point (Fig. 4 shows all extreme case). Some curves were much steeper than others; Fig. 5 shows two extremes. Some additional ex-

Jan 1, 1960

By C. L. Meyers, J. L. Lytton, T. E. Tietz

The recovery of tensile flow stress of 99.995-pct Al and Al-1 pct Mg alloy was investigated using a fractional recovery parameter. Tensile strainirg was conducted at room temperature, and recovery treatments were made in the range from 80° to 200°C. Equal values of fractional flow stress recovery were found to result in equivalent structural states. Identical recovery treatments were found to produce constant values of fractional flow stress re covery, independent of prestrain. The activation energy for recovery of the 99.995-pct A1 between 80" and 200°C was found to be 23,000 +2000 cal per mole, and the activation energy for the Al-1 pct Mg alloy was 27,500 cal per mole. 1 HE degree of recovery of a cold-worked metal may be studied by measuring the changes which take place in any of a number of properties. Some of the properties which have been used by past investigators include X-ray diffraction phenomena, electrical resistivity, hardness, creep strength, elastic limit, and flow stress. Despite the apparent preponderance of such studies, little is known concerning the effect of recovery on the strength of metals except as deduced from changes in various types of hardness measurements. Furthermore, little information is avail- able concerning the effects which specific solute atoms have on the recovery process. Limited studies have indicated that in some cases solid-solution additions greatly decrease the rate of recovery,' whereas in at least the case of magnesium additions to alluminum an increase in the rate has been reported.2 The purpose of this investigation was to determine the effect of a 1 pct Mg addition on the recovery of high-purity aluminum. Because of the particular interest in the effect of solute additions on the recovery behavior as related to mechanical properties, the degree of recovery was evaluated in terms of tensile flow stress. For the purposes of this study, a recovery process shall be defined as any process, short of recrystallization, whereby the properties, of work-hardened metals tend toward their values ill the unstrained state. EXPERIMENTAL PROCEDURE Test Materials. The materials used in this study were a 99.995-3 A1 and an Al-1 pct Mg alloy made from high-purity base metal. The high-purity aluminum contained the following wt pct impurities: 0.001 pct Cu, 0.002 pct Fe, 0.001 pct Si, and 0.0004 pct Mg. The Pil-1 pct Mg alloy contained 0.001 pct Cu, 0.002 pct Fe, 0.003 pct Si, and 0.99 pct Mg. Both materials were obtained in the form of as-rolled 0.125-in.-thick sheets, from the Alcoa Research Laboratories, New Kensington, Penn. Tensile specimens were cut from these sheets with the longitudinal axis in the rolling direction. Both materials were recrystallized in a molten salt bath; the high-purity aluminum at 450° C for 20 min and

Jan 1, 1962

By W. D. Ludemann, J. E. Dor, L. A. Shepard

Recovery of the creep resistance of 99.99 pct pure Al was studied at temperatures 540°, 573°, 600°, and 611°K. Poly-crystalline specimens crept under a stress of 950 psi to a strain of 5.5 pct were allowed to recover for periods of from 1 min to 16 days under a residual stress of 4.4 psi. Increased creep rates upon reapplication of the 950 psi stress evidenced softening of the material. The activation energy for the recovery process was found to be 64,000 cal-per mol. THREE major observations have clearly revealed that the creep of polycrystalline aluminum above about 510°K is controlled by the rate of climb of jogged edge components of dislocations past the barriers impeding their motion: 1) Extensive polygonization, characteristic of climb, takes place during creep.'9' 2) The activation energy for creep equals the estimated activation for self-diffusion. 3) The stress law for creep coincides with theoretical predictions based on the climb mechanism.4,5 The decreasing rate during the primary stage of creep must be ascribed to the introduction of additional barriers to the glide of dislocations. During secondary creep the density of barriers must remain constant, the rate at which new barriers are formed being equal to the rate at which they recover. For this reason the nature of the barriers, and their rates of formation and recovery, are significant to a complete understanding of creep. It is proposed here to study the kinetics of the recovery of barriers to creep of high-purity polycrystalline aluminum in the climb range. The technique will consist of creeping a series of tensile specimens under a prescribed stress to given state following which the specimens will be recovered for various times and temperatures under approximately zero stress. The amount of recovery will be determined by comparing creep curves following the recovery. EXPERIMENTAL PROCEDURE The material used for this investigation was a 99.99 pct pure Al supplied by the Aluminum Co. of America in sheets of 0.001-in. thickness having an H-18 temper. The spectroscopic analysis of impurities gave Cu-0.004 wt pct, Fe-0.002 pct, Si-0.001 pct, others-0.000 pct. Creep specimens were machined with their tensile axes in the rolling direction of the sheets. Annealing in a molten potassium nitrate-potassium nitrite bath for 1 hr at 686K, followed by air-cooling, resulted in a grain diameter of from 0.22 to 0.27 mm. Creep machines were equipped with constant stress lever arms of the type suggested by Fullman, Carreker, and Fishher,' which maintained the applied stress to within 0.04 pct of the reported value of 950 psi. Creep strains were calculated from extensions over a 6-in. gage section to the nearest 3 X 10"5. The temperatures of testing, 540°, 573", 600°, and 611°K, were obtained by immersing the specimen and extensometer assembly in a molten KNO2-KNO3 bath. Temperatures during the periods of creeping could be maintained constant to within better than ± 1°K. Correlation of creep data at different temperatures of testing demanded the use of an appropriate temperature-compensated time 8. Previous investigations have shown that the creep of pure metals at temperatures above about 0.55 of their melting temperatures can be correlated by the functional relationship3" e=f(0), s= const. [1] where e = total plastic strain during creep f = a function that depends on stress a = stress 6 = te-Q/RT = a temperature-compensated time t = time under test Q = 35,500 cal per mol = activation energy for creep R = gas constant, and T = absolute temperature In the present series of tests all of the creep was conducted under the same stress of 950 psi. To provide identical initial conditions for the recovery all specimens were first crept to a temperature-compensated time of = 47 X 10-14 min which resulted in a creep strain of 0.055 + 0.005 regardless of the creep temperature. During recovery, a small stress (4.4 psi) was permitted to remain upon the specimens to maintain tautness in the pulling assembly and to prevent mechanical damage to the soft specimen. After each recovery period, the full stress was reapplied and

Jan 1, 1961

By W. L. Phillips

The recovery properties of compression-deformed lithium fluoride single crystals were investigated as a function of prior strain, annealing time, and annealing temperature. The recovery process was studied by observation of etch pits and birefringence stress patterns. The recovery process involved first a redistribution of the dislocations and then a decrease in their number. Only by annealing at high temperatures after small strains (<0.02 in. per in.) was it possible to obtain complete recovery of mechanical properties. LITHIUM fluoride affords unusual opportunities to extend the knowledge of deformation mechanisms of nonmetallic crystalline compounds. Single crystals of high purity are readily available. These crystals deform by slip on the (110) <110> system.&apos; Unlike those of several other ionic crystals, the stress-strain curves of annealed lithium fluoride are reproducible.2 Dislocations generated in the crystals during deformation can be revealed by etch pits.3 This fact makes possible more detailed studies of mechanisms than is usually the case with metals. Also, because lithium fluoride is transparent, it is possible to follow the recovery process with birefringence stress patterns. It has been shown that with metals an increase in temperature increases the amount of recovery for a given time, and the amount of recovery increases with increasing time at the same temperature.4-6 The yield stress has also been shown to be dependent on the rate of cooling after annealing.&apos; Annealing germanium, a covalent-bond material, at high temperatures after deformation redistributes the dislocations and reduces their number. The purpose of the present paper is to extend the knowledge of recovery properties to an ionic crystal, lithium fluoride. The effect of strain, time, and temperature of recovery on the stress-strain curve was investigated. The recovery process was followed by observations of etch pits and birefringence stress patterns. EXPERIMENTAL PROCEDURE Specimens measuring approximately 0.10 by 0,10 by 0.30 in. long were cleaved from a single bulk

Jan 1, 1961