Search Documents

By E. A. Metzbower

STEREOGRAPHIC projections of hcp metals depend upon the c/a ratio. Hu1 has recently published standard projections for titanium (c/a = 1.5873) of the (000l), the basal plane, the (1010), the most prominent slip plane, and the (1012), the most prominent twinning plane. Caplan et a1.2 and Hul have also published tables of angles between poles of planes, between directions, and between directions and poles of planes. From these tables standard projections and double stereograms can be constructed. However, by using the on-line CALCOMP plotter with a CDC 3800 computer, direct plots of standard stereographic projections of titanium (c/a = 1.587) have been made.

Jan 1, 1970

By G. P. Tiwari

Recrystallization and grain growth in thoria dispersed nickel and nichrome were recently studied by Webster as a function of temperature and deformation. The unexpected part of these results was that specimens which had received heavier deformation developed greater resistance to recrystallization. Retardation of recrystallization was accompanied by the formation of voids around thoria dispersion. To explain these results, Webster suggested that the formation of void around the particles increased the effective size of thoria particles. This resulted in greater impediment to the grain-boundary migration and as a consequence the recrystallization of the matrix is retarded. In the present note an alternative and more probable explanation for the effect of voids on recrystallization is presented. The exact mechanism of void formation in thoria dispersed nickel or nichrome is not known. However, it is reasonably certain that it must be preceded by the stress concentration in the matrix around thoria dispersion during the deformation.'' The resulting stress concentration must be sufficient enough to supply the surface energy for the new surfaces created. Further, the decrease in the strain energy of the matrix surrounding the potential void nucleus must be larger than the surface energy of the newly created surface. The release of strain energy due to formation of crack results in a strain free cylinder of the material around the voids.13 If the void formation is not localized, at few points only (as is the case here), this process may lead to considerable amount of release of strain energy of the matrix. The pattern of recrystallization behavior of single phase homogeneous matrix as well as the matrix having a second phase dispersion is same except for the fact recovery and recrystallization are more clearly delineated.14 In general, the recrystallization temperature is lowered (i.e., recrystallization is easier) with increase in the amount of cold work. This is due to the increase in stored energy in the matrix with increasing amount of deformation. If somehow there is a relaxation of strain energy in the matrix, the recrystallization should become difficult because of the decrease in the amount of stored energy available for recrystallization. Since the formation of voids leads to a decrease in the strain energy of matrix, the recrystallization of the matrix would be inhibited due to the formation of voids during deformation prior to recrystallization. It has been observed by earlier workers15'16 that the presence of preexisting voids in a matrix retards the recrystallization. The essential issue here is how do the voids act to produce this effect. If the voids influence recrystallization only by blocking the grain boundary migration, then the effect should be maximum when they are present almost exclusively along grain boundary. These conditions are obtained during high temperature deformation. However, the voids produced due to creep along grain boundary are not able to prevent recrystallization17 suggesting that they are not effective in blocking grain boundary movement. Recently it was shown by Davies and Williams that the voids can act as sinks for vacancies." As a result the processes dependent on vacancy diffusion like recovery, recrystallization, dislocation climb, and so forth, will be hindered. This fact may be responsible for inhibition of recrystallization during subsequent deformation and annealing cycles. It is to be noted here that there is a large difference between the density of voids in creep experiments and the other experiments where retarding effect of voids on recrystallization is seen. The voids in former may number up to l04 to l05 per sq cm whereas in latter cases the voids density is typically around 1010 to 1013 per sq cm. It appears that the decrease in supply of vacancies in creep is insufficient to adversely affect the recrystallization due to low void population. The author is grateful to P. Das Gupta and S. P. Ray for helpful discussions. Author's Reply D. Webster Tiwari appears to have misunderstood the nature of grain boundary-particle interactions. Tiwari (quoting Cahn) states that second phase particles become more effective as they become smaller, therefore as the voids in TDNiC make the thoria particles effectively bigger their ability to resist grain boundary movement is impaired. This particle size argument was originally proposed in the form of an equation by Zener 20 years agol9 and is not necessarily valid as is discussed below. However, assuming it is valid, it predicts a greater boundary restraining effect by smaller particles simply because their combined cross sectional area is greater at a constant volume. If the number of particles remains the same and their effective size increases, as in the present case, Zener's equation predicts a greatly reduced grain size. This is because the effect

Jan 1, 1970

By E. Teghtsoonian, E. M. Schulson

The tensile behavior of bcc ordered P' AuZn single crystals (CsCl structure) has been investigated under varying conditions of temperature, composition, and orientation. Between -0.2 and 0.4 T, multi-stage hardening occurs fm stoichiometric and nonstoichio-metric crystals oriented near the middle of the primary stereographic triangle. At higher and lower temperatures, parabolic type hardening occurs, followed by work - softening at the higher temperatwes. Deviations from stoichiometry give rise to increased flow stresses. Multi-stage hardening was observed for most orientations, except along the [loll-[lll] boundary and near the [001] corner of the stereo -graphic triangle, where parabolic type hardening occurs. Along two slip systems, (hk0)[001] and (, operate simultaneously while in the [001] comer, slip occurs mainly on the system. Electron microscopy of deformed crystals revealed bundles of edge dislocations forming walls approximately Perpendicular to the glide plane. In general the plasticity of 4' AuZn closely resembles the plasticity of bcc crystals. In recent years, considerable interest has arisen concerning the mechanical properties of the CsCl type intermetallic compounds Ag Mg,'- Fe co,' and Ni Al.'-' The compound P'AuZn is structurally similar. It has a low and congruent melting point of 725"~,'" remains ordered up to the melting point,16 and pos-esses a range of solid solubility from 47.5 to 52.0 at. pct Au at room temperature.15 The present paper reports the results of an investigation on the general tensile behavior of material in single crystal form. Some dislocation configurations characteristic of the deformed state are also reported. The results of a detailed study of the slip geometry in AuZn are presented in a separate paper.17 PROCEDURE Alloy preparation, crystal growing techniques, and the procedure followed in selecting specimens of minimum composition variation are reported elsewhere.17 Dumb-bell shaped tensile specimens were prepared by carefully machining single crystals in a jewellers' lathe to a gage length of 0.80 in. and diam of 0.090 in. Back-reflection Laue X-ray patterns and room temperature tensile tests revealed that machining damage could be eliminated by electrochemically polishing 0.005 in. from the machined surface followed by annealing at 300°C for 1 hr. Specimens were polished in fresh 5 pct KCN solution (40°C, 12 v). Experiments were performed by gripping specimens in a self-aligning pin-chuck and threaded collet system, then straining in a floor model Instron tensile machine. All tests were performed in duplicate. Experimental variables included temperature, composition, and orientation. Unless otherwise stated the strain rate was 2.5 x 10"3 per sec. Liquid testing environments included nitrogen (WOK), nitrogen cooled petroleum ether (133" to 293"K), and silicone oil (293" to 488°K). Resolved shear stress-shear strain curves were electronically computed from autographically recorded load-elongation curves. Stress and strain were resolved on the macroscopic noncrystallographic (hkO) [001] system operative under the specific test conditions of temperature, strain rate, and orientation reported earlier.17 RESULTS The temperature dependence of the work-hardening curves is shown in Fig. 1 for gold-rich crystals of 51.0 at. pct Au oriented near the center of the stereo-graphic triangle. Over the range of intermediate temperatures from -200" to 400°K, they are very similar to those classically observed for fcc metals (reviewed by Nabarro et al.).'' The beginning of deformation is characterized by a region of decreasing hardening rate, stage 0, which is followed by a region of low linear hardening, stage I, and then a region of higher linear hardening, stage 11. At the higher temperatures, stage 111 is observed, a region of decreasing hardening rate. Over the intermediate temperature range, the extent of stage 0 and of the slow transition between stages I and I1 decreases with increasing temperature. Total ductility is large, often greater than 300 pct shear. As the temperature is either increased or decreased, the extent of stage I is decreased, giving rise to parabolic type flow and reduced ductility. Similar temperature effects have been reported for bcc ~r~stals.~~-~~ Below -14O°K, hardening is terminated in brittle fracture while above -400°K. initial hardening is followed first by work-softening and then by chisel-edge type ductile fracture. Stoichiometric (50.0 at. pct Au) and Zn-rich (51.0 at. pct Zn) crystals were also tested from 77" to -500°K. The effect of composition on the flow behavior is illus-

Jan 1, 1970

U.S. Steel Uncovers Massive Iron Ore Deposits in Nevada United States Steel Corporation has confirmed that mineral investigation in Lyon County, Nevada. has been under way since 1960. Confirmation followed press reports of a statement attributed to a Nevada State inspector of mines to the effect that the Corporation has found a major iron ore deposit that may also contain copper ill West Central Nevada. Drillings over the years in a number of locations have indicated extensive iron ore bodie containing a possible quarter of a billion tons of ore of a basically magnetite composition. analyzing less than 40% iron, which would require beneficiation for commercial use. Some of these deposits are deep- lying while others would permit open pit mining. These bodies contain copper in quantities of approxiimately 0.3%. More recent drilling in another area has disclosed evidence of additional deeply-lying deposits of a lower fe content but with more promising indications of copper. A realistic estimate of fe and cu ore reserves cannot be made until more drilling is completed.

Jan 1, 1970

Jan 1, 1970

By d&apos, C. McCoul, C. Antonio, R. Krohn

MOST of the commercial colored gold alloys for jewelry applications are based on the Au-Ag-Cu-Zn system. Although work has been done on the constitution of the Au-Ag-Cu system.'-4 there are no reports in the literature on the effects of zinc additions in these alloys. We have metallographically determined the a =al + a2 transformation temperatures in 91/2- and 131/2-karat alloys in which varying amounts of zinc have been substituted for copper and silver. Samples were cast in the form of 1/2-in. round bars

Jan 1, 1970

By John V. Beall

With some difficulty we framed the picture of the village on the mountain getting in the railroad bridge and tunnel at the base. It was a charming scene of red-tile roofs on a green mountain in the golden autumn sunshine with the black hole of the railroad tunnel looking like something out of the movie, "The Train." We clicked the shutter, advanced the film and started back to our rented Audi. At which point there was a hail from the other side of the railroad bridge. A man in uniform was brandishing an object in the air which looked suspiciously like a rifle. We peered around. We were the only other persons in view. He must be yelling at us. He was now closing the distance at a brisk, determined gait but was still 100 yards away. The car was handy but the road was straight, paralleling the railroad tracks for some distance. We dismissed the idea of running for it. Who knows, he might shoot. When he came up we didn't have much of a conversation because it had taken us a week to learn three words of Yugoslavian-zhiveli, long life, huhvalla, thank you, and schlivavitza, the national drink (plum brandy). None of these seemed appropriate. We got the Idea that photographs of railroad tunnels and bridges were prohibited. The guard, for such he seemed to be, took the Audi plate number, administered a last scowling reprimand and stalked off. This incident was the only one in a 15-day visit to Yugoslavia which we would have associated with "Iron Curtain restrictions."

Jan 1, 1970

By Walter Nummela

This acronym may be readily deciphered, and it represents the programming theme for the SME Sessions at the Centennial Meeting of AIME in New York in 1971. The Concentration Committee thus charged out to grab, to induce, and to accept volunteered papers within that framework. The program for the Concentration sessions is in and hopefully all deadlines will be met as specified in the instructions to authors. Without spelling out what is to be seen and heard in New York, how well did the Committee satisfy the theme described in the title? Perhaps it was by virtue of the international makeup of the Committee (Member Dan Pickett is with the Mines Branch in Ottawa) that an international slate of authors was assured. Four countries are to be represented-Bolivia, Canada, Italy, and the United States.

Jan 1, 1970

By J. R. Jargon, H. K. van Poollen

Non-Newtonian fluids may be injected into a reservoir during secondary recovery operations. The non-Newtonian fluid used in this work is a power-law type of fluid that is, the viscosity of the fluid decreases as the flow rate or rate of shear increases. This paper presents equations for steady-state linear and radial flow of such fluids, transient behavior results from a finite difference model of a radial system, and transient behavior results from a field test. The equations that describe the flow of a non-Newtonian fluid are non-linear and are solved numerically. Finite difference solutions are presented as curves of dimensionless pressure drop at the wellbore us dimensionless time for a constant injection rate. Solutions were obtained for 5-percent, 10-percent and 100-percent PV of a non-Newtonian fluid for injection rates of 1, 10, 100 and 1000 cc/sec and for a 5 percent PV of non-Newtonian fluid located at T = Tw' 3, 10, 20, 50 and 100 ft for a flow rate of 1 cc/sec. The buildup curves do not exhibit a stmight-line portion as is the case for Newtonian flow through porous media. Correlations also are shown for the productivity index vs rate for the computer model study and the field tests. INTRODUCTION During various secondary recovery operations non-Newtonian fluids are injected. Such fluids, in general, include thickened water and gelled fluids. The term "non-Newtonian" implies that the viscosity is not only dependent upon temperature and pressure, but also on the rate of shear that is applied to the fluid. For example, water, which is a Newtonian fluid, will have essentially the same viscosity no matter what rate of shear is applied. A pseudo-plastic fluid exhibits a decreasing viscosity when higher rates of shear are applied; a dilated fluid has an increasing viscosity with increasing rates of shear. The objective of studies performed and described in this report is to obtain relationships and mathematical and empirical descriptions of the flow of non-Newtonian fluids through porous media. Simple mathematical relationships, computer studies that include the unsteady-state behavior of such fluids, and field tests are used. PREVIOUS LABORATORY STUDIES Laboratory studies have been performed by several investigators. The fluids used in one investigationl were surfactant-stabilized dispersions of water in hydrocarbons. Its Fig. 6 is reproduced as our Fig. 1. This effective-viscosity vs frontal-velocity diagram shows that this fluid is of the power-law type over a fairly large range of frontal velocities. Gogartyl developed an equation for the effective viscosity as a function of shear rate that reduces to Eq. 2 for frontal velocities greater than about 2 ft/D. The fluid characteristics used in the present study are similar to those reported by Gogarty. Christopher and Middleman2 performed experiments with power-law fluids flowing through pipes packed with glass beads. They used a modified Blake-Koteny

Jan 1, 1970

By R. S. Shrode

By now most readers of this column are aware that it no longer has a regular editor. Tom Murphy, who did the job so well, has had to bow out because of his duties in Australia---duties that keep him from the luxuries of such things as typists and typewriters for rather extended periods of time. We will miss his regular contributions but hope and expect to hear from him as a guest columnist from time to time. Finding an editor to function on a regular basis turns out to be no simple task. This does not mean that there may not be candidates around who would secretly enjoy having their arm twisted into a "yes" position, but at the moment none has been found. Anyway, at the Salt Lake City business meeting it was agreed that we should try to spread the load around. To that end, the Regional Vice Chairmen were specifically singled out as one potential source of contributions. These fellows should have an opportunity for a hearing during their term in office. The existing organizational set-up of the IndMD Division may be a little unfair to this group of officers. The limited responsibility outlined in our Manual of Official Duties and Responsibilities does not offer them much chance for self-expression. Probably the by-laws were written so as to have a geographic representation of membership in case it should be needed at some time. But that is another subject. The point is that now these regional officers have an opportunity to speak out on topics of their own choosing through this column. Some have already done just that. There are also other potential contributors to the column. One is the Secretary, who twice a year uses the column for distributing the minutes of our business meeting to the members. Another is the outgoing Division Chairman. In Salt Lake City, it was decided that this officer should be challenged to contribute something each year as a means of reviewing events of the past year or explaining what should have happened but didn't. I am, therefore, trying to accept that challenge.

Jan 1, 1970

By Peter R. Morris, Alan J. Heckler

THREE angles are required to specify the orientation of a crystallite with respect to a physical reference frame. The distribution of crystallite orientations in a polycrystal is thus a function of three angular variables. The most widely used experimental techniques for studying orientation in polycrystals lead directly to the pole figure representation, i.e., the distribution of the poles of certain crystallographic planes in terms of two angular variables. In recent years1-5 methods have been developed which permit determination of the (three-angle) crystallite orientation distribution from several (two-angle) pole figure distributions. In this work Roe's method has been applied to the study of orientation in hcp materials. The method is illustrated for commercial purity titanium sheet (Ti-70) which was cold rolled (65 pct reduction), annealed at 1450°F for 3 min, and air cooled. The grain shape was observed to be equiaxed after this treatment. EFFECTS OF PHYSICAL, CRYSTALLOGRAPHIC SYMMETRY In Roe's method the crystallite orientation distribution, w(?,?,F), is expanded in a series of generalized spherical harmonics 11(?,?,F) = E E E W^Zirmtye-tote-in* [l] 1=o ,,,=-I ,,=-I where { = cos 8. The set of Euler angles employed here is illustrated in Fig. 1. The axis for each rotation is denoted by a double arrowhead. The positive sense of each rotation is that of a right-handed screw advancing in the direction of the double arrowhead. The X, Y, and Z directions correspond to the rolling direction, cross direction, and normal direction, respectively. In the initial orientation (10.O), (12.O), and (00 . 1) planes are perpendicular to the X, Y, and Z directions, respectively. The IC/ rotation about the Z axis is carried out first by rotating X into X', Y into Y', and leaving 2 unchanged, i.e., Z' = Z. The 8 rotation about the Y' axis is carried out second by rotating X' into X", 2' into Z", and leaving Y' unchanged, i.e., Y" = Y'. The I$ rotation about the Z" axis is carried out last by rotating X" into X"', Y into Y"', and leaving 2" unchanged, i.e., 2"' = 2". Any specified orientation of the X'", Y'", and Z'" crystal-fixed axis system relative to the X. Y, and Z physical axes (rolling direction, transverse direction, and sheet normal direction, respectively) can be obtained by appropriate IC/, 8, and (F rotations. The Zl,, of Eq. [l] are the Jacobi polynomials, augmented by the square root of the weight function. The Zl,, are symmetric in m,n, i.e., Zl,,= Zlnm. For orthotropic physical symmetry and hexagonal crystallographic symmetry, the coefficients, W!,,, of the series are all real, W!mn = Wzfi, = Wlm~ = Wlfi~, 1 and m are even and n is restricted to 6k, where k = ...,-2,-1, 0, 1, 2, .-.. The determination of the Wlmn from pole figure data has been previously described.'~~ The Zl,, may be written in multiple angle form

Jan 1, 1970

By David L. Holt, Walter A. Backofen, Anwar-ul Karirn

ANNEALING the binary alloy, Mg-0.5 wt pct Zr in a hydrogen atmosphere results in extensive precipitation of zirconium hydride. The morphology of these precipitates has already been investigated.lm3 Squires, Weiner, and phillips4 found, following creep testing of the hydrided alloy at 450" and 500°C, that hydride denuded zones formed along grain boundaries that were aligned approximately normal to the tensile axis. Zone formation was attributed to diffusional creep by magnesium transport down the prevailing stress gradients.4'5 Recently, electron microprobe analysis by Karim, Holt, and Backofen6 showed the zones indeed to be zirconium-free and furthermore it was shown that in compression, zones formed along boundaries approximately parallel to the stress axis. Thus it was confirmed that the zones are formed by diffusional creep. Typical zone-formation is shown in Fig. 1. Karim, Holt, and Backofen also measured the con- tribution to the total strain, from diffusional flow, slip creep, and grain boundary shear: results showed that diffusional strain tends to saturate with increasing imposed strain, while grain boundary shear eventually becomes the dominant deformation mode. It was suggested in explanation that the precipitate-denuded zones are soft and easily sheared, such deformation contributing to the grain boundary shear measurement. A point to be emphasized is that the Mg-0.5 Zr alloy was not superplastic for the index of strain rate sensitivity of flow stress, m = a log log 6 was only 0.25. It was recognized that diffusional creep in a poly crystalline aggregate must be accompanied by boundary shearing.' The suggestion was that the non Newtonian-viscous character of diffusional creep in the Mg-0.5 wt pct Zr alloy is due to resistance to sliding of boundaries lying approximately parallel to the tensile axis.= The work described in the present note should be seen against the above background for it represents initial efforts to observe in a similar way diffusional creep in a superplastic alloy. Previous work with the ternary-alloy Mg-6 Zn-0.5 Zr, pellet extruded, showed it to be superplastic however it does not contain resolvable precipitates to act as internal markers for diffusional creep. Also the fine grain size of the alloy (0.5 p) made conventional metallography rather difficult. Solubility relationships in the Mg-Zn-Zr system are not well known, however making reasonable guesses about the probable phase diagram of the ternary, Mg-Zn-Zr, various heat treatments were attempted to produce hydride precipitation. Finally a 16-hr anneal at 495' in hydrogen was found to pro-

Jan 1, 1970

By G. R. St. Pierre, A. Ghosh

In the Si-C-0 system at temperatures of interest in process metallurgy there are four stable condensed phases—silicon, carbon, silica, and silicon carbide (Sic). Silicon melts at 1683oK1 and shows negligible solubility for carbon and oxygen at 1700°K. However, silicon dissolves approximately 1.5 at. pct C at 2500oK.2 Carbon in the form of graphite remains pure and dissolves negligible amount of silicon.' Silica (crysto-balite) melts at 2001°K' and is essentially a stoichio-metric compound. Silicon carbide is a solid and shows negligible deviation from stoichiometry up to approximately 2800oK.2 Besides the condensed phases there is a gas phase

Jan 1, 1970

By H. J. de Haan, J. van Lookeren

In view of their size and favorable characteristics, Shell's heavy-oil fields on the eastern coast of Lake Maracaibo, Venezuela — known as the "Bolivar Coast" — are obvious candidates for the application of thermal recovery methods. During the last decade various methods have been tested, such as steam drive,', steam soak and in-situ combustion.3 Steam soak was discovered as a promising production method rather accidentally in 1969, during early steam drive testing in the Mene Grande Tar Sands1 When steam erupted at the surface due to breakdown of the overburden, the injection wells were back-flowed to relieve the reservoir pressure. This resulted in high oil production rates, all the more impressive because the reservoir is unproducible by primary means. It was concluded that injection of limited amounts of steam might be a very effective method for stimulation of heavy-oil wells. To obtain information that would be more widely applicable, testing of the process was continued in the eastern part of the Tia Juana field (Fig. 1). Here even more favorable results were obtained than in Mene Grande. This created sufficient confidence to prompt a large-scale project, which was considered essential for an adequate evaluation of ultimate recovery, steam requirements, mechanical problems and economic prospects. To obtain an early answer on the ultimate recovery a fairly depleted area was selected in the western part of the same field ("A" in Fig. 1). The first steam was injected in March, 1964. This paper describes the performance until the end of 1966. The production mechanism and well inflow performance are discussed in some detail. In view of the favorable results obtained so far, steam soak operations have expanded considerably since the start of this project. Presently, five other projects are under way, of which two are about the same size as the one under discussion, with further extensions being programmed. Description of the Project Reservoir Data Shell's part of the Main Tia Juana reservoir has a proven area of 8,800 acres and an average net oil sand thickness of 130 ft. It contained an initial quantity of 2,750 million bbl of stock tank oil (STOIIP), with an API gravity ranging from 10 to 15 API and a viscosity of 100 to 10,000 cp (at 122F). As a geological unit it is known locally as the Lower Lagun-illas member of the Lagunillas formation, which is early Miocene in age. The sand bodies are believed to be distributary channel sands deposited in a lower coastal plain. Most of the channel sands have lateral and some vertical communication. The field was developed mainly in the period from 1936 to 1950. The ultimate primary recovery is estimated at 18.1 percent of STOIIP, of which 12.5 percent STOIIP had been produced by the end of 1963 from some 540 wells. By then the average pressure had decreased from an initial value of 960 to 550

Jan 1, 1970

By Robert H. Carpenter

Major trends in exploration geochemistry during the past year included an increased level of geochemical exploration by both government and private industry: greater sophistication in sampling, analytical and interpretive techniques: and increased activity on the part of universities and state geological surveys. The evolution of applied geochemistry in North America from a useful prospecting tool to an invaluable exploration method is largely due to efforts of the mining industry, the USGS and the Geological Survey of Canada. In the U.S., there has been a distinct reluctance on the part of universities to conduct research or to offer courses dealing principally with applied geochemistry. Most university geochemists have not been responsive to industry needs because government sponsorship of geochemical research in universities has been overwhelmingly in favor of theoretical, rather than applied research: and, because of the mistaken notion that exploration geochemistry is not sufficiently academic. A critical shortage of specialists in this field has resulted. Specialists in Exploration Geochemistry Needed Based on the response to a brief questionnaire sent to universities in the U.S. and Canada, there is some evidence suggesting a reversal in this trend. Graduate courses devoted to exploration geochemistry are currently being offered in geology departments at the following universities: University of British Columbia, Colorado School of Mines, University of Idaho, McGill University, University of New Mexico, Pennsylvania State University and the University of Utah. Other departments report that applied geochemistry is included in general geochemistry courses. A survey of recent publications suggests increased research interest in exploration geochemistry by university geologists.

Jan 1, 1970

By Byoung Whie Lee

In order to investigate the change in surface energy as a function of cold work ad environment, the contact angles between a liquid and the surface of elec-tropolislzed aluminum with various degrees of cold work were measured. Specinlens cut from aluminum rod (99.99 pct Al) were annealed at 600°C for 24 hr and then cold compressed parallel to the drawing di-rectzon of the rod in increments of approximately 10 pcl from 0 to 70 pct. The sections, taken transversely to the drawing direction, were mechanically and electro chemically polished. Contact angles between the sessile drop of distilled water, glycerin, and glycol and the specimen surface were measured optically. The differences in interfacial energy were calculated from the contact angle data. The effects of chemical washing and surface roughness of the specimen on the contact angle were also studied. The liquid contact angle was a linear function of the degree of cold working (D) ad changed markedly with differed liquids. THE plastic deformation of polycrystalline metals induces a preferred orientation in crystal structure. A preferred orientation changes the atomic density of a metal surface. This change in surface atomic density brings about the changes in surface interactions of the metals."' Also, the plastic deformation of metals raises the internal energy by increasing the stored energy.' Consequently, the total Helmholtz free energy of the metal increases and, in turn, the surface free energy of the metal. In order to study the effect of plastic deformation on solid surface phenomena, the liquid contact angle of a sessile drop made on cold compressed and elec-trochemically polished aluminum was measured. The preferred orientation in aluminum, due to uniaxial compression, is known to be [110] direction parallel to the compression axis. However, this description is only a first approximation of a rather complex orientation. In actuality, half the crystallites are more than 10 deg from this orientation, regardless of the amount of compression." For randomly oriented fcc crystals, the average surface atomic density can be calculated as follows: The number of atoms in a unit volume is 4/a3, where a is a lattice constant. Hence, the number of atoms per unit surface area is about (4/a3)2/3 = 2.52/a2 However, when the preferred orientation took place along [110] direction, the surface atomic density is as follows: The area of (110) plane of a unit cell, considering ridges and valleys, is BYOUNG WHlE LEE, Member AIME, is Research Metallurgist, Atomic Energy Research Institute of the Republic of Korea, Seoul, Korea. Manuscript submitted May 29, 1968. IMD 2 x J2- a x Ga = 6a2 Since this plane contains 4 atoms, the surface atomic density is 4i6a2 = 2.3/a2 Upon changing from random to preferred orientations, the surface atomic density decreases about 10 pct. The increase in the stored energy and the change in surface atomic density due to plastic deformation would certainly alter the surface tension of a metal. EXPERIMENT High purity aluminum rod of 6-mm diam (99.99 pct Al, obtained from Johnson, Matthey & Co., Ltd, London, England) was cut into sections approximately 1 cm long. The transverse cross section was mechanically polished. Then, the specimens were annealed in air at 600°C for 24 hr. Thus, eight annealed specimens were uniaxially compressed at room temperature from 0 to 70 pct of cold working with an increment of 10 pct. The extent of cold working was determined by the percentage of reduction in axial length to the original length. The specimens were further polished mechanically and, then, electrochemically with the Modern Battelle Type 1 electropolishing solution with a current density of 0.3 to 0.4 amp per sq cm and an electrode potential of 8 to 12 v at the solution temperature of 78" to 82°C for approxirr~ately 5 min. The Modern Whlte Diffusing Screen \t/ --------------- re Goniometer for Mercury Lamp ^-^ Sessile Drop ¦=• Condenser c=> Microscope l_*~_i bJ Mlcromster Filer with Protmcter Fig. 1—Schematic diagram of apparatus set-up for liquid contact angle measurement.

Jan 1, 1970

By K. Tangri, M. Chaturvedi

The addition of 0.5 wt pct Cu to Zr-2.5 Cb alloy increases the as -quenched hardness of the hexagonal martensitic a' phase, produced by water-quenching bccß-Zr phase, by about 35 pct. This strengthening has been attributed to the solid -solution hardening of the matrix. On aging ternary martensite, a' phase reverts to equilibrium a and Zr2Cu and ß-Cb precipitate out, mainly at the twin and grain boundaries, causing a secondary hardening of the matrix. COLD-worked Zircaloy-2 pressure tubes have been in use in power reactors for a considerable period of time. The search for a better material led to the development of Zr-2.5 wt pct Cb alloy which in the quench-aged condition develops 50 pct more strength than that of cold-worked Zircaloy-2, however, its corrosion resistance in water and steam in the temperature range of 316" to 400°C, in absence of neutron flux, is inferior to that of zircaloy-2.' Work carried out by Ells et al.1 and Dalgaard2 has shown that the corrosion properties of Zr-2.5 wt pct Cb alloy can be considerably improved by the ternary addition of 0.5 wt pct Cu. This paper is concerned with the effect of 0.5 wt pct Cu on the formation of martensitic a and its aging characteristics in a Zr-2.5 wt pct Cb alloy. MATERIALS AND EXPERIMENTAL TECHNIQUES Zr-2.5 Cb-0.5 Cu (referred to as the ternary alloy) and Zr-2.5 Cb (referred to as the binary alloy) alloys, supplied by the Chalk River Nuclear Laboratories of the AECL were used. The detailed chemical analysis is given in Table I. Cold rolling and swagging with frequent intermediate anneal of 1000°C were used for the initial fabrication of the alloys. All the heat treatments were carried out after the specimens were wrapped in zirconium foils and encapsulated in silica tubes under a vacuum of 5 x 10-6 mm of Hg. For optical metallography and hardness measurements specimens were mechanically and then chemically polished in a 45 pct HNOj, 45 pct HzO, and 10 pct HF solution. Hardness was measured on a Vickers hardness tester using a 10-kg load. For each specimen at least fifteen indentations were made in order to obtain a representative value. The phase identification and structural analysis were carried out using X-rays and electron diffraction techniques. Wires of 1.5 mm diam reduced to 0.12 mm diam by chemical etching were used for making Debye-Scherrer powder patterns using Cu Ka radiation in a 114.6 mm diam camera. Carbon extraction replicas were prepared by etching the specimens, after depositing a layer of carbon on the metallographic specimen, in one part HF and thirty parts ethyl alcohol. Thin films were prepared by electropolishing heat-treated 3/4 by 1/2 by 0.005 in. thick strips using a modified Bollman-Window technique. The 10 pct perchloric acid-90 pct methyl alcohol bath was kept at -50°C and polishing was done at 5 to 10 V. The thinned specimens were washed in ethyl alcohol at -30º to -40°C and dried between filter papers. Replicas and thin films were examined in a Phillips 300 G electron microscope. For resistivity measurements thin strip specimens 0.02 by 0.3 by 10.0 cm long were used. The potential leads were spot welded to the specimens in order to maintain a fixed length for the initial and the final resistivity measurements. The resistivity was measured by a Kelvin bridge in a temperature controlled room. The temperature was maintained at 72º ±1°F and the accuracy of the resistivity measurements was 0.03 µa-cm. RESULTS As-Quenched Structures. In order to produce a homogeneous matrix to study the precipitation reaction the solution-treatments of both the alloys were carried out in the -field region. From the Zr-Cb phase diagram due to Lundin and cox3 ß/a + ß phase boundary for Zr-2.5 wt pct Cb alloy is 820°C. Ells et al.1 have reported this boundary for Zr-2.5 Cb alloy containing 1100 ppm 0 to be at 920°C. Also, the addition of 0.5 wt pct Cu reduces this temperature by 50°C. Therefore, the solution-treatments were carried out at 1000°C to ensure that the alloys were in ß-phase region. The soaking time was 1 hr and the specimens were water-quenched. The as-quenched hardness of the binary alloy was 245 Vpn whereas, that of the ternary alloy was 330 Vpn. The X-ray diffraction studies indicated that the as-quenched structure of both the alloys consists of martensitic hexagonal phase a', with a c/a ratio of 1.591, and some retained ß-Zr. The presence of a' phase was further confirmed by thin film electron microscopy. Electron micrographs of typical ß-quenched structures of the ternary and the binary alloys are shown in Figs. 1 and 2, respectively. Fig. 3 shows the diffraction pattern from an area similar to that shown in Fig. 1. Although, the as-quenched hardness of the ternary alloy is about 35 pct greater than that of the binary alloy, the structure of both the alloys seems to be the same. The matrix of both alloys is heavily twinned and shows very few dislocations. Furthermore, there is no evidence of any precipitation taking place in either of the two specimens during quenching from the solution-treatment temperature. Aging Behavior of Martensitic a'. The aging kinetics of the ternary alloy were followed by resistivity and hardness measurements. The as-quenched values

Jan 1, 1970

By R. M. Asimow, J. J. Svitak

Tile crilical resoll,r,d shear stress, CRSS, for slip of slow1y cooled Ag-All single crystals was measured at 201K. Tlze importance of short-range order and Suzuki sogregalion was inrestigated by deter~rlining llze ciic.cl of quenching on the CRSS. Thr obserz.ed rfrtenching effects were generally small and indicate that short-range ordcr and Slczuki srgregation do no1 account for n significant portion of the solid-solution strengthening in this system. However, all alloys slzozcwi yield drops ulhich rilere heat- lreat nrenl-sensiline THERE have been a number of mechanisms proposed to explain alloy strengthening in the Ag-Au system. The effectiveness of some of the proposed mechanisms, especially those that depend on Suzuki segregation1" or on short-range order,2-6 SRO? should be strongly dependent on heat treatment. Since internal friction investigations in this system indicate that there is stress-induced order,' we must also consider the possibility of local atomic rearrangement or short-range ordering in the stress field of a dislocation. There is not complete agreement whether these mechanisms should be most effective in raising the flow stress, in causing yield drops. or some combination of these two effects. This work was undertaken to determine the effects in the Ag-Au system of mechanisms that depend on segregation or order by using known but drastically different cooling rates following a high-temperature treatment. By comparing the critical resolved shear stress, CRSS, for slip measured after a very slow cool and again after a fast cool (quench) of the same crystal, it is possible to determine the effect of cooling rate on CRSS* and on yield drops. The single-crystal CRSS was determined at several compositions because there has been no data published across the phase field since the publication of room-temperature flow stress by Sachs and Weerts.' EXPERIMENTAL PROCEDURE Starting with materials of 99.999 pct purity, single-crystal specimens of random orientation 1.25 mm square by 4 cm long were prepared with 0, 10, 14, 25, 30. 50, 70. 75. 80, 90. and 100 at. pct Au. Crystals were grown in an inert atmosphere using a modified Bridgman technique with a growth rate of 1.5 cm per hr in a gradient of 3°C per cm. To obtain a maximum practical degree of SRO, the crystals were cooled at a rate of 275'C per hr to about 310°C and then cooled at 6°C per hr to approximately 200°C. Specimens were tested in tension immersed in an alcohol bath at -72°C (201°K) at a strain rate > = 0.003 mm"1 to determine the CRSS (7). The activation volume of several crystals was determined from the flow stress increment (72 - T1) for a tenfold increase in strain rate. The total shear strain varied from 0.05 to 2.3 pct but was generally less than 0.4 pct. After testing, each crystal was then held at 500°C for 10 min, quenched into brine at -35°C and. after storage at -71°C for 1 day, retested in tension using a procedure identical to that of the first test. The quenching apparatus, see Fig. 1, was designed to enable accurate temperature control and rapid quenching while preventing specimen contamination and accidental deformation. Test data from a specimen with a fine thermocouple spot-welded to it indicated a cooling rate of 104C per sec. The relatively low heat-treatment temperature was chosen to minimize quenching defects caused by a large vacancy

Jan 1, 1970

By John V. Beall

Thai means free. Historically accurate, as the country has never been subjugated by foreign occupation, the name "The Land of the Free" also seems to fit the attitude of the people. At the Bangkok airport, without so much as a kopkhun (thank you), travelers are found behind, beside and in front of ticket counters. A pretty Thai face on TV calls flights in English and Thai. Baggage disappears with alarming rapidity and your reporter and spouse despaired of ever being reunited with it. But at the entrance, all the parts came together and there was even a limousine from our hotel, The Oriental. Driving downtown English style, we noted that there were four lanes of traffic occupying the space we would allow for three lanes. Motorcycles and enclosed three-wheel motorcycle taxis were much in evidence, but the occasional water buffalo held up the slow lane. In the city, men wore European-type slacks and shirts but the women were colorful in traditional ankle-length wraparound skirts.

Jan 1, 1970

By S. S. Lisnyak, B. D. Lichter

An important question in the study of the "hot corrosion" phenomenon (i.e., accelerated oxidation of Ni-Cr-base and Co-Cr-base "superalloys" in the presence of sulfur) is the condition of formation and physico-chemical properties of different sulfides in the system Ni-Co-Cr-S. seyboltl has observed the presence of ((chromium-rich" sulfides of compositions M3S4, and M2S3 in the scales of superalloys after hot corrosion; however, as he points out, much confusion exists as to the identity of sulfides found on Ni-Cr and Co-Cr alloys. According to the literature,&apos; ternary sulfides, e.g., NiCr2S4, (monoclinic structure) and CoCr2S4 (spinel structure) exist in these systems. Therefore, it is likely that these compounds are found in the scale of alloys undergoing hot corrosion. At present this possibility has not been discussed in the literature. Accordingly, we have begun investigation on the properties of ternary sulfides and their mutual interaction. The magnetic and electrical properties of pure NiCr2S4 and pure CoCr2S2 have been previously determined."-&apos; In the present work we have studied the interaction between these sulfides at high temperatures by means of X-ray diffraction and magnetic susceptibility. The measurements were carried out at room temperature after appropriate thermai treatment of samples at high temperatures. For alloys containing the three elements nickel, chromium, and cobalt this interaction may be of importance in the study of the hot corrosion phenomenon. The compounds NiCr2S4 and CoCr2S4 were prepared from stoichiometric amounts of the elements and CoS in the case of CoCr2S4. Samples were mixed and sealed in evacuated silica tubes, slowly heated to 900&apos; to 100O°C, and held at temperature for a total of 120 hr (NiCr2S4) or 80 hr (CoCr2S4) with intermediate re-grinding~. X-ray diffraction showed a pure spinel structure for CoCr2S4 and a monoclinic structure for NiCr2S4. Samples of mixtures of the two ternary sulfides were prepared with different compositions, see Table I. Samples were heated for a total of 80 hr at 900&apos;C in evacuated silica tubes, with one intermediate regrind-ing. The capsules were slow-cooled to room temperature in the furnace. Samples for X-ray diffraction were prepared by placing powder on a glass slide with vaseline. Dif- fractometer traces were obtained on a G.E. XRD-5 diffractometer using a chromium tube and vanadium filter (40 kv and 31 ma). The size of the spinel unit cell was determined from the eight highest angle peaks (80 deg < 2b < 160 deg). Calculated lattice parameters were plotted vs cos B . ctn 0 and extrapolated to 6 = 90 deg. Measurements of the magnetic susceptibility were carried out at room temperature using the Faraday method in a magnetic field of 3000 G and using a Cahn RG automatic microbalance. The system was calibrated from the well-established susceptibilities of platinum and palladium: (Xpt = 0.968 x 10-6 g-1 and Xpd 7 5.04 x 10~6 g-1). The weight of samples were approximately 0.200 g. X-ray diffraction patterns for unsintered mixtures showed Bragg peaks from both the spinel (CoCr2S4) and monoclinic (NiCr2S4) structures. After sintering no monoclinic peaks were observed in samples containing up to 40 mol pct NiCr2S4. However, the spinel peaks were displaced to higher angles with increasing

Jan 1, 1970