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By D. W. Lillie

Property changes produced by irradiation of Al-0.4 wt pet Li alloys at 270°C to a burnup of 0.155 pct of all atoms are described. Metallographic evidence of the formation of internal pores and the concentration of gases at grain boundaries is shown. Some conclusions are drawn concerning desirable property characteristics for resistance to radiation swelling. RADIATION induced gases are of great practical significance in nuclear engineering since they affect the behavior of fissionable fuels and control rod materials. In fuels the gases xenon and krypton are the major offenders, producing serious em-brittlement at low irradiation temperatures and gross swelling at high irradiation temperatures. In control rod materials containing boron, the production of helium from the B 10 (n, 0) Li7 reaction produces similar reactions. Since the trend in reactor design is for operation at increasingly high temperatures, the phenomenon of high-temperature swelling by these induced gases has been the subject of considerable recent study. The objectives of such work have been to obtain engineering information and quantitative data on the effects in specific fuels and control rods and to obtain further understanding of the mechanism of gas damage so that more intelligent corrective steps can be made. Analogue systems are often useful for the latter objective and in this case alloys containing Li are suitable in view of the reaction Li6 + n - He4 + He 4. Both products are gases and no serious radiation problem is produced to complicate post irradiation handling. Considerable caution is, of course, necessary in any operations in which tritium release is possible. The present program was initiated to provide a detailed study of the effects of He + H3 generated by irradiation in Li-bearing alloys. The results on Mg-Li solid solution alloys have been reported elsewhere.' This paper presents information on irradiation of an A1-0.4 pct Li alloy in which the lithium was present as highly enriched Li6 in order to maximize the radiation burnup. PROCEDURE The original intent in the selection of the alloy content was to have Li in solid solution at all temperatures. It became apparent, however, that the solubility of Li in A1 was substantially lower than that reported in the original reference consulted.' This was substantiated by the work of Nowak3 who reported solubility of less than 0.01 pct Li at 100°C. The alloy used (0.4 pct Li) was therefore two phase at room temperature. The irradiation temperature was estimated to be about 270° C, and at that temperature all or almost all of the Li would be soluble under equilibrium conditions. The precise state of the alloy under irradiation is not known. Aluminum used was 99.996 pct purity (max. impurities Si 0.002 pct, Mg 0.001 pct, Fe 0.0005 pct, and Cu 0.0005 pct). The lithium was obtained from Oak Ridge National Laboratory; 96.1 + 0.1 pct of the lithium was ~i~, but chemical impurities were 0.25 pct Ca, 0.05 pct Fe, 0.02 pct Na, 0.02 pct Cu, 0.01 pct Sr, and 0.01 pct Ba. The two metals were melted in an alumina crucible in a resistance heated furnace in an atmosphere of helium. A l-in. ingot was cast in an iron mold, machined to %-in. round, hot swaged (350°C) to 0.080-in. round, cold swaged to 0.060-in. round, and finally cold drawn to 0.040-in. round. Four-inch wire lengths were then cut and annealed at 250°C for 4 hr in helium. Irradiations were carried out in a VT hole in the Argonne CP-5 reactor. The wires were held in an aluminum jig, sixteen wires per capsule, and were maintained in a helium atmosphere for maximum heat transfer. Eight wires of pure aluminum and eight of Al-Li alloy were placed in each capsule. Argome Laboratory statements were accepted as establishing flux and exposure levels. These were based on previous experience and flux map-

Jan 1, 1961

By A. W. Sommer, H. H. Kellogg

It is shown that SO3-O2 mixtures react with sphalerite at an appreciable rate ill the temperature range of 361° to 527°C to fornz ZnSO4. The rate of reaction follows a parabolle lax. Oxygen, or O2-SO2 mixtures, have a negligible effect on sphalcrite in the same temperatuee range. PRACTICAL roasting of sphalerite is usually performed at 800°C or higher. The calcine is composed of zinc oxide unless the roaster atmosphere contains relatively large amounts of SO2 and the temperature is held to 800oC or lower, in which case zinc sul-fate may also form. Ong, Wadsworth, and assell' have made a careful kinetic study of sphalerite oxidation under these "normal conditions" and have concluded that the rate of the reaction is controlled by the decomposition of an activated complex adsorbed on the sphalerite surface. They found the rate of oxidation to be small at 700°C. Extrapolation of their data to 400°C would indicate an almost negligible rate at this temperature. In our work sphalerite was reacted with air, mixtures of SO2, O2, and N2, and mixtures of SO3, O2, and N2 in the temperature range 361o to 527OC. Negligible rates of oxidation were found, except for the gas mixtures containing SOs. With this latter gas, the oxidation of finely divided sphalerite was fairly rapid and zinc sulfate was the product. Based on the limited evidence available, the rate of sphalerite oxidation by SO3 is postulated to be controlled by gaseous diffusion through pores or cracks in the zinc-sulfate coating. This evidence for the direct reaction of sphalerite and SO, at low temperature may prove of importance to the understanding of zinc-sulfate formation in the dust-collecting equipment usually associated with zinc roasters. The roaster gas carries off fine dust, much of which may be unreacted sphalerite. The temperature in dust-collecting equipment drops from the roaster temperature (about 800°C) through the range of temperature we studied, to ambient temperature. Such dusts are known to contain far larger amounts of zinc sulfate than the primary calcine. It has been assumed in the past that this sulfate is formed by reaction of ZnO dust with SO3 (or SO, plus 0,) in the partly cooled gases. Our work shows that an alternative possibility exists—the direct reaction of SO3 with ZnS dust. EXPERIMENTAL Reaction rates for sphalerite at 350° to 600°C are relatively small so that it was necessary to use finely divided material with a relatively large surface area in order to obtain measureable amounts of reaction. In the preliminary experiments, pure mineral sphalerite, ground to pass a 325-mesh sieve, and chemically precipitated ZnS (in the form of an impalpable powder) were used. In the quantitative rate experiments the ground mineral sphalerite was processed in an Infrasizer to obtain a product with particle size between 9 and 18 µ. The analysis of this material was 66.7 pct Zn, 0.09 pct Fe, and 32.7 pct S (theoretical sphalerite is 67.1 pct Zn, 32.9 pct S). The sized powder was carefully mixed and divided into l-g samples. The apparatus used for the quantitative rate measurements is shown in Fig. 1. For the preliminary experiments the following change was made: The external catalyst furnace (B, C)* was not used. *Letters refer to Fig._______1 .___- Rather, when catalysis of the SO2 + O2 reaction was desired, the glass beads in basket M were replaced by vanadium-oxide pellets. Procedure—A l-g sample of ZnS was placed on a shallow stainless-steel tray, I, and spread evenly to a depth of about 1mm. The tray was placed in the reaction assembly and the assembly inserted in the cold furnace. The furnace tube was flushed with dry argon and then heated to the desired reaction temperature. The temperature was controlled to ±0.5oC. Gas mixtures (O2 + N2 or O2 + SO2) were prepared from tank gases by means of a mixing device identical to that employed by Darken and Gurry.2 The total flow rate of gas was 205 ml per min to point A of Fig. 1. The accuracy of the individual and

Jan 1, 1960

By Hsun Hu, R. S. Cline

The effect of rate of deformation on texture formatiotz has been studied with cube-oriented single crystals of 3 pct Si-Fe, compressed 80 pct at two widely different rates. Compression at a low rate (crosshead speed, 0.1 ipm) produces large orienta-tional changes and coarse deformation bands, whereas little change in orientation is observed, particularly at the surface of the crystal, when compressed at a high rate (impact velocity, -500 ips). Thin plates of mechanical twins are produced at the high rate, but their contribution to the deformation texture is practically negligible. The crystal deformed at a high rate has a lower hardness and a more uniform dislocation structure and is morc resistant to recrystallization. There is also a dilference in the recrystallization texture between the slowly and rapidly compressed crystals. These results indicate that plastic flow is less "turbulent" at high strain rates than at low strain ratcs. THE behavior of metals under high-speed deformation has been the subject of wide study in the past decade. Most of these works were concerned with mechanical properties during testing at high rates of loading, the resulting structures, and the theoretical aspects of the observed phenomena. The present status of knowledge and research activities in this field has been documented in recent publications.17' There is, however, very little information available in the literature concerning the effect of high-speed deformation on the texture formation in metals. The possibility of an effect of rate of deformation on texture is suggested by the microstructural differences observed between normally and very rapidly deformed samples. Aside from the strong tendency for twinning (and phase transformation in certain metals) in high-speed deformation, the slip-line patterns and the dislocation configurations show marked differences as a result of large differences in the strain rates. For instance, in mild steel in static and dynamic compression, Campbell and co-worker3,4 observed that coarse slip occurred on several systems in specimens deformed at normal strain rates, whereas specimens deformed rapidly showed only fine slip on fewer systems, the slip-line pattern being very similar to that in specimens deformed at low temperatures and at normal strain rates. The absence of multiple slip was also noticed by Dieter5 in shock-loaded nickel. The dislocation configuration in an iron shock loaded at 70 kbar pressure was shown by Leslie et al.6 to be similar to that produced by light rolling at low temperature—the dislocation lines were mostly straight and uniformly distributed. These observations suggest that the mode of deformation at high strain rates is notably different from that at low strain rates. Consequently, the nature and the extent of lattice reori-entation during deformation should also be different. This investigation was undertaken to test this idea. MATERIAL AND METHOD The remaining part of a single-crystal ingot of a 3 pct Si-Fe alloy,* prepared for an earlier investi- gation,1 was used in the present studies. Specimens 9/16 in. square and 0.365 in. thick were cut from this ingot with (001) planes parallel to the square surfaces, and the [loo] and 1010] directions parallel to the edges of the specimen, within ±1 deg. These machined crystals were etched to remove distorted metal, and annealed at 1300°C for 24 hr in a purified helium atmosphere. The annealed crystals had a hardness of 161 Dph. The crystal orientation was rechecked with X-ray back-reflection techniques. In high-strain rate experiments the crystal was compressed in a Dynapak machine to approximately 80 pct reduction in thickness (from 0.360 to 0.070 in. with an impact velocity of -500 ips). Thus, the duration of loading was approximately 6x 10-4 sec, and the average strain rate was about 103 sec-1. As a result of this rapid, severe deformation, the specimen became a roughly circular thin disc. The original shape of the crystal, however, could still be recognized by a diffusely outlined square area in the center of the disc. For compression at a low speed, the crystal was deformed in a universal testing machine at a rate of crosshead movement of 0.1 ipm. Compared with

Jan 1, 1965

By D. M. Schuster, E. Scala

The elastic effects occurring in the matrix of a composite reinforced by discontinuous fibers were studied by means of photoelastic techniques. A hirefringent plastic was employed as the matrix material with high-strength a Al2O3 whiskers as the reinforcing fibers. It was found that for whiskers aligned parallel to the tensile load direction: (I) Matrix reinforcement occurred along the length of the whisker to within about 5 diameters of the whisker tip for a length to diameter ratio, L/D, of 40. (2) Significant stress concentrations were created in regions immediately surrounding the tips; the fine as-formed tapered ends exhibited the minimum stress concentration whereas the square-ended whisker produced relatively high values, K r 2.5 for L/D = 40. (3) The axial and radial stress distributions could he determined quantitatively; the stress distribution at the whisker-matrix interface was in general agreement with theoretical calculations. (4) The highest source of stress concentration occurred at points of fracture in whiskers which had ruptured after incorporation into the composite. Whiskers aligned perpendicular to the load direction neither reinforced nor caused appreciahle stress concentrations in the matrix. ThE properties of composites have generally been formulated empirically on the basis of macroscopic tests. There are still many questions concerning the mechanical and chemical interactions occurring at the interface between the reinforcing fiber and its matrix. Continuously reinforced plastics and dispersion-hardened metals represent the two extremes of composite reinforcement. Whether artificially produced or formed in situ, the whisker composite falls between these two extremes and is an example of discontinuous fiber reinforcement. The effect of fiber shape, size, surface condition, and end configuration on the stress distribution in the matrix is important since the presence of stress concentrations, especially in any high-strength, thin-wall structure, could become the cause of catastrophic failure. DOW,' in his theoretical discussion of discontinuous fiber reinforcement, has pointed out that appreciable stress concentrations occur at the tips or ends of the reinforcing fibers. It is the purpose of this study to examine directly, by means of the photoelastic technique, the stresses which occur in the vicinity of a discontinuity or whisker tip and to measure qualitatively and quantitatively the effects of whisker geometry when embedded in a birefringent matrix material. The use of sapphire (a A1,O3) whiskers was decided upon as the reinforcing agent because of their high elastic modulus (E- 60 X 106 psi) and in some cases strengths in excess of one and a half million psi. Sapphire whiskers are of further practical interest since they retain large fractions of their strength up to temperatures approaching the melting point (3720oF).2 The whiskers were grown, by the vapor-phase reaction commonly employed,3 as part of this study to insure a physically uniform supply. Tensile and bend tests were performed to verify that the whiskers were of the expected ultra-high strength. The high-strength whiskers can be identified and selected from the combustion boats by surface perfection, shape, and size; otherwise, strength values can vary by a factor of ten or more. Macroscopic defects are quite common on the surface of large bladed whiskers and the principal experiments were conducted with hexagonal whiskers of about 0.002 in. diameter and lengths ranging from 0.1 to 0.4 in. Upon completion of these two phases of the experiment, several birefringent resins were evaluated. A plastic, developed by Zandman,4 which is supplied by the Budd Co., was found most suitable and was used as the matrix material for the whisker composite throughout the study. It has a sensitivity of 60.5 lb per in. order, calibrated in tension and cures without introducing residual stresses. Young's modulus for this matrix material is 430,000 psi in the fully cured condition. Since good wetting and bonding between the sapphire and the matrix material is essential to the interpretation of the results, a wettability test was performed. The contact angle was measured to be 168 deg where perfect wetting is defined as 180 deg; therefore, the Budd Plastic wets the sapphire

Jan 1, 1964

By W. S. Row

This mine is operated at 4000 to 4500 tons daily through a single shaft, with one rock hoist and one senice hoist. Latest shaft construction is concrete with wooden dividers. Economics of drifters and air-leg drills are compared, as well as costs of shrinkage and sub-level stoping. Economy of large haulage equipment and underground crushing is shown. THE property of Kerr-Addison Gold Mines is located in the Larder Lake district of Ontario about 3 miles from the Quebec boundary on the highway between Kirkland Lake and Noranda. It is roughly 320 miles due north of Toronto and 365 miles north of Buffalo, N. Y. The property was staked in 1906 and after several development efforts finally came into continuous production at 500 tons per day in 1937. In 1939 the daily tonnage -was increased to 1200 and in 1941 to 2100 tons. At the end of the war, because of the shortage of labor, tonnage was down to 1100 tons per day, rising to 2200 in February 1947. A further plant expansion inaugurated in 1946 was completed by December 1948, bringing the capacity of the mine and mill to a production rate of 4000 tons per day. Current production, with 880 men employed, is 4400 tons per day. Changes in mining methods and equipment, required by the recently completed expansion program, have yielded interesting comparative results, some of which are described in this paper. Hoisting of ore and waste from the mine, as well as all service facilities for handling men and supplies underground, are provided for in a single vertical five-compartment shaft. Ore and waste are hoisted in 12½-ton skips in balance by a 14-ft diam hoist with drums 115 in. wide, grooved for 2?-in. wire ropes. This hoist, with a total rope pull of 85,000 lb, was designed to operate at a speed of 2600 ft per min to a depth of 4000 ft, hoisting 15 tons of ore in each skip. It is amplidyne-controlled and powered with dual drive dc motors of 2250-hp each, through flexible couplings to two pinion shafts, one on each side of the main gear. Each motor has a peak load rating of 4500-hp at point of greatest duty. Direct current power to the hoist motors is supplied from a motor generator set consisting of a 5000-hp synchronous motor driving two 1750-kw dc generators. The loading pockets used so far are at depths of 1500 and 2725 ft respectively. Consequently the present hoisting speed is 2000 ft per min and the skips capacity only 12½ tons. Now that the shaft has been deepened the new pockets at 3934 ft will be increasingly used so that the speed and the skip size will be increased up to original specifications as required. Some difficulty in meeting the required hoisting cycle is expected because of the shape of the skips. As now in use the cross-sectional dimensions of the inside of the skip are 4 ft 6 in. x 3 ft 8 in. To hold 121/2 tons, therefore, they are 14 ft 10 in. deep. Since the skips are the conventional overturning or Kim-berley type, considerable hoisting time is lost in retardation in entering the headframe dump and in acceleration when leaving. It is expected that to obtain the specified tonnage from this hoist when the skip size is increased to 15 tons it may be necessary to resort to bottom dump skips. This type of skip could reduce considerably the present excessive acceleration and retardation times. Analyses of the skip-hoisting operation are made monthly, and every effort is made to reduce controllable delays. For a nine-month period in 1951 such an analysis shows that the hoist was in operation 92.5 pct of the available time, which was allotted as shown in Table I. Overall hoisting costs, cage and skip, for the year 1951, averaged $0.168 per ton of ore milled. The mine is serviced entirely by means of a single cage, capacity 35 men or 15,700 lb, operating in con-

Jan 1, 1954

By D. H. Baldwin, R. E. Reed-Hill

Six compositions of polycrystalline ZY-0 alloys, containing up to 4.2 at. pct 0, were tested in tension between 77° and 600° K. The data obtained from each of the compositions corresponded closely to a rela-ion between yield stress and absolute temperature of the form In s/so = BT, where oo is the yield stress extrapolated to zero degrees and B is a constant. In agreement with others who have observed this relationship, it is shown that the activation energy may be expressed as Ho In so/s. In the present specimens Ho is approximately 18,000 cal per mole and is apparently independent of temperature and composition inside the limits of the investigation. It is also demonstrated that this form of activation energy cowesponds to a strain rate sensitivity parameter RT/Ho. Oxygen was also noted to have an effect upon the operative deformation mechanisms. With increasing oxygen concentration there was an increased tendency to observe both nonbasal slip and cross-slip phenomena. Oxygen does not seriously inhibit twinning more than it does slip. Twins were observed in all specimens tested. It is becoming increasingly evident that interstitial atoms in solid solution are able to interact strongly with mobile dislocations. Stein, Low, and seybolt,&apos; have shown that, if the carbon concentration in bcc iron is lowered below the solubility limit, its flow stress temperature dependence is markedly reduced. This suggests that carbon atoms in interstitial solid solution may be responsible for the pronounced temperature dependence of the flow stress normally observed in iron. This view has recently been challenged by Leslie and sober2 who observed a strong flow stress temperature dependence in iron to which a trace of titanium had been added in order to remove carbon atoms from solution. Since the interstitial concentration must be reduced below approximately 1 ppm in order to produce a pronounced effect on the flow stress temperature dependence,&apos; studies of the effect of interstitials on the flow stress in iron necessarily involve serious experimental difficulties in alloy preparation. There are other metals, however, in which strong effects of interstitial solutes upon both the flow stress and its temperature dependence are observed. Of particular significance is zirconium which, according to Domagala and Mcpherson, 3 is capable of dissolving 28.6 at. pct O. The O-Zr alloy system is an almost ideal system for studying the interaction of interstitial atoms with deformation modes since it is possible to form alloys capable of study over an extensive range of compositions. Mills has made such a study using single crystals oriented primarily for single prismatic slip4 and has found an effect of oxygen concentration on the flow stress temperature dependence analogous to that observed in iron due to carbon by Stein, Low, and Seybolt. The present paper is specifically concerned with the effect of oxygen on deformation in polycrystalline zirconium. Although plastic flow in this type of specimen is much more complex than that reported for the single-crystal work, and involves both slip (on several different types of planes) and mechanical twinning, the results of this investigation are in general agreement with the single-crystal observations concerning the effect of oxygen on the temperature dependence of the flow stress. In addition, they also demonstrate that oxygen affects the acting deformation systems. This is in contrast to single-crystal results4 that showed only single slip on a prism plane. EXPERIMENTAL PROCEDURE Material. High-purity hot-rolled zirconium strip, 0.2 in. thick by 4 in. wide, of 0.10-mm average grain diameter, was used for forming alloys. It was obtained from the Carborundum Metals Co., Akron, N.Y., whose analysis indicated the major impurities were, in wt ppm: Hf, 540, C, 145; Fe, 100; and 0, <80. The plate texture was similar to a wire texture, with basal planes generally parallel to the rolling direction and basal poles randomly distributed about the rolling direction. The heat treatments described below did not appreciably alter the basic texture. specimen Preparation. Small threaded-end tensile specimens were machined from the plate with axes perpendicular to the rolling direction. These transverse specimens had gage sections 1 in. long by 0.060 in. in diam. The small gage section diameter was dictated by the fact that the alloys were formed by dif-

Jan 1, 1969

By C. H. Li, R. D. Carnahan, R. J. Stokes, T. L. Johnston

When silver chloride deforms by pencil glide at temperatures of 26ºand 72°C, grain size has no effect upon the proportional limit and the material necks down to a knife edge under tension. At -196ºC, deformation takes place on fewer slip systems to produce straight slip traces, the flow stress becomes sensitive to grain size and fracture occurs by cleavage from an intergranular source without any reduction in area. THERE are significant differences between the appearance of the slip bands formed in silver chloride and in the alkali halides at room temperature. The bands in sodium chloride, e.g., are fine and geometrically straight, whereas in silver chloride they are coarse and wavy.&apos; Such differences in the slip behavior prompted us to inquire what the effects of grain boundaries might be on the mechanical properties of these solids. As an introduction to a general study of ionic poly-crystal behavior, we have investigated the effect of grain size on the stress-strain relationships in silver chloride at different temperatures. We have chosen silver chloride chiefly because polycrystals can be easily prepared free from cracks and macroscopic voids by conventional techniques. Moreover, as we shall see, the slip behavior can be readily modified by changing the temperature. It will be shown that the effect of grain size on the yield stress of silver chloride is strikingly dependent upon the temperature of deformation and that this temperature effect comes about through a change in the number of slip systems which operate at the onset of plastic flow. EXPERIMENTAL PROCEDURES Polycrystalline tensile specimens were made by recrystallizing cold-rolled AgCl sheet. Thirty-gram quantities of AR grade silver chloride powder were melted in a low heat capacity furnace, cast into cylindrical forms 3/4 in. in dim and approximately 1 in. in length and then extruded with a 16:l reduction ratio into rods 3/16 in. in dim. Extrusion temperatures were varied from room temperature to 350°C. In order to impart various degrees of cold&apos;work to the extruded rod. All extrusions were then cross rolled to sheet 0.040 in. in thickness at room temperature and machined to form tensile specimens having a gage length of 0.750 in. with a width of either 0.250 or 0.145 in.* Annealing was carried out in an air oven at 200°C for periods up to 20 hr. specimens having average grain diameters ranging from 0.024 to 0.40 mm were prepared by varying the extrusion temperature and annealing time in the conventional manner. To obtain specimens with grain sizes larger than 0.40mm, lightly deformed thin prisims of silver chloride single crystals (supplied by Harshaw Chemical Co.) were recrystallized. Grain size determinations were made by an intercept method and revealed that the grains were equi-axed. Laue back-reflection X-ray patterns showed little tendency to form a preferred orientation texture. Specimens which were to be used for the slip band studies were polished by immersion in fresh boiling concentrated NH,OH for 60 sec. They were then etch polished for 10 sec on each side by hand lapping on a stationary velveteen lap wetted with a dilute Hypo solution (5 g of Kodak Acid Fixer in 100 cc H20). Finally the specimens were rinsed in warm water and alcohol, blown dry and carefully mounted in the tensile machine for testing. Tensile tests were performed at three temperatures, namely, 26º, -72º, and -196°C. A screw-driven hard tensile machine was used at a constant strain rate of 0.006 in. per in. per min. Loads were determined with a light- proof ring fitted with A-18 strain gages and extensions were measured with a 0.0001 in. dial gage. Constant level baths of alcohol with dry ice and liquid nitrogen were used to maintain the two lower test temperatures. EXPERIMENTAL RESULTS Reproducibility—In view of the light sensitivity and reactive nature of silver chloride, it was necessary to determine whether reproducibility depended upon either exposure to light or to the condition of the surface. However, during the course of the work it became clear that variation of laboratory lighting

Jan 1, 1962

By J. A. Coll, R. W. Cahn, A. Lawley

WHILE the creep properties of pure face-centered-cubic and close-packed-hexagonal metals have been thoroughly investigated and are well established, body-centered-cubic metals have been studied less extensively. Moreover, very few fundamental studies on the creep of solid solutions, irrespective of crystal structure, have been reported. The present study is concerned with the creep of a series of body-centered-cubic solid solutions. The present position concerning creep of pure metals is, briefly, as follows.1"3 Creep at first takes place at a steadily decreasing rate; this is the stage termed primary or transient creep. Except at the lowest temperatures this is succeeded by a stage of secondary or steady-state creep. At high temperatures and stresses, this may be succeeded by an accelerating stage, termed tertiary creep, with which we shall not here be concerned. There is no well-defined physical model at present for the transient stage; in general terms, transient creep is best regarded simply as a manifestation of work-harden ing. Steady-stage creep can certainly take place by several different mechanisms: the choice of dominant mechanism depends primarily on temperature. We shall here be concerned only with high-temperature steady-state creep, a term usually reserved for creep at absolute temperatures higher than 0.5 Tm, where T, is the melting point. In this range, the activation energy for creep is, for many metals, equal to the activation energy for self-diffusion, and this is generally interpreted in terms of a "climb mechanism.1-4 The creep rate is determined by the speed at which dislocations, impeded by obstacles the nature of which is disputed but which are probably established during transient creep, can climb by means of a diffusion process, until they are able to by-pass the obstacle. In solid solutions, the intrinsic resistance to the slip motion of dislocations may be much larger than in the solvent, to the extent that the motion of dislocations in the glide plane, rather than their escape by climb out of this plane, may become the rate-controlling factor. weertman5 has considered this possibility from a theoretical point of view, and concluded that some form of "viscous slip" is likely to be rate-controlling at comparatively low stresses. The resistance to slip may arise from "atmospheres" of impurities forming around dislocations; a high Peierls force in materials of high cohesion; or some structural peculiarity such as clustering or ordering of solute atoms.= We shall be concerned here with the case of ordering. The only published investigations concerned explicitly with the effect of order on creep refer to creep in ß-brass by Herman and Brown,7 and in Ni-Fe alloys, by Kornilov and panasyuk8 and by Suzuki and Yamamoto.9 Recently, Herman and Brown&apos;s paper has been supplemented by a determination of the tensile yield point of ß-brass as a function of temperature.10 Both studies showed a sharp drop in resistance to deformation of ß-brass over a range of a few degrees just above the critical temperature Tc at which order finally disappears. These observations are especially noteworthy, because in ß brass the degree of order diminishes steadzly to zero as the temperature approaches Tc. It is, therefore, the disappearance of the last traces of long-range order which has the largest effect on the resistance of the alloy to plastic deformation. In the Ni/Fe alloys of various compositions, resistance to creep at a given temperature and stress is maximum at the stoichiometric composition, both below Tc, (long-range order), and above T,. (short-range order).&apos; Near Tc, the creep resistance of an ordered alloy is much higher than that of the same alloy in the disordered condition.9 The aim of the present investigation was to study the creep behavior in the neighborhood of Tc, of another system of ordering alloys. The iron-aluminum alloys were considered the most suitable. because: i) The order again diminishes steadily to zero as the temperature approaches Tc; there is no sudden drop in order at Tc, and it therefore is

Jan 1, 1961

By F. H. Callaway, W. O. Keller

The various theories as to the well spacing-recovery relationship are reviewed in considerable detail and these theories analyzed in terms of their consistency with modern reservoir engineering concepts. It is concluded that the well spacing problem must be analyzed in terms of recovery efficiency and that a positive answer to the relation between well density and recovery efficiency is not available from direct comparisons of the production histories of wells and fields. The results of an engineering analysis designed to permit approximate calculation of recovery efficiencies as a function of well spacing in a depletion type reservoir from basic reservoir data is presented. Results of this type analysis indicate that the effect of well spacing on recovery efficiency in depletion type reservoirs can be expected to be very small. Limitations of this approach are pointed out, particularly with respect to its application in lenticular reservoirs. Testing techniques are outlined which should indicate whether or not a reservoir is continuous between wells and whether or not satisfactory drainage is being obtained with present spacings. A mass of data of this type indicates continuity to exist in most fields. INTRODUCTION The purpose of this paper is to review critically the engineering aspects of the well spacing problem, both from the standpoint of certain concepts and from the standpoint of reservoir mechanics. The well spacing problem is primarily an economic problem in which the optimum well density for a particular field is that density which will yield the greatest oil recovery consistent with justifiable development costs. The well spacing answer in terms of economic conditions, however, is extremely sensitive to the variation in recovery efficiency with well density. The variation in recovery efficiency with &apos;References given at end of paper. Manuscript received at the office of the Petroleum Branch October 2, 1949. Paper presented at the Petroleum Branch Meeting in San Antonio. Texas, October 5-7. 1949. well density is properly an engineering problem. Different opinions as to the correct answer to this engineering problem is the basis for most of the wide difference in opinion among various members of the industry as to optimum well spacing. This paper will be confined to the engineering problem of the relation between well density and ultimate oil recovery; economic considerations necessary for the evaluation of optimum well density for any particular field will not be discussed. The paper can be logically divided into two parts. The first part deals with a critical examination of the background and logic of the Cutler Rule and of similar studies by other authors and of related well spacing concepts. It is indicated that the variations in recoveries with well density* observed by Cutler and. others can be logically attributed to regional migration. Theoretical justification of the Cutler type relation wherein observed variations in recovery with well density in the same field is attributed to variations in recovery effiiency, in terms of energy relations, is refuted. The second part consists of a review of concepts of reservoir mechanics with regard to the well density-recovery relation. It is indicated that little variation of recovery efficiency with well density can be expected in a depletion type reservoir, unless lenticular conditions prevent communication between wells. The significance of field test data with regard to the existence or non-existence of lenticular conditions is pointed out. THE CUTLER RULE The first published article concerning the engineering aspects of the well spacing problem to receive wide attention was the work of W. W. Cutler&apos; of the U. S. Bureau of Mines, published in 1924. In a study of decline curves from a large *The expression "well density" as utilized herein refers to the number of acres attributed to each well in a uniform well pattern, and is expressed in acres per well. The term "well spacing" Is utilized to denote the average distance between adjacent wells in a uniform well pattern. †Although the Cutler rule is treated critically in this discussion the authors intend no personal criticism of W. W. Cutler or of his hark The currently accepted concepts of reservoir mechanics were no": existent at the time of Cutler&apos;s work, as were even the moat basic tools (such as the bottom hole pressure bomb) for observing reservoir behavior.

Jan 1, 1950

By C. G. Dunn, F. Lionetti

The energy associated with grain boundaries in polycrystalline aggregates is believed to play a major role in grain growth processes and, when growth ceases, to determine the final equilibrium grain boundary angles. Further, the energy of grain boundaries of recrystallization nuclei is a factor in nucleation processes. It is important to know, therefore, how the energy per unit area of a grain boundary, that is, the grain boundary surface tension y, depends on the difference in orientation of the two lattices of the grains producing the boundary. Although the problem is important, surprisingly little has been done toward a quantitative evaluation of the effect of orientation difference on grain boundary energies. C. S. Smith1 recently has discussed this problem and in addition to showing effects of orientation difference on equilibrium angles has shown a variety of interesting effects of surface tension on the appearance of microstructures. Fig 1 and the following relations expressed in Eq 1, which connect equilibrium grain boundary angles and surface tensions, illustrate equilibrium conditions which are believed to hold true in metals. ?l2 _ ?23 _ ?l3 [1] sin ?3 sin ?1 sin ?2 Clearly any two of these surface tensions can be expressed in terms of the third when the equilibrium angles ?1, ?2, and ?3 are known. Applied to the present problem for solid state equilibrium of three grains, the angles ?1,?2 and ?3 must be measured in a plane perpendicular to the line of junction of the three grains. Normally a direct determination of these angles from random microsections is impossible. Consequently Harker and Parker2 and Smith1 (except for some measurements on flat specimens) resorted to a statistical method to determine equilibrium grain boundary angles. Smith reported that grain boundaries meet the surface of a piece of metal nearly perpendicularly. He reported also, in connection with direct angle measurements on flat specimens with grains extending through the thickness, that angles varied appreciably from 120" and concluded that there was a measurable effect of orientation difference on surface tension. Another direct way of determining equilibrium angles and a method adaptable to studying particular configurations, recently suggested by Dunn,³ is to use a three-grain flat specimen with orientations of grains so chosen that the junction line of the three grains will be straight throughout the thickness and perpendicular to the surface of the specimen. Choice of orientations is possible when individual grains of each group can be grown to predetermined orientations through the reorienting and growth of " seed crystals " as described.³ Not only is it possible, for example, to have grains with the same crystallographic plane in the plane of the specimen, but a given orientation difference between two grains can be made a common factor to an unlimited number of three-grain groups while a series of orientation differences is investigated. Any effect of anisotropy of gas-solid surface tension due to grain orientation should be minimized by having all gains oriented the same with regard to crystallographic plane in the plane of the specimen. Another feature of the three-grain group is the notched grain boundaries as shown in Fig 2 for one specimen (S4). The notches serve to anchor the end positions of the grain boundaries (especially at high temperatures) while the central and junction point of the grains moves toward an equilibrium position. Final equilibrium should produce straight grain boundaries if the notches are very narrow and if changes in orientation* of the grain boundary do not alter the surface tension.† If one assumes the straight line condition and no change of surface tension with small changes in grain boundary orientation and finds the equilibrium configuration by a minimization of the grain boundary energy, one obtains the relations given in Eq 1. The approach to straight line boundaries or to minimum energy configurations in specimens containing large grains, such as those used in the present investigation, may be very slow compared with the approach to equilibrium conditions for the grain boundary angles. It may be desirable, as proved to be the case in the present investiga-

Jan 1, 1950

By W. F. Hosford, E. W. Kelley

Deformation studies have been conducted at room temperature on single crystals of magnesium and magnesium alloys with thorium and with lithium. Single crystals oriented to suppress shear on the easily activated basal slip systems were deformed by plane-strain compression. Compression along the C axis was accommodated by {1011} banding. Compression perpendicular to the unconstrained c axis activated {1012} twinning, and, after virtually complete twinning, deformation continued by {1011) banding in the twinned material. Compression perpendicular to the constrained c axis was accommodated by the simultaneous operation of (1012) twinning against the constraint and (1011 ) banding. Although this orientation was favorable for {1010)(1210) prism and {1011}(1~10) pyramidal slip, these modes were not observed in pure magnesium or in Mg-0.5 pct Th. However, {10i0)(1~10) prism slip was observed in crystals of Mg-4 pct Li during compression perpendicular to the constrained c axis. Fracture in all materials occurred parallel to (1124) or {l~il) depending on the orientation and composition of the specimen. THE mechanical behavior of the hcp metals is strongly anisotropic. Although several slip systems have been reported the slip is cpmmonly in the directions of closest packing, the (1210),&apos; and this does not produce strains parallel to the c axis. Hence the inherent anisotropy. The deformation mode most easily activated in magnesium at room temperature is (0001)(1210)- basal slip. Also {1010}(1~10) prism slip and {1011)(1210) pyramidal slip have been reported, primarily at elevated temperatures.2"4 However, at room temperature the shear stresses to activate the prism and pyramidal modes are roughly a hundredfold greater than that required for basal slip.&apos;j4 Thus prism and pyramidal slip may be expected only under special conditions of loading. Strains normal to the basal plane can be produced by twinning, however. Many twinning modes have been reported for magnesium,&apos; with (1012) twinning the most common and relatively easy to activate. Magnesium can deform by (1012) twinning when stressed along the c axis jn tension, but not in compression. In contrast, (1011) twinning is activated by compression along the c axis and not by tension. In addition to primary twinning, secondary twinning or slip can occur within the reoriented material of primary twins.&apos; In general at least five independent shear systems must be active to bring about an arbitrary shape change such as that in the individual grains of a deforming polycrystalline material.&apos; Because basal slip can_ provide only two independent shear systems and (1012) twinning can only accommodate an extension of the c axis, other deformation modes must be active in magnesium for an arbitrary shape change to occur. The purpose of this investigation has therefore been to study the various deformation modes in magnesium at room temperature, with special emphasis on those modes that are less easily activated. The effect of the alloying elements, thorium and lithium, has also been investigated. In polycrystalline aggregates, unambiguous identification of deformation modes is extremely difficult and the direct evaluation of the resolved shear stresses to activate them is not feasible. On the other hand, uni-axial tension and compression experiments on single crystals may not activate some of the- deformation modes because basal slip and/or {1012) twinning cannot be suppressed in most orientations. However, it should be possible to activate all possible deformation modes using oriented single crystals and plane-strain compression. Identification of active deformation systems and evaluation of the resolved shear stresses required to activate them should be facilitated. Wonsiewicz and Backofen have recently completed an investigation of the plasticity of pure magnesium crystals at various temperatures utilizing plane-strain compression and selected crystal orientations. This technique has also been used in the present work. The seven orientations selected for study are indicated in Table I. Plane-strain compression along the c axis (orientations A and B) should activate some deformation mode _other than basal, prism, or pyramidal slip, or (1012) twinning. In orientations C and D, prism or pyramidal slip would be expected to take place. When the compressive load is applied perpendicular to an unconstrained c axis (orientations E and F) the three slip modes should be suppressed but not (10i2) twinning. In orientation G, basal slip should occur.

Jan 1, 1969

By G. R. Speich

The age-hardening of Fe-18 to 21 pct Ni marten-sites containing small amounts of titanium, aluminum, copper, or molybdenum has been studied by hardness measurements, transmission electron microscopy, extraction replicas, and X-ray and electron diffraction. Electyon-probe microanaly-sis of the extracted precipitates was also performed. The effects of temperature and composition on the aging kinetics have been studied in detail for Fe-20 pctNi-Ti martensites. All the martensites hardened on aging at 400" to 500 "C with a single aging peak. In the Fe-20 pct Ni-Ti martensites hardening was associated with the formation of a fine dispersion of NisTi. No precipitation was observed in an Fe-21 pct Ni-2.6 pct A1 alloy, although the hardness increased from 327 to 545 Dph during aging at 500°C. Copper was precgitated from an Fe-20 pct Ni-10.7pct Cu alloy, at least during the later stages of age-hardening. Hardening in an Fe-18 pctNi-5pct Mo alloy was associated with the precipitation of an intemzetallic compound tentatively identified as NisMo. The formation of austenite and the recovery of the defect structure of the martensite occur simultaneously with the normal precipitation processes &ring aging of these alloys. THE age-hardening of substitutional iron-base martensites is an important subject for study since age-hardening is one of the principal means of strengthening the substitutional iron-base martensites in precipitation-hardening stainless steels1 and maraging steels.a~4 In contrast to Fe-C martensites, these martensites are relatively soft and ductile in the as-quenched condition, due to the low solid-solution hardening effect of the substitutional elements as compared to carbon. Also, these martensites are hardened by aging at low temperatures in contrast to Fe-C martensites which generally soften on tempering. Titanium and aluminum, singly or in combination, as well as copper and molybdenum, have been the principal alloying additions to stainless steels to obtain an age-hardening reaction.&apos; Ti-A1 or Co-Mo-Ti combinations have been used in the case of maraging steels.3"4 The present work has been confined to a study of the age-hardening characteristics of an Fe-18 to 21 pct Ni martensite to which small amounts of titanium, aluminum, copper, and molybdenum were added in order to study the effects of each alloying element separately. The age-hardening characteristics of these alloys were studied by hardness measurements, transmission electron microscopy, extraction replicas, and X-ray and electron diffraction. Electron-probe micro-analysis of the extracted precipitates was also performed. The types and dispersion of precipitates, the formation of austenite, and the recovery of the defect structure of the martensite all were studied. EXPERIMENTAL PROCEDURE Alloys. The compositions of the alloys studied are listed in Table I. The level of 18 to 21 pct Ni was chosen to assure complete transformation to martensite on quenching and is the same nickel level used in maraging steels. The concentrations of titanium, aluminum, copper, and molybdenum were chosen after a study of the and Fe-Ni-MO&apos; ternary diagrams indicated how much of each alloying element could be dissolved in austenite. Alloys with 2 and 4 pct Cu were also studied, but these did not show precipitation hardening at the nickel levels studied and will not be discussed further. The alloys were prepared from electrolytic iron and high-purity* nickel, titanium, aluminum, copper, and molybdenum by vacuum melting of 20-lb heats. These were vacuum-cast into two 8-lb ingots. The ingots were hot-rolled at 1100°C to 1/2-in. plate and subsequently cut into 3/8-in. cubes. The cubes were sealed in evacuated quartz capsules and solution-treated for 16 hr at 1100°C, except for the Fe-20 pct Ni-10.7 pct Cu alloy and Fe-21 pct Ni-2.6 pct A1 alloys which were solution-treated for 16 hr at 1300" and at 1250"C, respectively. Metallographic examina-

Jan 1, 1963

By C. Zener

HE present paper has its origin in an attempt A by the author, extending over the last several years, to understand the influence of the magnetic properties of the constituent atoms upon the various properties of metals and alloys. During this study the author has been impressed by the important role which magnetism plays in the many facets of metallurgy. In writing this paper he has attempted to convey to his colleagues some concept as to the role magnetism will play in the future development of metallurgy. In some of the subjects herein discussed, such as the influence of magnetism upon phase boundaries and upon mechanical properties, only general thermodynamical properties associated with ferromagnetism are introduced. For these subjects, it is not anticipated that any serious differences of opinion will be encountered. A discussion of the other subjects requires the adoption of a quite specific model of the magnetic structure of the metal. This model is discussed under "Magnetic Shells and Their Interactions." The simple model adopted in this paper has been criticized&apos; as being mathematically inconsistent. This criticism has been ably silenced by Dr. W. J. Carr&apos; of this laboratory. The simple model adopted in this paper has been criticized as being inconsistent with observations on magnetic structure using neutron diffraction. This apparent discrepancy has been resolved by Bader3 who has shown that the finite velocity of neutrons prevents neutron beams from detecting the anti-ferromagnetic structure of the type predicted by the simple model adopted in this paper. Magnetic Shells and Their Interactions An electronic shell of an atom is specified by two symbols.&apos; The first symbol is a number and denotes the total quantum number of the shell. The second symbol is a letter and denotes the orbital angular momentum of each electron within the shell. The letters s, p, d, f are used to denote an orbital angular momentum of 0, 1, 2, 3, respectively, in units of h/2a, where h is Planck&apos;s constant. As we pass from scandium to nickel in the first transition period, we eraduallv fill the 3d shell. This shell is responsible for ferromagnetism and hence may be called the magnetic shell. The component of the orbital angular momentum along some specified direction must be an integral multiple of h/2~. Thus, for a d electron this component can have any one of the values —2, —1, 0, 1, 2 times h/2a. In addition to its orbital angular momentum, each electron has an intrinsic angular momentum, hereafter called spin, due to a rotation about its own axis. This spin can have either of two components + Yz (h/2a) or — Yz (h/2~) along the specified direction. A fundamental principle of atomic structure, known as Pauli&apos;s exclusion principle, is that no two electrons in a given shell may have identical components of orbital angular momentum simultaneous with identical components of spin. The 3d shell thus may have at most ten electrons. Since an intrinsic angular momentum of a charged particle is necessarily associated with a magnetic moment, the spin of an electron may be thought of as referring to either this angular momentum or to the associated magnetic moment. The electron configuration of the ground state of the isolated atoms in the first transition row is reproduced in Table I. The superscript represents the number of electrons in each shell. For the purpose of this paper, the most important principle of atomic structure relates to the manner in which electrons are added to a shell as the atomic number is increased. This principle, commonly known as the principle of highest multiplicity or more simply as Hund&apos;s rule, states that within a given shell the maximum number of electrons have spins pointing in the same direction as is consistent with Pauli&apos;s exclusion principle. An application of this principle to the d shell is illustrated in Fig. 1, where the spin structure is given for shells containing from 1 to 10 electrons. The physical basis of Hund&apos;s rule is the exchange energy discussed first by Heisenberg in 1928. This is a coupling between electrons with parallel spins (spins pointing in the same direction), the coupling

Jan 1, 1956

By Nicholas J. Grant, A. W. Mullendore

Measurements of grain boundary sliding were made on polycrystal and bicrystal tensile creep specimens of Al-2 pct Mg at 500oand 700oF. Grain and pain boundary orientation factors were studied with respect to their effect on the magnitude and direction of grain boundary sliding. It was concluded that a large part of the observed sliding may be caused by the operation of slip crossing the grain boundaries. Supporting evidence for this model from other investigations is also given. GRAIN boundary sliding in metals during elevated temperature deformation has frequently been thought of as an independent mechanism with its own characteristic stress, temperature, and structure dependence. Further, it is common to regard the grain boundary as the weak link during creep deformation since: 1) the strength of apolycrystallinemetal, as meas-sured by creep rate or rupture life, decreases at\a more rapid rate when sliding comes into action, and 2) grain boundary sliding, as revealed by "boundary darkening" and fold formation is often the first visible deformation. On the other hand, more quantitative observations, in both polycrystals and bicrystals, have shown boundary deformation to be closely related to the over-all deformation of the specimen. The curve of grain boundary contribution to elongation vs time takes a shape similar to that of the total creep curve,&apos;,&apos; and the apparent activation energy for sliding appears in most cases to have the same value as that for total creep.3 In order to reconcile these observations, one is left with these possibilities: 1) The grain boundary and grain deformation rates are both controlled by the same rate limiting processes. 2) The rate of sliding is limited by accommodation deformation in the grains. 3) Sliding is the consequence of grain deformation. 4) Grain deformation is dependent on prior grain boundary deformation. Alternatives 2) and 3) would view grain boundary sliding as occurring in series with another deformation process which could be rate controlling. McLean prefers item 3) as the sliding basis,4 where subgrain rotation results from dislocation accumulation in the substructure at the grain boundary. Crussard and Friedel&apos;s5 treatment of grain boundary migration considers that dislocations are forced into the grain boundary and are dissociated into dislocations with Burgers&apos; vectors nearly parallel to the grain boundary. The movement of these partial grain boundary dislocations then produces the sliding. The results of this investigation have indicated alternative 3) to be the most appropriate and it is this aspect of grain boundary sliding which will be analyzed. EXPERIMENTAL PROCEDURE Three types of tensile creep tests were employed in this study: (I) A constant load test of one very coarsegrained polycrystalline specimen at 500° F, 3600 psi, 1 pct per/hr strain rate to examine the grain and grain boundary orientation factors in grain boundary sliding. (II) Constant strain rate tests of polycrystalline specimens at 510o and 715o F, 2 pct per/hr strain rate to determine the grain boundary contribution to elongation at very low total strains. (m) Constant strain rate tests of bicrystals of various grain and grain boundary orientations at 500°F, 2 pct per/hr strain rate to obtain further information on the orientation effects in grain boundary sliding. The material used in the tests was a high-purity Al-1&apos;.92 mg alloy, kindly furnished by Alcoa. Its composition is given in Table I. The alloy is a solid solution at the test temperatures. The coarse grained polycrystalline specimen for test (I) was prepared by recrystallizingthe machined specimen, straining it about 1pct intension at room temperature and annealing at 900°F for 8hr. The constant strain rate specimens (11), with an 178 in. sq. by 1/2 in. long gage section, were cut from 1/8 in. thick sheet of cold rolled and annealed (8 hr at 1000oF) material. The latter specimens were supported in a special jig during the milling operations to avoid any bending, and the gage section was subsequently heavily electropolished to remove the cold-worked surface layer. The bicrystals (ID) were machined in the same

Jan 1, 1963

By F. D. Rosi

The plastic properties of extended silver and copper crystals of varying purity were studied as a function of crystal orientation in the early stages of flow. Variations in the gross shape of the shear stress-shear diagram and in the properties of critical Variationsshear stress and shear-hardening coefficient were correlated with changes in slip-band developments. The phenomenon of work hardening is discussed in terms of the existing dislocation theory. IT appears certain from the early studies on the deformation characteristics in metal crystals1-3 that plastic flow takes place in a preferred crystallo-graphic slip system which is determined by the geometry of the crystal (law of maximum shear stress), and that the value of shear stress for this system is independent of crystal orientation (law of critical shear stress). Experimentally, it has been demonstrated further that the law of critical shear stress can be extended to include extensive plastic flow.&apos; Thus, the shear-hardening coefficient, which is defined as the slope of the shear stress-shear curve, also is considered to be independent of orientation. It is noteworthy that deviations from this empirical shear-hardening law have been reported in cubic crystals whose initial orientation favors slip on more than two systems.&apos; Moreover, this law appears to have been derived from stress-strain data relating to relatively high values of shear strain (0.5 to 4), where widespread slip and complex distortions can be expected, regardless of crystal orientation. Since existing data indicate that the strain inhomogeneity in a crystal is manifested particularly in the early stages of flow, it would appear that a more exacting test as to the fundamental nature of the shear-hardening law would be to investigate systematically the shape of the stress-strain curve as a function of crystal orientation in the earlier stages of deformation. With regard to the general form of the shear stress-shear curve for cubic crystals, early studies show a parabolic hardening law, where the shear 1 stress is proportional to the square root of the shear-strain. Since this law was predicted theoretically by Taylor" in his original dislocation model for hard- ening, it has been accepted widely as a fundamental flow characteristic of cubic metals. However, it was recently pointed out by Masing6 hat the parabolic law is not the elementary form of hardening in cubic crystals, but instead is a consequence of complexities in the flow process (e. g., deformation bands and unpredicted secondary slip). Thus, in the very early stages of deformation (< 2 pct extension) where the occurrence of such complexities is unlikely, a different strain-hardening behavior might be anticipated. This view is supported by the recent work of Rosi and Mathewson7 on high purity aluminum where a linear law was obtained for extensions up to 2 pct. A linear hardening over a wider range of deformation also was reported by Rohm and Kochendorfer8 ho deformed aluminum crystals under conditions approximating pure shear. Even more pertinent is the recent evidence of Masing and Raffelsieper9 on high purity aluminum crystals. It was found that for crystals having initial orientations near a <l00> or <1ll> axis, a high hardening was obtained, whereas crystals with a <110> orientation exhibited a low and linear hardening curve followed by a region of more rapid hardening. Since much still remains obscure concerning the details of strain hardening as well as slip-band formation in face-centered-cubic crystals in the early stages of deformation, the present study was undertaken to evaluate the effect of crystal orientation on these two important manifestations of glide. It is important to note here that at the time of this study, Lucke and Lange11 presented information on the orientation-dependence of the shape of the strain-hardening curve in aluminum of various purities. Their work, which essentially represents an extension of that of Masing and Raffelsieper, in many respects is parallel to that of the present study. Experimental Procedure Production of Single Crystals: Single crystals of silver and copper of varying purity were used in

Jan 1, 1955

By R. E. Barnes

An overall view of the perlite industry is concisely presented. The geology, mining, milling, processing, and applications of perlite, as well as the present status of the perlite industry are treated. Perlite, in strict petrological usage, describes a specific variety of volcanic glass in which strain, incident to cooling, yielded a concentric structure of fracturing which may be visible either to the naked eye or under a microscope. In commercial usage, the term perlite includes any naturally occurring acidic glass of volcanic origin that will expand when heated to a suitable temperature. The name perlite is a derivation of perlstein which originally defined "certain glassy rocks (hyaloliparites, hyalo-rhyolites) with numerous concentric cracks, from the fancied resemblance of broken out fragments to pearls."1 While perlite has been known to geologists for many years, it was not until 1941, while investigating perlite for use in enamel, that an assayer in Superior, Ariz., noted the unusual expansion characteristics of the ore. Further investigations were delayed until following World War II when many small plants were built and experimentation in the treatment and uses of perlite began. The Perlite Inst. was organized in 1949 to promote the development of the new industry, establish commercial standards through research, and to explore new uses and markets. The Institute, located in New York, represents some 50 producers in the U.S., Canada, Australia, England, France, Germany, Greece, Japan, Mexico, and New Zealand. In 1949, 71,l002 short tons of crude perlite were produced, sold or used by U. S. producers, and this figure increased to 325,0003 short tons by 1959. Such a rate of increase indicates the rapid and continuing growth of the perlite industry. GEOLOGY Perlite ore in its crude form has been found in seven of the mountainous western states, since un-devitrified siliceous volcanic rocks are limited to this section of the U. S. Commercially operated perlite deposits are normally of Eocene and Oli-gocene age.4 These deposits are often several hundred feet thick and may extend over hundreds of acres. In 1959, 13 companies in six states produced crude perlite, although the output in New Mexico comprised 79 pct of the total domestic crude output. Other states in order of their production were: Nevada, Arizona, California, Colorado, and Utah.5 Foreign deposits of perlite which are either producing or under exploration are Australia, Canada, Greece, Hungary,6 Iceland, Ireland, Japan, Mexico, New Zealand, and Sardinia. The ore may exhibit a variety of characteristics depending partially on its water content and eruption history and may range through many shades from black to white. While these characteristics may vary slightly among deposits, perlite ore from a particular source is normally quite uniform. Available chemical analyses of perlites from a large sampling of domestic deposits were recently assembled by the Technical Committee of Perlite Institute and are presented in Table I. While the ranges given do not apply to a particular perlite, they are an indication of the chemical analysis which may be expected from any presently commercially operated deposit. The specific gravity of the perlite ore ranges between 2.2 and 2.4, and its bulk density when crushed and sized is 75 to 90 Ib per cu ft. MINING AND MILLING Perlite ore is quarried from open pits by conventional power equipment, although blasting has been occasionally employed. The rock is then stock-piled until needed. While the milling of perlite may seem a simple process compared to that required for basic metals, or even other nonmetals, the need for accurate control of particle size becomes extremely important in further processing. The first step in this operation is the primary crusher, which is normally a jaw crusher. Following crushing, the material is dried, if necessary, in a rotary dryer and conveyed to a secondary grinder which may be a rod mill, hammer-mill, or cone crusher. However, the crushing characteristics of the perlite, caused by incipient cooling fractures, requires it be removed from the grinding operation once it is reduced to the required size so as to prevent overgrinding. Following the grinding operations, various size screens are used to separate the ore according to particle sizes required for particular uses. Most plants use two or more stages of crushing with perhaps four stages of screening.

Jan 1, 1961

By K. R. Janowski, H. Conrad

As part of a program to establish the effect of crystal imperfections on laser output, a detailed study was made of the dislocation structure of ruby crystals obtained from varioius sources. Using KHSO4 as an etchant, a detailed mapping of the dislocation structure on the (0001) and the (1150) planes was carried out. A less extensive study was made of the rhombohedral planes. The average dislocation density on the basal plane was 1.5 to 3 x 106 cm&apos;2 and on the (1120) planes -5 x 10&apos; cm-2. Howe7!er, considerable variation existed between areas on a given plane. The subboundaries in the basal plane tended to lie along [1100] type directions while those on the (1120) plane tended to lie: a) parallel to the basal plane, b) along truces of the (1101) plane, and c) along normals to the traces of the (0001) planes. The orientations suggest that mang of the dislocations lie on the (0001), (1701), and (1150) planes A Laue back-rellection nnalysis Of c-axis wander in one crystal revealed a gradual increase in misorientation from me end of the crystal to the other, with a maximum variation of 1°35&apos;. Slight etching of a mechanically polished crystal revealed mumerous polishing scratches, suggesting the existence of a plastic flow layer. It is recognized that chromium concentration, lineage, and other crystalline imperfections play a role in the efficiency of ruby lasers.&apos; Consequently, it is desirable to establish in detail the imperfection structure of ruby crystals to be used as lasers. Some exploratory work along this line had already been done by Barnes&apos; and Dils and Martin.&apos;" How- referred to as the morphological system, as described by Kronberg.4 The Miller indices given in the present paper will be based on this morphological system. In this system, the three common growth planes are the (0001), the {1120}, and the {1101}.5 Since these planes are of high stability, it is expected that they are most suitable for study by the etch-pit technique. In the present investigation, a detailed mapping of the dislocation structure was carried out for the (0001) and the (1130) planes. A less extensive study was made of the etch-pit structure on rhombohedra1 planes. An analysis of dislocations in sapphire (the ruby host) was first made by kronberg,4 who postulated that slip on the (0001) plane occurred by motion of dislocations with Burgers vector 1/3 <1150> and that these dislocations might dissociate into quarter partials. An etch-pit technique using boiling phosphoric acid was developed by Scheuplein and Gibbs6, 7 for identifying dislocations intersecting the (0001) planes and the planes near (2021) in sapphire. Al-ford and Stephens8 were able to reveal dislocations on the (0001) and {1120} planes in sapphire and ruby by etching in fused potassium bisulfate (KHS04) at 675°C. The termini of basal dislocations [(000l), <1120>] were revealed by Palmour and Kriegel9 on {1120} and {1010} by thermally etching sapphire. Bond and Harvey10 were able to decorate dislocations in sapphire by adding 1 pet by weight of ZrO2 to the Al2O3 powder used in the growth of the crystals by the Verneuil technique and then heating the grown crystals for 4 hr at 1500°C. They found, using optical transmission microscopy, that many dislocations had straight segments which were parallel to one of the six [1120] directions in the basal plane. Single dislocation lines curved smoothly from one alignment to the other, turning through angles of 60 to 120 deg. Also observed were isolated hexagonal loops, approximately 10 µ in diameter, the sides of which lay along the same directions as did the longer dislocations. MATERIAL AND ETCHING PROCEDURE The ruby specimens used in this study (all containing approximately 0.04 pet Cr) had been obtained from four different sources: Linde Co., Meller Co., Valpey Crystal Corp., and those grown at Aerospace Corp.* For the initial phase of this study, several specimens were cut from the slab shown schematically in Fig. 1 which had previously been cut from a disk boule obtained from the Linde

Jan 1, 1964

By Peter Beardmore, Michael B. Bever

The effects of the temperature of deformation and the degvee of deformation on the annealing spectrum of a Au-Ag alloy have been determined by vesistance measurements. Specimens were deformed in torsion at 4°, 78K and room temperature up to strains nd/l of about 1.0 and were isochronally annealed. Discrete annealing stages similar to those found for pure metals were observed. Stage A occurred below room temperature; the decrease in reszstance associated with this stage increased as the temperature of deformation was lowered or the strain was increased. Stage B manifested itself as an increase in resistance; this is attributed to the restoration of short-range order promoted by vacancy or vacancy aggregate migration. At temperatures above 48S0K, recrystallization or Stage C occurred. Stages A, B, and C in the annealzng curves of this alloy may be considered to correspond to Stages II, Ill, and V, respectively, in the terminology used to describe the annealing spectrum of pure metals. ThE annealing behavior after deformation below room temperature has been thoroughly investigated on pure metals, in particular gold and copper. The occurrence of several discrete stages in the annealing spectrum of these metals has been established, but the interpretation of some of these stages in terms of specific mechanisms is still controversial.&apos; The annealing of alloys deformed below room temperature has been the subject of only a few investigations. In the investigation reported here, a Au-Ag alloy was annealed after deformation at and below room temperature. This continues a research program on the deformation and annealing behavior of Au-Ag alloys.2-8s EXPERIMENTAL PROCEDURE An alloy rod of composition 82.6 wt pct Au-17.4 pct Ag was reduced to wire, 0.0428 in. diam, by swaging and drawing. After a recrystallization treatment, the grain size was 0.031 mm, as obtained from the average linear intercept.7 The ends of wires about 6 in. long were flattened and sealed into short brass tubes with cold setting cement to form the grips of the torsion specimens. The equipment used for deformation has been described elsewhere.6 The specimens were deformed at room temperature, 78", and 4°K to various strains nd/l, where n is the number of turns, d the diameter of the specimen, and 1 its length between grips. The strain rate ?max was 0.1 min-&apos; at the sur- face of the specimen except where noted otherwise. The specimens were annealed isochronally for 30 min at intervals of approximately 30°K from the temperature of deformation to approximately 800°K, except that after deformation at 4°K the lowest annealing temperature was 78°K. A potentiometric method was used to measure the resistance: all measurements were made at 78°K with the exception of some measurements at 4°K mentioned below. Data obtained with a single specimen yielded a complete annealing curve: in several cases duplicate specimens were used to confirm the reproducibility of the curves. Since the surfaces of the specimens were rough after deformation, their diameters could not be measured accurately. The resistance increments after deformation and annealing are therefore reported as percentages of the resistance of the same specimen measured after completion of the annealing, that is, after full recrystallization. The corresponding resistivity values can be calculated by obtaining the effective diameter of a deformed specimen from the ratio of its resistance after recrystallization to the true resistivity, which was determined with a smooth specimen of known dimensions. This method of calculation was used to obtain data shown in several of the figures. RESULTS AND DISCUSSION The isochronal annealing curves after deformation to various strains at 4", 78K, and room temperature are shown in Figs. 1, 2, and 3, respectively. The resistance increment of the as-deformed specimens as a function of strain is shown in Fig. 4. For the specimens deformed at 4°K. values measured at 78°K are plotted with the exception of those for the as-deformed

Jan 1, 1970

By S. R. Titley

The recent emphasis placed upon the use of molybdenum as a geochemical indicator has stimulated considerable inquiry into the behavior of molybdenum in the zone of oxidation. This paper represents a summary of recent and continuing experimental work and calculations in an investigation of a portion of the system Mo-Fe-S-H20 and treats the stability of various iron and molybdenum compounds with respect to oxidation potential and pH. Using experimentally determined free energy values for ferrimolybdite, diagrams of the stability fields of this mineral have been calculated with respect to ilsemannite (?), molybdenite, pyrite and limonite. This theoretical approach is the one utilized by Garrels3&apos;4 in studies of the relationships of various minerals in the zone of oxidation. Use of this approach is particularly suited to the study of geochemistry in the zone of supergene processes because of the low temperatures, low pressures and other relatively easily determined and duplicated factors that exist in the near surface environment. Such a study of molybdenum, however, is complicated by several factors. One of these is the fact that the strong amphoteric behavior of molybdenum makes possible a wide variety of substances and complexes whose exact chemical natures are unknown. The second factor is the dearth of thermodynamic data for many of the simplest of the possible compounds and ions important to the study. For the purpose of this study, the problem of complexes has been approached through considering only the simpler possibilities realizing that the complexes and systems so treated may be gross oversimplifications. All the complexes considered, however, have been suggested in the chemical 2,7,9,12 or geologi-cal literature. EXPERIMENTAL WORK Studies of the behavior of molybdenum ions and ferrimolybdite have been carried out in aqueous sys- tems, and reactions have been followed by simultaneous measurement and recording of pH and oxidation potential. A major problem involved in this study was the long periods of time necessary for equilibrium to be established in some of the systems considered; in a few instances, these periods exceeded four weeks, that is, four weeks during which measured conditions changed continuously. Another problem, in some instances, was the indeterminate nature of the reactions that have taken place. Because of the tendency of molybdenum to complex, reactions which take place under some of the more extreme imposed conditions of oxidation and acidity or alkalinity are unknown. However, useful data for the present work were obtained from studies of the molybdate ion and ferrimolybdite between pH 2 and 8 and under only moderately oxidizing to nonoxidizing conditions. Instruments used in the experiments were a Hewlitt-Packard Model 412A VTVM, a modified Beckman Zeromatic pH Meter and two Varian model 11 recorders. pH was measured between glass and calomel electrodes and Eh was measured between calomel and platinum electrodes. Conditions of pH were varied with 1N H2SO4 and 1N NH4OH and 1N NaOH. Eh was varied with gaseous nitrogen, oxygen or aqueous H202. Ambient temperature was essentially uniform at 24ºC and was increased in the reaction vessel by the positioning of a magnetic stirrer whose temperature was sufficient to bring the temperature to 2S°C in the reaction. The temperatures of reaction did not vary more than 1/2ºfrom 25°C. Two reactions were investigated, the ferrimolybdite-limonite-water reaction and the reduction of molybdate ion. Studies of both reactions yielded useful data that were used in preparation of the Eh-pH diagrams. The traces of the reactions are shown on Fig. 1. Ferrimolybdite-Limonite- Water: Studies of this reaction involved analysis of the solution of ferrimolybdite and simultaneous formation of ferric hydroxide. The data are summarized on Fig. 1. In this reaction, equilibrium was attained at various pH&apos;s when coexistence of the two solid phases (ferrimolybdite and ferric hydroxide) was attained. At the proper pH, controlled by the amount of ferrimolybdite and thus the dissolved content of molybdate species, both phases were observed and reaction times to complete the transition were on the order of weeks. The reac-

Jan 1, 1963

By W. A. Tiller

The conventional techniques1 for determining the liquidus and solidus surfaces of an alloy system containing more than two components are extremely tedious to use and do not provide a complete picture of the equilibrium relations between solid and liquid alloys. These techniques are unable to yield "tie-line" information concerning solid and liquid phase equilibrium, a very important parameter in the solidification description of the liquid alloy and a very necessary parameter in the preparation of "zone-levelled" alloy crystals. The tie-line in a polycomponent system is analogous to the partition coefficient, k, in a binary system, it gives the composition of the solid, Cs, in equilibrium with a liquid of composition CL. That is, CS = kCL, where CL = [CO, c1,...Cn] denotes the concentrations of the n + 1 constituents, and k = [ko, kb ,...kon] denotes the gross partition coefficient for the elements between the two phases; thus, k is the tie-line in this system. To provide complete information concerning the two-phase equilibrium in a polycomponent system it is necessary to know both the liquidus surface and the gross partition coefficient. From these two the solidus surface is obtainable. The conventional techniques are unable to provide this information in other than a binary system so we must look elsewhere. In recent years considerable insight has been gained into the correct description of the liquid-solid transformation, 2,3 and controlled solidification experiments may now be designed to both facilitate and enhance equilibrium diagram studies. In the present paper consideration is given to two methods for obtaining the liquidus surface and the tie-lines in polycomponent systems. The methods to be described below deal with the solidification of an n + 1 constituent liquid alloy of initial composition [co, Co ,...Con], where the superscripts refer to the elements present and the Oth element is considered as the solvent in which the n solutes are dissolved. The general assumptions made in the treatment are the following: (i) the solid and the liquid at their interface are in equilibrium during the growth of the solid phase, (ii) there is no diffusion in the solid phase, and (iii) the liquid phase is completely mixed and is therefore homogeneous in concentration. METHOD I In this section a general experimental method will be described which, in principle, is capable of giving an exact description of the liquidus surface and tie-lines. Consider the unidirectional solidification of the liquid alloy specimens L cm in length (freezing either horizontally or vertically). Allow the sample to be frozen very slowly from one end, as indicated in Fig. 1, with complete mixing in the liquid, and then analyze the solid bar to determine its chemical constitution as a function of position, x, along the bar. Let Fig. 2 represent a possible distribution of the ith constituent along the bar. At the point x&apos; the concentration of the ith constituent is C1/5(x&apos;), and the average concentration of the rest of the bar between x&apos; and L is given by C:(X&apos; - L) where [ A(x) c1s(x)dx c1/s(x&apos;-L) = f A(x) dx x * and A(X) is the cross-sectional area at x. In a similar manner. all the Cf(x&apos; - L) may be determined. Thus, the gross artition coefficient k for liquid of composition [Cs(x - L),...Cs(X&apos; - L)] is given by -ko= CUs&apos;)/Cos(x&apos; - L)" k0 = csn{x&apos;)/cs(x&apos;- L) During the freezing of a charge of length L, the liquid composition may vary over a wide segment of the phase diagram and the gross partition coefficient over this segment of the phase diagram may be determined from one, bar. Fig. 3 illustrates the magnitude of Cs(g)/C,&apos; as a function of the fraction g of the bar which has Solidified.2 We can see that the concentration in the bar will vary over a range of about 15 wt pct for C,&apos; = 10 wt pct and k0 = 0.5. It appears that 4 or 5 specimens would be adequate to study a simple binary eutectic phase diagram.

Jan 1, 1960